SUEMENTARY INRMATIN - Nature · NATURE CHEMISTRY | 1 SUEMENTARY INRMATIN.10/.2597 A stable heavier group 14 analogue of vinylidene Arnab Rit,1 Jesús Campos,1 Haoyu Niu,1 and Simon

NATURE CHEMISTRY | www.nature.com/naturechemistry 1

SUPPLEMENTARY INFORMATIONDOI: 10.1038/NCHEM.2597

A stable heavier group 14 analogue of vinylidene Arnab Rit,1 Jesús Campos,1 Haoyu Niu,1 and Simon Aldridge*,1

Supplementary Information 1. General considerations and starting material preparations 2 2. Synthetic, spectroscopic and analytical data for new compounds 3 3. X-ray crystallographic studies 14 4. Computational details 18 5. TD-DFT 77 6. References for supporting information 79

A stable heavier group 14 analogue of vinylidene Arnab Rit,1 Jesús Campos,1 Haoyu Niu,1 and Simon Aldridge*,1

Supplementary Information 1. General considerations and starting material preparations 2 2. Synthetic, spectroscopic and analytical data for new compounds 3 3. X-ray crystallographic studies 14 4. Computational details 18 5. TD-DFT 77 6. References for supporting information 79



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1. General considerations and starting material preparation All manipulations were carried out using standard Schlenk line or dry-box techniques under an atmosphere of argon. With the exception of Et2O and THF, solvents were degassed by sparging with argon and dried by passing through a column of appropriate drying agent using a commercially available Braun SPS and stored over potassium1; Et2O and THF were dried by refluxing over Na/benzophenone, distilled, sparged and stored over potassium (Et2O) and activated molecular sieves (THF). NMR spectra were measured in C6D6; C6D6 was dried over potassium and was stored under argon in Teflon valve ampoules. 1H, 11B{1H} and 13C{1H} NMR spectra were recorded on Bruker AVII HD NanoBay 400 or Bruker AVII-500 spectrometers and chemical shifts are referenced to the residual protons of the deuterated solvents for proton chemical shifts, the 13C{1H} signal of deuterated solvents for carbon chemical shifts, and Et2O.BF3 for 11B{1H} chemical shifts. Chemical shifts are quoted in δ (ppm) and coupling constants in Hz. Elemental analyses were carried out at London Metropolitan University and at Elemental Microanalysis Ltd., Devon. UK. The cyclic voltammetry measurements were performed with a silver quasi-reference electrode, a platinum working electrode and a platinum wire auxiliary electrode in a supporting electrolyte of a solution of 0.10 M [nBu4N][PF6] electrolyte in THF. UV-vis spectra were collected on a Scintio UV S-2100 UV/Vis spectrometer.

Starting materials IPr2Me2 (Ref. 2), (thf)2Li{B(NDippCH)2} (Ref. 3), (IPr2Me2)GeCl2 (Ref 4.), and

[{HC(MeCMesN)2}Mg]2, (Ref. 5) were prepared according to literature procedures and KC8 was synthesized by minor modification of the reported procedure.6 All other chemicals were sourced commercially and used after appropriate purification.



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2. Synthetic, spectroscopic and analytical data for new compounds

[(IPr2Me2)GeCl{B(DippNCH)2}] (1) To a solution of (IPr2Me2)GeCl2

(0.648 g, 2.0 mmol) in Et2O (10 mL) at -35 ̊C was slowly added a pre-cooled (-35 ̊C) solution of (thf)2Li{B(NDippCH)2} (1.074 g, 2.00 mmol) in Et2O (10 mL). After stirring for 30 min at this temperature, the reaction mixture was gradually warmed to ambient temperature and stirred for 2.5 h. The reaction mixture was subsequently evaporated to dryness and extracted with toluene. The filtrate was evaporated and triturated with hexane (5 mL). After storing at -35 ̊C overnight the precipitated pale-yellow solid was isolated and dried in vacuo. Yield: 1.013 g (1.5 mmol, 75%). Crystals for X-ray crystal structure determination were obtained by cooling a saturated toluene solution of the compound.

Spectroscopic data: 1H NMR (400.2 MHz, C6D6, 298 K): 0.93 (br. s, 6H, CH(CH3)2, NHC), 1.11 (br. s, 6H, CH(CH3)2, NHC), 1.13 (d, 6H, 3JHH = 6.9 Hz, CH(CH3)2, Dipp), 1.22 (d, 6H, 3JHH = 6.9 Hz, CH(CH3)2, Dipp), 1.32 (d, 6H, 3JHH = 6.8 Hz, CH(CH3)2, Dipp), 1.56 (s, 6H, C4/C5-CH3), 1.58 (d, 6H, 3JHH = 6.8 Hz, CH(CH3)2, Dipp), 3.46 (sept, 2H, 3JHH = 6.8 Hz, CH(CH3)2, Dipp), 3.61 (sept, 2H, 3JHH = 6.9 Hz, CH(CH3)2, Dipp), 5.63 (s, 2H, CH(CH3)2, NHC), 6.31 (s, 2H, C4/C5-H), 7.09-7.13 (m, 2H, p-Ph), 7.23-7.24 (m, 4H, m-Ph) ppm. 11B{1H} NMR (128.4 MHz, C6D6, 298 K): 34.9 ppm (B-Ge). 13C{1H} NMR (100.6 MHz, C6D6, 298 K): 10.32 (C4/C5-CH3), 21.2 and 22.3 (CH(CH3)2, NHC), 23.7, 24.7, 26.5 and 27.0 (CH(CH3)2, Dipp), 29.0 and 29.1 (CH(CH3)2, Dipp), 53.2 (CH(CH3)2, NHC), 122.6 (C4/C5-C, Dipp), 123.8 (p-Ph), 124.0 (m-Ph), 126.4 (C4/C5-C, NHC), 127.7 (m-Ph), 141.8 (o-Ph), 146.7 and 147.0 (i-Ph), 172.7 (CNHC).

Anal. Calcd. for C37H56BClGeN4 (675.73 g/mol): C 65.76, H 8.35, N 8.29; found C 65.66, H 8.43, N 8.18.

Supplementary Figure 1. 1H NMR spectrum of [(IPr2Me2)GeCl{B(DippNCH)2}] (1) in C6D6.



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(IPr2Me2){(HCDippN)2B}GeGe{B(NDippCH)2} (2) A mixture of 1 (0.203 g, 0.30 mmol) and [{HC(MeCMesN)2}Mg]2 (0.107 g, 0.15 mmol) was dissolved in toluene (5 mL) at room temperature. The color of the reaction mixture started to change to deep red. After stirring for 30 min, the reaction mixture was filtered into a Schlenk containing BPh3 (0.038 g, 0.15 mmol) to sequester the liberated carbene. After stirring for 30 min, the reaction mixture was evaporated to dryness and was extracted with pre-cooled (-30 ̊C) pentane. After concentration, the filtrate was stored at -35 ̊C for ca. 2 days. The obtained deep red crystalline compound was isolated, washed with small amount of cold pentane and dried in vacuo. Yield: 0.080 g (0.727 mmol, 49%). Crystals for X-ray crystal structure determination were obtained from a saturated solution in hexane at 4 ̊C.

Spectroscopic data: 1H NMR (400.2 MHz, C6D6, 298 K): 0.73 (d, 6H, 3JHH = 7.1 Hz, CH(CH3)2, NHC), 0.79 (d, 6H, 3JHH = 7.1 Hz, CH(CH3)2, NHC), 1.13-1.14 (br. m, 24H, CH(CH3)2, Dipp), 1.21 (d, 12H, 3JHH = 6.9 Hz, CH(CH3)2, Dipp), 1.24 (d, 12H, 3JHH = 6.9 Hz, CH(CH3)2, Dipp), 1.55 (s, 6H, C4/C5-CH3), 3.23 (sept, 4H, 3JHH = 6.8 Hz, CH(CH3)2, Dipp), 3.35 (sept, 4H, 3JHH = 6.9 Hz, CH(CH3)2, Dipp), 5.56 (s, 2H, 3JHH = 7.1 Hz, CH(CH3)2, NHC), 6.21 (s, 2H, C4/C5-H), 6.36 (s, 2H, C4/C5-H), 7.10 (d, 4H, 3JHH = 7.6 Hz, m-Ph), 7.14 (d, 4H, 3JHH = 7.0 Hz, m-Ph), 7.18-7.23 (m, 4H, p-Ph) ppm. 11B{1H} NMR (128.4 MHz, C6D6, 298 K): 33.6 and 41.5 ppm (B-Ge). 13C{1H} NMR (100.6 MHz, C6D6, 298 K): 10.3 (C4/C5-CH3), 20.2 and 21.2 (CH(CH3)2, NHC), 24.1, 24.5, 26.3 and 26.6 (CH(CH3)2, Dipp), 28.7 and 29.0 (CH(CH3)2, Dipp), 53.4 (CH(CH3)2, NHC), 122.0 and 122.3 (C4/C5-C, Dipp), 123.7 and 123.9 (m-Ph), 126.3 (C4/C5-C, NHC), 127.0 and 127.4 (p-Ph), 142.1 and 142.9 (o-Ph), 146.8 and 147.0 (i-Ph), 171.8 (CNHC).

UV-vis (toluene): λmax, nm (ϵ, L mol-1 cm-1): 434 (22200), 359 (25100).

Anal. Calcd. for C63H92B2Ge2N6 (1100.35 g/mol): C 68.77, H 8.43, N 7.64; found C 68.49, H 8.28, N 7.73.

Supplementary Figure 2. 1H NMR spectrum of (IPr2Me2){(HCDippN)2B}GeGe{B(NDippCH)2} (2) in C6D6.



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K2[{(HCDippN)2B}GeGe{B(NDippCH)2}] (3) A mixture of 1 (0.303 g, 0.45 mmol) and excess KC8 (0.306 g, 2.25 mmol) was dissolved/suspended in toluene (5 mL) at room temperature. The reaction mixture was sonicated for 2 h with occasional manual stirring, resulting in a brown colored solution. The reaction mixture was then filtered into an ampoule equipped with a J Young’s valve. The filtrate was concentrated and layered with hexane (3 mL). Storing at 4 ̊C overnight gave a dark brown crystals suitable for X-ray crystallography, which were isolated, washed with small amount of cold hexane and dried in vacuo. Yield: 0.130 g (0.13 mmol, 58%).

Spectroscopic data: 1H NMR (400.2 MHz, C6D6, 298 K): 1.28 (d, 24H, 3JHH = 6.8 Hz, CH(CH3)2), 1.37 (d, 24H, 3JHH = 6.9 Hz, CH(CH3)2), 4.11 (sept, 8H, 3JHH = 6.8 Hz, CH(CH3)2), 6.62 (s, 4H, C4/C5-H), 6.74-6.78 (m, 4H, p-Ph), 6.82 (d, 8H, 3JHH = 6.9 Hz, m-Ph) ppm. 11B{1H} NMR (128.4 MHz, C6D6, 298 K): 55.3 ppm (B-Ge). 13C{1H} NMR (100.6 MHz, C6D6, 298 K): 25.0, 25.7 (CH(CH3)2), 29.0 (CH(CH3)2), 120.9 (C4/C5-C), 123.2 (m-Ph), 125.5 (p-Ph), 146.8 (o-Ph), 150.4 (i-Ph).

UV-vis (toluene), λmax, nm (ϵ, L mol-1 cm-1): 428 (20100).

Anal. Calcd. for C52H72B2Ge2K2N4 (998.25 g/mol): C 62.57, H 7.27, N 5.61; found C 62.33, H 7.32, N 5.58.

Supplementary Figure 3. 1H NMR spectrum of K2[{(HCDippN)2B}GeGe{B(NDippCH)2}] (3) in C6D6.



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Reaction of 2 with H2: synthesis of (IPr2Me2){(HCDippN)2B}GeGe(H)2{B(NDippCH)2} (4)

Supplementary Figure 4. Generation of 4 via the reaction of 2 with dihydrogen

A solution of 2 (0.040 g, 0.036 mmol) in hexane (10 mL) was degassed by the freeze-pump-thaw method (3 times) and treated with H2 (1 atm) at room temperature. The reaction mixture was then either heated at 45 ̊C for 75 min or stirred at 25 ̊C for 36 h. By this time, the color of the reaction mixture changed from dark red to yellow. The reaction mixture was then filtered and concentrated to incipient crystallization. After standing overnight at 25 ̊C, the crystalline product were isolated, washed with small amount of hexane and dried in vacuo. Yield: 0.030 g (0.272 mmol, 75%). Crystals for X-ray crystal structure determination were obtained from a saturated solution in hexane at 25 ̊C.

Spectroscopic data: 1H NMR (400.2 MHz, C6D6, 298 K): 0.43 (br. s, 3H, CH(CH3)2, NHC), 0.45 (d, 3H, 3JHH = 7.1 Hz, CH(CH3)2, NHC), 0.53 (br. d, 3H, 3JHH = 5.9 Hz, CH(CH3)2, Dipp), 0.75 (br. d, 3H, 3JHH = 5.9 Hz, CH(CH3)2, Dipp), 0.83 (br. s, 6H, CH(CH3)2, Dipp), 1.06 (d, 3H, 3JHH = 7.1 Hz, CH(CH3)2, NHC), 1.26 (d, 3H, 3JHH = 7.1 Hz, CH(CH3)2, NHC), 1.09 (br. s, 3H, CH(CH3)2, Dipp), 1.17-1.24 (m, 21H, Dipp), 1.26 (d, 3H, 3JHH = 7.1 Hz, CH(CH3)2, NHC), 1.34 (s, 1H, Ge-H), 1.49 (br. d, 3H, 3JHH = 5.9 Hz, CH(CH3)2, Dipp), 1.54 (s, 3H, C4/C5-CH3), 1.56 (d, 6H, 3JHH = 5.9 Hz, CH(CH3)2, Dipp), 1.60 (br. s, 3H, CH(CH3)2, Dipp), 1.66 (s, 3H, C4/C5-CH3), 2.42 (s, 1H, Ge-H), 2.82 (br. m, 1H, CH(CH3)2, Dipp), 2.89 (sept, 2H, 3JHH = 6.9 Hz, CH(CH3)2, Dipp), 3.08 (br. m, 1H, CH(CH3)2, Dipp), 3.57 (sept, 4H, 3JHH = 6.9 Hz, CH(CH3)2, Dipp), 5.85 (sept, 1H, 3JHH = 7.1 Hz, CH(CH3)2, NHC), 6.12 (s, 3H, C4/C5-H), 6.26 (s, 3H, C4/C5-H), 6.36 (sept, 1H, 3JHH = 7.1 Hz, CH(CH3)2, NHC), 6.91 (d, 1H, 3JHH = 6.7 Hz, CH(CH3)2, m-H), 7.06-7.14 (m, 4H, m/p-Ph), 7.18-7.28 (m, 7H, m/p-Ph) ppm. 11B{1H} NMR (128.4 MHz, C6D6, 298 K): 31.4-34.6 ppm (br. B-Ge). 13C{1H} NMR (125.7 MHz, C6D6, 298 K): 10.27 and 10.35 (C4/C5-CH3), 20.3, 20.8, 21.9 and 22.4 (CH(CH3)2, NHC), 23.2, 23.4, 23.7, 24.2, 24.4, 24.5, 25.8, 26.3, 26.5, 26.7, and 27.3 (CH(CH3)2, Dipp), 28.2, 28.5, 28.8, 28.9 and 29.4 (CH(CH3)2, Dipp), 53.0 and 54.5 (CH(CH3)2, NHC), 121.8 and 122.1 (C4/C5-C, Dipp), 122.6, 122.7, 123.2, 123.6, 123.8, 124.5, and 124.7 (m/p-Ph), 126.0 and 126.5 (C4/C5-C, NHC), 127.3, 127.5, 127.6 (m/p-Ph), 141.9, 142.3, 143.2, 145.3, 146.1, 146.5, 146.8, 148.8, 149.1 (o/i-Ph), 173.5 (CNHC).


H2 (1 atm.)

NNiPr

iPrGe Ge

B

B N

N

N

NDipp

Dipp

Dipp

Dipp

2

NNiPr

iPrGe Ge

B

B N

N

N

NDipp

Dipp

Dipp

Dipp

4

HH



7

Supplementary Figure 5. 1H NMR spectrum of (IPr2Me2){(HCDippN)2B}GeGe(H)2{B(NDippCH)2} (4) in C6D6 (*).



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{(HCDippN)2B}2GeGe (5) A mixture of 3 (0.150 g, 0.15 mmol) and [Ph3C][B(C6F5)4] (0.278 g, 0.30 mmol) was dissolved/suspended in benzene (6 mL) was added at room temperature. After sonicating for 5 min, the reaction mixture was stirred at 25 ̊C for 1 h, resulting in a yellow-brown solution. The reaction mixture was then evaporated to dryness and the remaining solid extracted with pre-cooled (-45 ̊C) pentane. Removal of all volatiles from the filtrate gave brownish yellow solid. Yield: 0.092 g (0.10 mmol, 67%). Crystals for X-ray crystal structure determination were obtained from a saturated solution in pentane at 4 ̊C.

Alternate synthesis: A mixture of 3 (0.01 g, 0.01 mmol) and [Cp2Fe][BArf4] (0.021 g, 0.02

mmol) was dissolved/suspended in C6D6 (0.5 mL) in a Young’s valve NMR tube at room temperature. After sonicating for ca. 10 min, all the solid dissolved to give a yellow solution. 1H NMR analysis showed quantitative conversion to 5 and ferrocene in 1:2 ratio.

Spectroscopic data: 1H NMR (500 MHz, C6D6, 298 K): 1.13 (d, 24H, 3JHH = 6.9 Hz, CH(CH3)2), 1.29 (d, 24H, 3JHH = 6.9 Hz, CH(CH3)2), 3.22 (sept, 8H, 3JHH = 6.9 Hz, CH(CH3)2), 6.19 (s, 4H, C4/C5-H), 7.03-7.06 (m, 4H, p-Ph), 7.08-7.10 (m, 8H, m-Ph) ppm. 11B{1H} NMR (128.4 MHz, C6D6, 298 K): 38.3 ppm (B-Ge). 13C{1H} NMR (100.6 MHz, C6D6, 298 K): 24.8, 25.5 (CH(CH3)2), 29.3 (CH(CH3)2), 123.3 (C4/C5-C), 126.0 (m-Ph), 128.6 (p-Ph), 140.37 (o-Ph), 146.4 (i-Ph).

UV-vis (toluene), λmax, nm (ϵ, L mol-1 cm-1): 460 (21850), 377 (16400).


Supplementary Figure 6. 1H NMR spectrum of {(HCDippN)2B}2GeGe (5) in C6D6.



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Supplementary Figure 7. 1H NMR spectrum of {(HCDippN)2B}2GeGe (5) and [Cp2Fe] in 1:2 ratio in C6D6.

Supplementary Figure 8. Variable temperature 1H NMR spectra of {(HCDippN)2B}2GeGe (5) in toluene-d8 in the temperature range 183 – 298 K



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Reaction of 5 with H2: synthesis of {(HCDippN)2B}(H)2GeGe(H)2{B(NDippCH)2} (6)

Supplementary Figure 9. Generation of 6 via the reaction of 5 with dihydrogen

A solution of 5 (0.045 g, 0.049 mmol) in pentane (3 mL) was degassed by the freeze-pump-thaw method (3 times) and treated with H2 (4 atm). The reaction mixture was then heated at 45 ̊C for 6 h. By this time, the color changed to pale yellow, and the reaction mixture was then filtered and concentrated. Upon storing at -35 ̊C, a pale yellow crystalline solid started to precipitate. After standing for ca. 2 d, the crystals were isolated and dried in vacuo. Yield: 0.025 g (0.027 mmol, 55%). Crystals for X-ray crystal structure determination were obtained from a saturated solution in pentane at 4 ̊C.

Spectroscopic data: 1H NMR (500 MHz, C6D6, 298 K): 1.14 (d, 24H, 3JHH = 6.9 Hz, CH(CH3)2), 1.19 (d, 24H, 3JHH = 6.9 Hz, CH(CH3)2), 2.22 (s, 4H, Ge-H), 3.07 (sept, 8H, 3JHH = 6.9 Hz, CH(CH3)2), 6.26 (s, 4H, C4/C5-H), 7.09 (d, 3JH-H = 7.8 Hz, 8H, m-Ph), 7.18 (t, 3JH-H = 7.8 Hz, 4H, p-Ph) ppm. 11B{1H} NMR (160.4 MHz, C6D6, 298 K): 27.3 ppm (B-GeH2) 13C{1H} NMR (125 MHz, C6D6, 298 K): 24.1, 25.7 (CH(CH3)2), 29.0 (CH(CH3)2), 122.1 (C4/C5-C), 123.9 (m-Ph), 128.7 (p-Ph), 139.9 (p-Ph), 146.3 (i-Ph).


Supplementary Figure 10. 1H NMR spectrum of {(HCDippN)2B}(H)2GeGe(H)2{B(NDippCH)2} (6) in C6D6.

Ge GeB

B N

N

N

NDipp

Dipp

Dipp

Dipp

6

H2 (4 atm.)

5

Ge Ge

N BN

Dipp

NN

BDipp

iPr

iPr

iPr

iPrH

H

HH



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NMR tube experiments Reaction of 5 with IPr2Me2: generation of (IPr2Me2){(HCDippN)2B}GeGe{B(NDippCH)2} (2) To a yellow solution of 5 in C6D6 (0.5 mL) generated in situ from 3 (0.010 g, 0.01 mmol) and [Cp2Fe][BArf

4] (0.021 g, 0.02 mmol), was added the solid IPr2Me2 (2.0 mg, 0.011 mmol) in a J Young’s NMR tube inside a glove box. Immediately, the color of the reaction mixture changed to deep red. 1H NMR monitoring of the reaction mixture showed quantitative conversion to 2 (Fig. S11, upper).

Reaction of 5 with KC8: regeneration of K2[{(HCDippN)2B}GeGe{B(NDippCH)2}] (3) To a yellow solution of 5 in C6D6 (0.5 mL) generated in situ from 3 (0.010 g, 0.01 mmol) and [Cp2Fe][BArf

4] (0.021 g, 0.02 mmol)) was added solid KC8 (6.0 mg, 0.044 mmol, excess) in a J Young’s NMR tube inside a glove box. The color of the reaction mixture started to change to dark brown. After sonication for ca. 5 mins, 1H NMR monitoring of the reaction mixture showed quantitative conversion to 3 (Fig. S11, lower).

Supplementary Figure 11. 1H NMR monitoring of the reactions of 5 with IPr2Me2 and KC8 in C6D6. (upper) Reaction of 5 with 1 equiv. of IPr2Me2; (center) spectrum of in situ generated 5 and ferrocene in a 1:2 ratio; and (lower) reaction of 5 with KC8. $ denotes ferrocene.



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Cyclic voltammograms

Supplementary Figure 12. Cyclic voltammogram of 2 (left) and 5 (right) in a 0.1 M solution of tetrabutylammonium hexafluorophosphate in THF, referenced to a silver quasi-reference electrode and scanned at 0.5 V s-1.



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UV-visible spectra

Supplementary Figure 13. UV-vis spectra of toluene solutions of compounds containing Ge=Ge double bonds: 2 (0.34 mM, upper left), 3 (0.5 mM, upper right) and 5 (0.54 mM, lower).

The extinction coefficients associated with the features in these spectra are as follows: 2: = 359 nm, ε = 25100 mol-1 dm3 cm-1; = 434 nm ε = 22200 mol-1 dm3 cm-1; 3: = 428 nm, ε = 20100 mol-1 dm3 cm-1; 5: = 377 nm, ε = 16400 mol-1 dm3 cm-1; = 460 nm ε = 21850 mol-1 dm3 cm-1; = 515 nm, ε = 2300 mol-1 dm3 cm-1.



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3. X-ray crystallographic studies Crystals of compounds 1-6, suitable for X-ray structural determinations were mounted on MiTeGen MicroMounts using perfluoropolyether oil and cooled rapidly in a stream of cold N2 using an Oxford Cryosystems Cryostream unit. Crystallographic measurements were performed on an Enraf-Nonius Kappa CCD diffractometer using Mo-Κα radiation (2, 4, 5 and 6) or on an Oxford Diffraction SuperNova machine operating at using Cu-Κα radiation (1 and 3). All structures were solved by direct methods using SHELXT and refined against F2 on all data by full-matrix least squares with SHELXL-2014 (Refs. 7-9). All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were placed in ideal positions and refined using a riding model, except for those directly bound to germanium atoms that were located in the Fourier difference electron density map. Complete details of the X-ray analyses reported herein have been deposited at The Cambridge Crystallographic Data Centre (CCDC 1447808-1447813); key details are given in Supplementary Table 1.

Additional details for 2: An extreme case of whole molecule disorder was found in the crystal structure of 2. Of the twelve molecules of the germanium dimer per unit cell, four appeared fully disordered over at least two main positions and lying over the c glide plane. Modeling this disorder proved to be extremely difficult and the refinement recurrently became unstable. Given the fact that the same unit cell contains other eight well-behaved molecules of 2, we took the decision of treating the heavily disordered component as a diffuse contribution to the overall scattering without specific atom positions by using the SQUEEZE/PLATON routine9.

Additional details for 3.½(C7H8): The central Ge2 core, as well as the bonded NHC ligands, were found to be disordered over an inversion center and have been modelled using PART -1/-2 cards. In order to obtained reasonable anisotropic displacement parameters SIMU/DELU instructions were employed.

Alert level A

PLAT910_ALERT_3_A Missing # of FCF Reflection(s) Below Th(Min) ... 58 Report Author Response: To avoid other particular problems related to the X-Ray instrument employed the theta minimum value is set up to 4.0. This is the reason for the missing reflections at low angle. However this does not present a problem due to the high number of independent reflections (7933) collected and the high data/parameter ratio (ca. 22).

Additional details for 4: A small contribution (ca. 8%) of a second component of the main molecule was observed, but only the heavier Ge centres could be modelled, being their anisotropic displacement parameters constrained to be identical to those of the main component by using EADP.

Alert level B



15

PLAT987_ALERT_1_B The Flack x is >> 0 - Do a BASF/TWIN Refinement Please Check Author Response: The structure was refined as an inversion twin and the refinement converged for a volume fraction of 0.45, in good agreement with the (unrefined, calculated only) conventional Flack parameter (0.0449(16)), thus confirming the presence of two-component inversion twin close to racemic twining.



Supplementary Table 1: Crystallographic details for compounds 1-6.

1 2 3.½(C7H8): 4 5 6

Molecular formula C37H56BClGeN4 C63H92B2Ge2N6 C33H44BGeKN2 C63H94B2Ge2N6 C52H72B2Ge2N4 C52H76B2Ge2N4

Mr 675.73 1100.22 591.20 1102.24 919.93 923.96

Crystal system monoclinic monoclinic monoclinic orthorhombic monoclinic monoclinic

Space group C2/c C2/c C2/c P 212121 P21/n P21/n

Unit cell dimensions

(Å/o)

a = 31.5447(4)

b = 15.1571(2)

c = 16.3260(3)

β = 102.9399(7)

a = 51.3040(2)

b = 13.7692(6)

c = 27.1756(5)

β = 101.731(3)

a = 26.718(5)

b = 18.519(4)

c = 14.938(3)

β = 108.53(3)

a = 16.8587(2)

b = 19.0488(2)

c = 19.5197(2)

a = 22.4542(7)

b = 10.5244(3)

c = 23.6510(8)

β = 112.271(4)

a = 13.6923(3)

b = 12.3401(2)

c = 15.7584(4)

β = 97.648(2)

Cell volume (Å3) 7607.7(2) 18796.2(12) 7008.00(3) 6268.52(12) 5172.2(3) 2638.92(10)

Z 8 8 8 4 4 2

ρc (mg m-3) 1.180 0.778 1.121 1.168 1.181 1.163

T (K) 150 150 150 150 150 150

λ (Å) 0.71073 1.54180 0.71073 1.54180 1.54180 1.54180

Reflections (independent) 15997 (8603) 19571 (13324) 7933 (5286) 12415 (12190) 10189 (8365) 5226 (4605)

R(int) 0.027 0.074 0.040 0.024 0.039 0.030

R1 and wR2 [I > 2σ(I)] 0.0469, 0.1011 0.0793, 0.2115 0.0639, 0.1663 0.0290, 0.0975 0.0337, 0.0884 0.0299, 0.0826

R1 and wR2 [all reflns] 0.0631, 0.1164 0.1066, 0.2418 0.0985, 0.1797 0.0297, 0.0992 0.0442, 0.0979 0.0346, 0.0881

Residuals (e Å-3) 2.32, -0.82 0.77, -1.30 1.19, -1.60 0.42, -0.45 0.50, -0.35 0.27, -0.54

CCDC reference 1447808 1447809 1447810 1447811 1447812 1447813



Supplementary Figure 14. Thermal ellipsoid (50%) drawing of 1 (hydrogen atoms are not shown and Dipp groups are drawn in wireframe format for clarity). Selected bond distances and angles are as follows: Ge(1)-B(5) 2.111(3) Å, Ge(1)-C(34) 2.084(2) Å, Ge(1)-Cl(2) 2.338(1) Å, Cl(2)-Ge(1)-B(5) 101.7(1)o, Cl(2)-Ge(1)-C(34) 94.8(1)o, B(5)-Ge(1)-C(34) 99.5(1)o.

Supplementary Figure 15. Thermal ellipsoid (50%) drawing of 2 (hydrogen atoms are not shown and boryl/carbene substituents are drawn in wireframe format for clarity). Selected bond distances and angles are as follows: Ge(1)-Ge(2) 2.279(1) Å, Ge(1)-B(1) 2.094(5), Ge(2)-B(2) 2.057(4) Å, Ge(2)-C(53) 2.003(5) Å, B(1)-Ge(1)-Ge(2) 111.6(1)o, B(2)-Ge(2)-Ge(1) 118.6(1)o.

B5

Ge1

Cl2

C34

C53

B2

B1

Ge1

Ge2



18

Supplementary Figure 16. Thermal ellipsoid (50%) drawing of 4 (most hydrogen atoms are not shown and boryl/carbene substituents are drawn in wireframe format for clarity). Selected bond distances and angles are as follows: Ge(1)-Ge(2) 2.454(1) Å, Ge(1)-B(1) 2.106(3), Ge(2)-B(2) 2.058(3) Å, Ge(2)-C(53) 2.069(3) Å, B(1)-Ge(1)-Ge(2) 104.5(1)o, B(2)-Ge(2)-Ge(1) 115.1(1)o.

Supplementary Figure 17. Thermal ellipsoid (50%) drawing of 6 (most hydrogen atoms are not shown and Dipp substituents are drawn in wireframe format for clarity). Selected bond distances and angles are as follows: Ge(1)-Ge(2) 2.411(1) Å, Ge(1)-B(1) 2.042(2), B(1)-Ge(1)-Ge(1') 114.2(1)o.

Ge1 Ge2

H1B H2B B1

B2 C53

Ge1

Ge1’ H1B

H2B

H1B’ H2B’

B1

B1’



19

4. Computational details DFT calculations were performed using the Amsterdam Density Functional (ADF) 2013 software package. Calculations were performed using the Vosko-Wilk-Nusair local density approximation with exchange from Becke10, and correlation corrections from Perdew11, and 3-dimension dispersion effect (BP86-D3). Slater-type orbitals (STOs)12 were used for the triple zeta basis set with an additional set of polarization functions (TZP). The large frozen core basis set approximation was applied with no molecular symmetry. General numerical quality was good. Run files for the geometry calculations are given below and complete output files will be provided upon request.

Supplementary Figure 18. DFT Optimized structures of {(HCDippN)2B}2GeGe (5) (left) and the hypothetical 1,2 isomer {(HCDippN)2B}GeGe{B(DippNCH)2} (right) along with the corresponding DFT calculated energies.

#! /bin/sh

# ==============================

# {(HCDippN)2B}2GeGe (5) # ==============================

"$ADFBIN/adf" <<eor

ATOMS

1 Ge 1.141065347000 6.497645877000 11.939525040000 R=2.033

2 Ge 0.726001415600 6.547099166000 14.297782670000 R=2.033

3 N 3.999626507000 7.048913268000 12.818026250000 R=1.608

4 N 4.191601247000 6.391020471000 10.632966320000 R=1.608



20

5 N -1.852720532000 5.986576639000 11.807987290000 R=1.608

6 N -1.277095067000 6.550068403000 9.664329500000 R=1.608

7 B 3.195423485000 6.659820788000 11.659939340000 R=1.792

8 B -0.695917206900 6.327304308000 10.980319130000 R=1.792

9 C 5.356068425000 7.006112924000 12.468177580000 R=1.700

10 C 3.803142134000 3.503766127000 10.277946300000 R=1.700

11 C 5.469239873000 6.611631220000 11.174283390000 R=1.700

12 C -2.678979740000 2.494974468000 12.300251970000 R=1.700

13 C 3.630816716000 7.358252908000 14.171049180000 R=1.700

14 C 3.319831278000 8.701931040000 14.521640040000 R=1.700

15 C 3.135196458000 9.007580549000 15.875992510000 R=1.700

16 C 5.012608476000 2.550724016000 10.344180080000 R=1.700

17 C 3.244689330000 8.025695423000 16.862622050000 R=1.700

18 C -0.120584008600 6.600929497000 6.116692616000 R=1.700

19 C 3.523113240000 6.710462827000 16.507862570000 R=1.700

20 C -0.761484370800 9.421303187000 9.348913704000 R=1.700

21 C 3.718458296000 6.341252519000 15.163802570000 R=1.700

22 C 3.274493179000 9.804171752000 13.471882300000 R=1.700

23 C 0.135615726600 7.958479688000 5.934498129000 R=1.700

24 C 2.102103281000 10.775520790000 13.676535090000 R=1.700

25 C 2.482481040000 2.716847591000 10.230881390000 R=1.700

26 C -2.639502903000 8.201024222000 13.570354510000 R=1.700

27 C -1.913419168000 10.369118320000 8.961277661000 R=1.700

28 C 4.615806876000 10.565661520000 13.427307430000 R=1.700

29 C -2.023598802000 9.283800894000 14.472001220000 R=1.700

30 C -3.006573431000 6.008179660000 11.012661230000 R=1.700

31 C -0.053287174840 8.846911766000 6.991310285000 R=1.700

32 C 4.133537211000 4.912426231000 14.828170550000 R=1.700

33 C -2.665122430000 6.347436619000 9.743404342000 R=1.700

34 C 5.609612032000 4.672061042000 15.209160180000 R=1.700

35 C 0.503457162900 10.212936110000 9.721731787000 R=1.700

36 C -1.972433644000 5.732001552000 13.216236430000 R=1.700

37 C -1.815531793000 4.403453950000 13.701384220000 R=1.700



21

38 C 3.234444554000 3.858123838000 15.495200350000 R=1.700

39 C -2.108792098000 4.150993099000 15.047647190000 R=1.700

40 C -0.496182483300 8.403174727000 8.245985239000 R=1.700

41 C -2.536807886000 5.170242737000 15.900125260000 R=1.700

42 C 4.107173673000 5.866767607000 9.295504005000 R=1.700

43 C 4.318207564000 6.736699747000 8.199005573000 R=1.700

44 C 4.322036852000 6.186060822000 6.909413566000 R=1.700

45 C -4.153159457000 8.449603286000 13.399713040000 R=1.700

46 C 4.135956263000 4.820198337000 6.706215217000 R=1.700

47 C -2.660959295000 6.470578934000 15.423578790000 R=1.700

48 C 3.946048393000 3.976701051000 7.799028243000 R=1.700

49 C -0.897867292000 4.622699797000 7.491920123000 R=1.700

50 C 3.934970475000 4.474656637000 9.110384678000 R=1.700

51 C 4.591023994000 8.225295955000 8.384970463000 R=1.700

52 C -2.381605081000 6.786939086000 14.080833870000 R=1.700

53 C 3.697922996000 9.103721265000 7.493451121000 R=1.700

54 C -1.425868978000 3.261525329000 12.772620600000 R=1.700

55 C 0.241805726400 3.712821242000 7.005017530000 R=1.700

56 C -0.403835250200 2.302839260000 13.402614980000 R=1.700

57 C 6.078036939000 8.551006576000 8.133636215000 R=1.700

58 C -2.207419214000 4.278693867000 6.752641312000 R=1.700

59 C -0.734350659900 7.018967812000 8.416784410000 R=1.700

60 C -0.563987617200 6.103737110000 7.350623250000 R=1.700

61 H 6.138877553000 7.265877338000 13.172609940000 R=1.350

62 H 3.796581510000 4.098254186000 11.201668540000 R=1.350

63 H 6.366822644000 6.458173210000 10.585219670000 R=1.350

64 H -2.395715161000 1.693576082000 11.601929550000 R=1.350

65 H -3.385806662000 3.160077755000 11.785970810000 R=1.350

66 H -3.200744674000 2.034608572000 13.152898220000 R=1.350

67 H 2.910800239000 10.034686420000 16.166566610000 R=1.350

68 H 5.956376461000 3.108565579000 10.420478010000 R=1.350

69 H 5.068793227000 1.913075353000 9.449131908000 R=1.350

70 H 4.932800120000 1.891445586000 11.221183170000 R=1.350



22

71 H 3.106164937000 8.290230255000 17.912444070000 R=1.350

72 H 0.020157920000 5.912333411000 5.281793975000 R=1.350

73 H 3.602444198000 5.949400577000 17.285387990000 R=1.350

74 H -1.074501744000 8.864760602000 10.242821970000 R=1.350

75 H 3.132987869000 9.314419892000 12.498145220000 R=1.350

76 H 0.477552418200 8.325807426000 4.965121689000 R=1.350

77 H 2.206447093000 11.360616480000 14.602193250000 R=1.350

78 H 1.147229331000 10.234086490000 13.714089850000 R=1.350

79 H 2.059618792000 11.489677730000 12.841809480000 R=1.350

80 H 1.619532110000 3.396461956000 10.247685480000 R=1.350

81 H 2.406899538000 2.049821490000 11.101783240000 R=1.350

82 H 2.413573675000 2.095851789000 9.325417567000 R=1.350

83 H -2.169004687000 8.280081808000 12.580065210000 R=1.350

84 H -2.130979887000 11.064465910000 9.785418051000 R=1.350

85 H -2.831520178000 9.809198587000 8.734940143000 R=1.350

86 H -1.656885533000 10.968988710000 8.075157398000 R=1.350

87 H 5.454289342000 9.889269703000 13.213161280000 R=1.350

88 H 4.814904623000 11.063948000000 14.388188870000 R=1.350

89 H 4.591340362000 11.336752830000 12.643066620000 R=1.350

90 H -0.948699682900 9.108009759000 14.620176920000 R=1.350

91 H -2.504966735000 9.316141143000 15.460645140000 R=1.350

92 H -2.154428331000 10.273343660000 14.010808280000 R=1.350

93 H -3.986052410000 5.774825688000 11.415977990000 R=1.350

94 H 0.132524625900 9.911639413000 6.836561266000 R=1.350

95 H 4.040855739000 4.793613870000 13.739422240000 R=1.350

96 H -3.304867321000 6.471963851000 8.876518877000 R=1.350

97 H 6.280160161000 5.373981883000 14.696217910000 R=1.350

98 H 5.912067366000 3.650823822000 14.934861240000 R=1.350

99 H 5.756996162000 4.789629643000 16.293266020000 R=1.350

100 H 1.303066098000 9.539393667000 10.059012780000 R=1.350

101 H 0.284321443900 10.916324870000 10.538004340000 R=1.350

102 H 0.881978187600 10.795665380000 8.868894531000 R=1.350

103 H 3.516430235000 2.852911257000 15.150197240000 R=1.350



23

104 H 2.177662399000 4.029089784000 15.244981470000 R=1.350

105 H 3.333139636000 3.869699314000 16.590752410000 R=1.350

106 H -2.009728894000 3.136248617000 15.435252910000 R=1.350

107 H -2.768729547000 4.946873491000 16.943018280000 R=1.350

108 H 4.479988644000 6.839100145000 6.049418475000 R=1.350

109 H -4.330663829000 9.459822622000 13.002572650000 R=1.350

110 H -4.672957812000 8.369189371000 14.366248900000 R=1.350

111 H -4.607230493000 7.728497636000 12.707486260000 R=1.350

112 H 4.145461979000 4.411208570000 5.694128255000 R=1.350

113 H -2.991684758000 7.261042047000 16.098650360000 R=1.350

114 H 3.819626471000 2.904854429000 7.633826283000 R=1.350

115 H -1.053383518000 4.423167843000 8.561434921000 R=1.350

116 H 4.365735331000 8.470686728000 9.432326059000 R=1.350

117 H 3.860135486000 10.165842870000 7.729216445000 R=1.350

118 H 2.635149014000 8.874445354000 7.639073451000 R=1.350

119 H 3.929621086000 8.964786575000 6.426946403000 R=1.350

120 H -0.954722454600 3.713281152000 11.888314910000 R=1.350

121 H 1.188811910000 3.953400405000 7.503561799000 R=1.350

122 H 0.399020202800 3.806524161000 5.920176453000 R=1.350

123 H -0.002440889892 2.660432386000 7.211933283000 R=1.350

124 H -0.084979365570 1.557550406000 12.660026090000 R=1.350

125 H -0.824502956700 1.752954722000 14.257397630000 R=1.350

126 H 0.485559494700 2.848968198000 13.744815260000 R=1.350

127 H 6.739235028000 7.975580722000 8.795422729000 R=1.350

128 H 6.270715711000 9.620285255000 8.306549421000 R=1.350

129 H 6.357652001000 8.320556152000 7.094422307000 R=1.350

130 H -2.105677271000 4.462349965000 5.672292819000 R=1.350

131 H -3.051436407000 4.879138754000 7.117871628000 R=1.350

132 H -2.459600444000 3.217026916000 6.892776543000 R=1.350

END

GUIBONDS

1 1 7 1.0 2 1 8 1.0 3 1 2 2.0



24

4 3 9 1.0

5 3 13 1.0

6 3 7 1.0

7 4 11 1.0

8 4 7 1.0

9 4 42 1.0

10 5 30 1.0

11 5 36 1.0

12 5 8 1.0

13 6 33 1.0

14 6 8 1.0

15 6 59 1.0

16 54 12 1.0

17 9 11 2.0

18 54 56 1.0

19 13 14 1.5

20 13 21 1.5

21 14 15 1.5

22 14 22 1.0

23 59 40 1.5

24 15 17 1.5

25 10 25 1.0

26 17 19 1.5

27 10 16 1.0

28 19 21 1.5

29 21 32 1.0

30 59 60 1.5

31 22 24 1.0

32 22 28 1.0

33 49 55 1.0

34 60 18 1.5

35 60 49 1.0

36 26 45 1.0

37 18 23 1.5

38 26 29 1.0

39 30 33 2.0

40 32 38 1.0

41 32 34 1.0

42 36 52 1.5

43 36 37 1.5

44 49 58 1.0

45 23 31 1.5

46 37 39 1.5

47 37 54 1.0

48 42 43 1.5

49 42 50 1.5

50 43 44 1.5

51 43 51 1.0

52 39 41 1.5

53 44 46 1.5

54 20 27 1.0

55 46 48 1.5

56 41 47 1.5

57 48 50 1.5

58 50 10 1.0

59 31 40 1.5

60 51 57 1.0

61 51 53 1.0

62 40 20 1.0

63 47 52 1.5

64 52 26 1.0

65 20 35 1.0

66 132 58 1.0

67 131 58 1.0

68 61 9 1.0

69 62 10 1.0

70 63 11 1.0

71 64 12 1.0

72 65 12 1.0

73 66 12 1.0

74 67 15 1.0

75 68 16 1.0

76 69 16 1.0

77 70 16 1.0

78 71 17 1.0

79 72 18 1.0

80 73 19 1.0

81 74 20 1.0

82 75 22 1.0

83 76 23 1.0

84 77 24 1.0

85 78 24 1.0

86 79 24 1.0

87 80 25 1.0

88 81 25 1.0

89 82 25 1.0

90 83 26 1.0

91 84 27 1.0

92 85 27 1.0

93 86 27 1.0

94 87 28 1.0

95 88 28 1.0

96 89 28 1.0

97 90 29 1.0

98 91 29 1.0

99 92 29 1.0

100 93 30 1.0

101 94 31 1.0

102 95 32 1.0



25

103 96 33 1.0

104 97 34 1.0

105 98 34 1.0

106 99 34 1.0

107 100 35 1.0

108 101 35 1.0

109 102 35 1.0

110 103 38 1.0

111 104 38 1.0

112 105 38 1.0

113 106 39 1.0

114 107 41 1.0

115 108 44 1.0

116 109 45 1.0

117 110 45 1.0

118 111 45 1.0

119 112 46 1.0

120 113 47 1.0

121 114 48 1.0

122 115 49 1.0

123 116 51 1.0

124 117 53 1.0

125 118 53 1.0

126 119 53 1.0

127 120 54 1.0

128 121 55 1.0

129 122 55 1.0

130 123 55 1.0

131 124 56 1.0

132 125 56 1.0

133 126 56 1.0

134 127 57 1.0

135 128 57 1.0

136 129 57 1.0

137 130 58 1.0

END

SOLVATION

Surf Esurf

Solvent name=Hexane cav0=0.0 cav1=0.0067639

Charged method=CONJ

C-Mat POT

SCF VAR ALL

CSMRSP

END

BASIS

type TZP

core Large

createoutput None

END

XC

GGA Becke88 Perdew86

DISPERSION Grimme3

END



26

GEOMETRY

optim Delocalized

END

SAVE TAPE21 TAPE13

NumericalQuality Good

NOPRINT LOGFILE

eor

-----------------------------------------------------------------------

#! /bin/sh

# ==============================

# 1,2 isomer {(HCDippN)2B}GeGe{B(DippNCH)2}

# ==============================

"$ADFBIN/adf" <<eor

ATOMS

1 Ge 32.202635605788 7.318439982113 15.072774048693 R=2.033

2 Ge 31.021435273613 5.393927781049 15.539651929618 R=2.033

3 B 31.346792804558 3.639243340793 16.605417991118 R=1.792

4 N 30.580780950003 2.457133056752 16.924038120159 R=1.608

5 C 31.454353674338 1.509741126625 17.480654173288 R=1.700

6 C 32.714219208507 2.024622716457 17.531373693338 R=1.700

7 N 32.689316565202 3.329819872585 17.035332114334 R=1.608

8 C 33.860254182040 4.151603581567 16.903976097334 R=1.700



27

9 C 34.076490938055 5.185569089528 17.844847987450 R=1.700

10 C 35.202533756263 5.998229726852 17.665166313872 R=1.700

11 C 36.078069696327 5.795282108264 16.594491736220 R=1.700

12 C 35.832266752677 4.781931780440 15.671572578476 R=1.700

13 C 34.710551094991 3.947030939180 15.801192167055 R=1.700

14 C 34.417818704248 2.884830371583 14.748986316758 R=1.700

15 C 34.180621416283 3.520961039552 13.368122940692 R=1.700

16 C 35.531695497187 1.824523191078 14.693950297476 R=1.700

17 C 33.094608976736 5.417477215944 18.988404161791 R=1.700

18 C 33.290170485226 4.394117483599 20.123134467564 R=1.700

19 C 33.135551480112 6.846008727596 19.538190043153 R=1.700

20 C 29.168597569882 2.200452898653 16.854971925545 R=1.700

21 C 28.559278474467 1.994712032078 15.596383882979 R=1.700

22 C 29.365191313730 2.092974478661 14.303458670434 R=1.700

23 C 30.349223751052 0.916289289088 14.146597588596 R=1.700

24 C 28.497739342879 2.213975365715 13.045249634493 R=1.700

25 C 27.189789007511 1.689440229271 15.580992597882 R=1.700

26 C 26.455892191445 1.590206000071 16.763557430683 R=1.700

27 C 27.075063460865 1.816624016428 17.993000478498 R=1.700

28 C 28.440058252667 2.129511512299 18.065464672666 R=1.700

29 C 29.113193237294 2.432050861215 19.403157182825 R=1.700

30 C 29.245096376028 3.953252224897 19.606742951615 R=1.700

31 C 28.420086872913 1.784154087848 20.609445726898 R=1.700

32 N 30.871391681588 10.171536730789 15.366792970146 R=1.608

33 C 32.047930550715 10.879233140064 14.961127236429 R=1.700

34 C 33.160181456713 10.927829628930 15.831486343824 R=1.700

35 C 33.120601558606 10.238116842486 17.194180453171 R=1.700

36 C 32.272046733249 11.032079676788 18.206207928867 R=1.700

37 C 34.509841706088 9.937737998985 17.768601016872 R=1.700

38 C 34.290282519456 11.639130580056 15.401279098376 R=1.700

39 C 34.315245201942 12.271490018774 14.156457886984 R=1.700

40 C 33.213934454134 12.187118210014 13.304303110444 R=1.700

41 C 32.062310075531 11.482269040443 13.683609078869 R=1.700



28

42 C 30.895149973807 11.292988685368 12.717949867273 R=1.700

43 C 31.065702790090 9.972039305102 11.940336846603 R=1.700

44 C 30.694015864953 12.469442159039 11.752271155074 R=1.700

45 B 30.651801983990 8.744552629671 15.391306178556 R=1.792

46 N 29.243168253907 8.619098252018 15.730493593257 R=1.608

47 C 28.452159280278 7.445198047816 15.932621414095 R=1.700

48 C 28.032309581490 7.111799145503 17.243321658809 R=1.700

49 C 27.241800378815 5.964769338855 17.401541387732 R=1.700

50 C 26.903177271785 5.162804524504 16.313184504612 R=1.700

51 C 27.331747929137 5.503635826968 15.031929495798 R=1.700

52 C 28.101519076662 6.655774763259 14.807363326976 R=1.700

53 C 28.492311330557 7.087341752883 13.398185516293 R=1.700

54 C 28.566338680662 5.927150487202 12.400942257645 R=1.700

55 C 27.550078481136 8.194259659266 12.886682082570 R=1.700

56 C 28.452118941929 7.958324362161 18.443125828782 R=1.700

57 C 29.912655630451 7.673755406918 18.838684120830 R=1.700

58 C 27.532401964277 7.797737630490 19.661943195290 R=1.700

59 C 28.699811800888 9.902829562902 15.877089352841 R=1.700

60 C 29.671409433405 10.830700001441 15.665776201604 R=1.700

61 H 31.105223212554 0.529548944580 17.786376853180 R=1.350

62 H 33.632846095194 1.557628979710 17.868031011569 R=1.350

63 H 35.393702012508 6.816628286806 18.358189205374 R=1.350

64 H 36.945867487619 6.444667777767 16.473067326531 R=1.350

65 H 36.507165298104 4.646563952100 14.824380523798 R=1.350

66 H 33.488304764901 2.374565636671 15.035989578222 R=1.350

67 H 35.085897543804 4.030173728611 13.003233338364 R=1.350

68 H 33.370848553909 4.264449990325 13.412851753869 R=1.350

69 H 33.906337638188 2.747982680152 12.634115262779 R=1.350

70 H 36.491404141463 2.272261604703 14.393691254113 R=1.350

71 H 35.281746858106 1.042067658780 13.961522926297 R=1.350

72 H 35.674143957635 1.347168123978 15.674620500991 R=1.350

73 H 32.086362663943 5.264887961750 18.573304422499 R=1.350

74 H 33.178213080061 3.364377072830 19.758549950150 R=1.350



29

75 H 32.542862505238 4.556897573200 20.915042237259 R=1.350

76 H 34.292015739125 4.498578534863 20.569050863074 R=1.350

77 H 34.093018911460 7.069614745307 20.032339855174 R=1.350

78 H 32.340770905743 6.981541823959 20.283740655409 R=1.350

79 H 32.976232508714 7.576971217115 18.734618043260 R=1.350

80 H 29.964523513320 3.016449031585 14.372963169365 R=1.350

81 H 30.928854043251 1.030479688926 13.218068972094 R=1.350

82 H 29.800003849123 -0.037049551407 14.093406218365 R=1.350

83 H 31.057037857356 0.861469084979 14.983375096385 R=1.350

84 H 29.136479215461 2.417835218699 12.174612585664 R=1.350

85 H 27.771355936696 3.032839231955 13.126231894516 R=1.350

86 H 27.947618867612 1.282834492285 12.839974064042 R=1.350

87 H 26.685506708996 1.525590461587 14.629666865712 R=1.350

88 H 25.393371081298 1.346811127889 16.725212475889 R=1.350

89 H 26.486895133397 1.750757848781 18.908262853379 R=1.350

90 H 30.135363152486 2.029447068102 19.360770884613 R=1.350

91 H 29.848891443575 4.173557484809 20.499999575556 R=1.350

92 H 28.253045285577 4.409452651567 19.737878977929 R=1.350

93 H 29.720324304160 4.432314480270 18.740081344983 R=1.350

94 H 28.285571792343 0.701744704750 20.469770706863 R=1.350

95 H 27.431564690320 2.229070823010 20.799515840015 R=1.350

96 H 29.025735270636 1.941110813883 21.513820023892 R=1.350

97 H 32.612631360234 9.270601017819 17.052930333894 R=1.350

98 H 32.215100788147 10.488092772986 19.161308828527 R=1.350

99 H 31.248260601880 11.176992787323 17.835794791225 R=1.350

100 H 32.720195112782 12.020292148907 18.394915610074 R=1.350

101 H 35.061184767979 10.859567027425 18.007165268974 R=1.350

102 H 35.113237091535 9.339940911149 17.070786440895 R=1.350

103 H 34.408840963777 9.369010210632 18.702572988528 R=1.350

104 H 35.168930440956 11.695423230640 16.042879986692 R=1.350

105 H 35.202868321627 12.823901473821 13.844943729552 R=1.350

106 H 33.254903092695 12.669336487984 12.327182516820 R=1.350

107 H 29.977194239819 11.196714292244 13.314708580056 R=1.350



30

108 H 31.958331216344 10.018227815986 11.296655478714 R=1.350

109 H 30.187057618209 9.783546277553 11.304575698374 R=1.350

110 H 31.184458750765 9.120998900303 12.626296917154 R=1.350

111 H 30.611205360448 13.425490155694 12.289275537700 R=1.350

112 H 29.773115841882 12.320653970924 11.169547153886 R=1.350

113 H 31.522316483782 12.553121693623 11.032881086234 R=1.350

114 H 26.892824251050 5.682552790715 18.393224162307 R=1.350

115 H 26.314426892599 4.259000533897 16.467126596354 R=1.350

116 H 27.057535585286 4.866074324684 14.192483018688 R=1.350

117 H 29.500645604090 7.522016678476 13.461743480516 R=1.350

118 H 29.224471198288 5.129535205363 12.774884523280 R=1.350

119 H 28.970204407733 6.284833436964 11.442903261021 R=1.350

120 H 27.574974477859 5.493941365693 12.198292138303 R=1.350

121 H 27.564569580432 9.067845942276 13.552871630063 R=1.350

122 H 26.515395408361 7.822349949086 12.819734715184 R=1.350

123 H 27.863444511091 8.524416143506 11.884512850739 R=1.350

124 H 28.406694974949 9.013195070718 18.134320934797 R=1.350

125 H 30.589429451128 7.765353189870 17.979371963975 R=1.350

126 H 30.010424058749 6.651602628807 19.232023579521 R=1.350

127 H 30.242783991982 8.376412839417 19.618569864401 R=1.350

128 H 27.816070073682 8.521971456053 20.439077318380 R=1.350

129 H 27.622002528475 6.794536282163 20.105283558610 R=1.350

130 H 26.476330636570 7.965053790595 19.405069144963 R=1.350

131 H 27.653444181006 10.055272096757 16.117173745812 R=1.350

132 H 29.605253744816 11.912534342807 15.700768485416 R=1.350

END

GUIBONDS

1 1 45 3

2 1 2 3.0

3 2 3 3

4 3 4 1.0

5 3 7 1.0

6 4 5 1.0

7 4 20 1.0

8 5 61 1.0

9 5 6 2.0

10 6 62 1.0

11 6 7 1.0

12 7 8 1.0

13 8 9 1.5

14 8 13 1.5

15 9 10 1.5



31

16 9 17 1.0

17 10 63 1.0

18 10 11 1.5

19 11 64 1.0

20 11 12 1.5

21 12 65 1.0

22 12 13 1.5

23 13 14 1.0

24 14 66 1.0

25 14 15 1.0

26 14 16 1.0

27 15 68 1.0

28 15 69 1.0

29 15 67 1.0

30 16 72 1.0

31 16 71 1.0

32 16 70 1.0

33 17 73 1.0

34 17 19 1.0

35 17 18 1.0

36 18 74 1.0

37 18 75 1.0

38 18 76 1.0

39 19 79 1.0

40 19 78 1.0

41 19 77 1.0

42 20 28 1.5

43 20 21 1.5

44 21 25 1.5

45 21 22 1.0

46 22 80 1.0

47 22 24 1.0

48 22 23 1.0

49 23 83 1.0

50 23 81 1.0

51 23 82 1.0

52 24 85 1.0

53 24 84 1.0

54 24 86 1.0

55 25 87 1.0

56 25 26 1.5

57 26 88 1.0

58 26 27 1.5

59 27 89 1.0

60 27 28 1.5

61 28 29 1.0

62 29 90 1.0

63 29 30 1.0

64 29 31 1.0

65 30 93 1.0

66 30 91 1.0

67 30 92 1.0

68 31 94 1.0

69 31 96 1.0

70 31 95 1.0

71 32 60 1.0

72 32 33 1.0

73 32 45 1.0

74 33 34 1.5

75 33 41 1.5

76 34 38 1.5

77 34 35 1.0

78 35 97 1.0

79 35 37 1.0

80 35 36 1.0

81 36 99 1.0

82 36 98 1.0

83 36 100 1.0

84 37 102 1.0

85 37 103 1.0

86 37 101 1.0

87 38 104 1.0

88 38 39 1.5

89 39 105 1.0

90 39 40 1.5

91 40 106 1.0

92 40 41 1.5

93 41 42 1.0

94 42 107 1.0

95 42 43 1.0

96 42 44 1.0

97 43 110 1.0

98 43 109 1.0

99 43 108 1.0

100 44 111 1.0

101 44 112 1.0

102 44 113 1.0

103 45 46 1.0

104 46 59 1.0

105 46 47 1.0

106 47 48 1.5

107 47 52 1.5

108 48 49 1.5

109 48 56 1.0

110 49 114 1.0

111 49 50 1.5

112 50 115 1.0

113 50 51 1.5

114 51 116 1.0



32

115 51 52 1.5

116 52 53 1.0

117 53 117 1.0

118 53 54 1.0

119 53 55 1.0

120 54 118 1.0

121 54 119 1.0

122 54 120 1.0

123 55 121 1.0

124 55 123 1.0

125 55 122 1.0

126 56 124 1.0

127 56 57 1.0

128 56 58 1.0

129 57 125 1.0

130 57 127 1.0

131 57 126 1.0

132 58 130 1.0

133 58 128 1.0

134 58 129 1.0

135 59 131 1.0

136 59 60 2.0

137 60 132 1.0

END

SOLVATION

Surf Esurf


Charged method=CONJ

C-Mat POT

SCF VAR ALL

CSMRSP

END

BASIS

type TZP

core Large

createoutput None

END

XC


DISPERSION Grimme3

END

GEOMETRY

optim Delocalized

iterations 100



33

END

SAVE TAPE21 TAPE13

SCF

iterations 200

END

BeckeGrid

Quality Good

End

STOFIT

NOPRINT LOGFILE

eor

---------------------------------------------------------



34

Supplementary Figure 19. DFT Optimized structure of the 1,1 (left) and 1,2 isomers (right) of Ar'2Ge2 along with the corresponding DFT calculated energies. where Ar' = 2,6-(2,6-iPr2C6H3)2C6H3}2.

---------------------------------------------

#! /bin/sh

# ==============================

# {2,6-(2,6-iPr2C6H3)2C6H3}2GeGe

# ==============================

"$ADFBIN/adf" <<eor

ATOMS

1 H -1.922422000000 3.312875000000 0.926728000000 R=1.350

2 C 0.903538000000 10.093328000000 0.922664000000 R=1.700

3 C 0.455440000000 11.347143000000 1.428255000000 R=1.700

4 C 1.211895000000 12.006240000000 2.418837000000 R=1.700

5 H 0.791705000000 12.909099000000 2.856577000000 R=1.350

6 C 2.442234000000 11.544573000000 2.858219000000 R=1.700

7 H 3.018367000000 12.097728000000 3.599641000000 R=1.350

8 C 2.881936000000 10.318823000000 2.377649000000 R=1.700

9 H 3.801547000000 9.875809000000 2.762665000000 R=1.350

10 C 2.104247000000 9.563444000000 1.482584000000 R=1.700

11 C 2.599301000000 8.139286000000 1.458208000000 R=1.700

12 C 3.737577000000 7.767844000000 0.686079000000 R=1.700



35

13 C 4.423705000000 6.592915000000 1.017470000000 R=1.700

14 H 5.307514000000 6.305996000000 0.447764000000 R=1.350

15 C 3.982900000000 5.770683000000 2.060032000000 R=1.700

16 H 4.532719000000 4.860822000000 2.303905000000 R=1.350

17 C 2.838624000000 6.103899000000 2.778289000000 R=1.700

18 H 2.499268000000 5.453333000000 3.585816000000 R=1.350

19 C 2.131438000000 7.292412000000 2.507166000000 R=1.700

20 C -0.830273000000 12.068695000000 1.150990000000 R=1.700

21 C -0.796414000000 13.427092000000 0.724096000000 R=1.700

22 C -1.993118000000 14.158739000000 0.712003000000 R=1.700

23 H -1.985523000000 15.188219000000 0.348495000000 R=1.350

24 C -3.174464000000 13.623791000000 1.215698000000 R=1.700

25 H -4.084813000000 14.224311000000 1.240461000000 R=1.350

26 C -3.180638000000 12.319827000000 1.705632000000 R=1.700

27 H -4.086263000000 11.926014000000 2.168244000000 R=1.350

28 C -2.041792000000 11.509297000000 1.637080000000 R=1.700

29 C -2.101023000000 10.112906000000 2.249695000000 R=1.700

30 H -1.210644000000 9.560385000000 1.927063000000 R=1.350

31 C -2.035403000000 10.193805000000 3.784820000000 R=1.700

32 H -1.122295000000 10.718563000000 4.105186000000 R=1.350

33 H -2.024046000000 9.184422000000 4.224671000000 R=1.350

34 H -2.904954000000 10.736709000000 4.188590000000 R=1.350

35 C -3.307532000000 9.292036000000 1.771562000000 R=1.700

36 H -3.236792000000 8.264900000000 2.160408000000 R=1.350

37 H -3.333761000000 9.238641000000 0.672873000000 R=1.350

38 H -4.261937000000 9.715793000000 2.120631000000 R=1.350

39 C 0.501423000000 14.190914000000 0.427449000000 R=1.700

40 H 1.334607000000 13.476380000000 0.467189000000 R=1.350

41 C 0.747545000000 15.272601000000 1.503285000000 R=1.700

42 H 0.698161000000 14.872355000000 2.524603000000 R=1.350

43 H -0.009610000000 16.068211000000 1.425843000000 R=1.350

44 H 1.737509000000 15.733312000000 1.363316000000 R=1.350

45 C 0.545842000000 14.857027000000 -0.953171000000 R=1.700



36

46 H 0.515801000000 14.106649000000 -1.745319000000 R=1.350

47 H 1.473489000000 15.441379000000 -1.056377000000 R=1.350

48 H -0.303305000000 15.540316000000 -1.105651000000 R=1.350

49 C 4.204042000000 8.650792000000 -0.465628000000 R=1.700

50 H 3.313109000000 9.198028000000 -0.816296000000 R=1.350

51 C 5.256127000000 9.688116000000 -0.026114000000 R=1.700

52 H 4.854725000000 10.382304000000 0.722459000000 R=1.350

53 H 5.587062000000 10.277157000000 -0.895345000000 R=1.350

54 H 6.137918000000 9.184610000000 0.400661000000 R=1.350

55 C 4.752965000000 7.822831000000 -1.638198000000 R=1.700

56 H 4.083840000000 6.987391000000 -1.882335000000 R=1.350

57 H 5.747823000000 7.412688000000 -1.406379000000 R=1.350

58 H 4.858035000000 8.454978000000 -2.531311000000 R=1.350

59 C 1.002293000000 7.729950000000 3.439419000000 R=1.700

60 H 0.557549000000 8.642025000000 3.020745000000 R=1.350

61 C 1.565873000000 8.095307000000 4.826723000000 R=1.700

62 H 2.342213000000 8.869619000000 4.745220000000 R=1.350

63 H 2.005998000000 7.214118000000 5.319187000000 R=1.350

64 H 0.760886000000 8.481619000000 5.470019000000 R=1.350

65 C -0.123420000000 6.693265000000 3.558924000000 R=1.700

66 H -0.886173000000 7.048589000000 4.268025000000 R=1.350

67 H 0.245408000000 5.722433000000 3.923399000000 R=1.350

68 H -0.605287000000 6.539947000000 2.584089000000 R=1.350

69 Ge -0.014354000000 8.672691000000 -0.334450000000 R=2.033

70 C -1.518590000000 8.593675000000 -1.815534000000 R=1.700

71 C -1.667585000000 7.260980000000 -2.299636000000 R=1.700

72 C -2.638949000000 6.938830000000 -3.262376000000 R=1.700

73 H -2.705996000000 5.905307000000 -3.605263000000 R=1.350

74 C -3.406877000000 7.927053000000 -3.863809000000 R=1.700

75 H -4.120978000000 7.683942000000 -4.650451000000 R=1.350

76 C -3.176863000000 9.242700000000 -3.489346000000 R=1.700

77 H -3.683814000000 10.044777000000 -4.021582000000 R=1.350

78 C -2.288597000000 9.603898000000 -2.454157000000 R=1.700



37

79 C -2.188906000000 11.091501000000 -2.296258000000 R=1.700

80 C -3.363474000000 11.851792000000 -2.031908000000 R=1.700

81 C -3.304058000000 13.248686000000 -2.150721000000 R=1.700

82 H -4.190030000000 13.841975000000 -1.916079000000 R=1.350

83 C -2.162350000000 13.887837000000 -2.623577000000 R=1.700

84 H -2.151084000000 14.970521000000 -2.756885000000 R=1.350

85 C -1.040054000000 13.129549000000 -2.948169000000 R=1.700

86 H -0.171015000000 13.622021000000 -3.385557000000 R=1.350

87 C -1.010142000000 11.744606000000 -2.749611000000 R=1.700

88 C 0.232016000000 10.977553000000 -3.196629000000 R=1.700

89 H 0.156346000000 9.951932000000 -2.819183000000 R=1.350

90 C 0.280920000000 10.885866000000 -4.732467000000 R=1.700

91 H -0.623276000000 10.391736000000 -5.119206000000 R=1.350

92 H 0.345318000000 11.888218000000 -5.184653000000 R=1.350

93 H 1.156774000000 10.304777000000 -5.059909000000 R=1.350

94 C 1.533898000000 11.552098000000 -2.619557000000 R=1.700

95 H 2.375433000000 10.887903000000 -2.868772000000 R=1.350

96 H 1.763110000000 12.548792000000 -3.027394000000 R=1.350

97 H 1.475834000000 11.631061000000 -1.523743000000 R=1.350

98 C -4.738881000000 11.220868000000 -1.776650000000 R=1.700

99 H -4.608877000000 10.132360000000 -1.712035000000 R=1.350

100 C -5.698731000000 11.519421000000 -2.950215000000 R=1.700

101 H -5.274195000000 11.244255000000 -3.925051000000 R=1.350

102 H -6.643457000000 10.969330000000 -2.820806000000 R=1.350

103 H -5.936059000000 12.593856000000 -2.987214000000 R=1.350

104 C -5.410279000000 11.669704000000 -0.472786000000 R=1.700

105 H -6.414736000000 11.225108000000 -0.396812000000 R=1.350

106 H -4.821313000000 11.355375000000 0.390863000000 R=1.350

107 H -5.518331000000 12.763837000000 -0.425227000000 R=1.350

108 C -0.720766000000 6.103175000000 -2.112931000000 R=1.700

109 C -1.064375000000 5.001234000000 -1.281705000000 R=1.700

110 C -0.381086000000 3.784005000000 -1.458433000000 R=1.700

111 H -0.649516000000 2.923989000000 -0.844927000000 R=1.350



38

112 C 0.639048000000 3.664686000000 -2.401500000000 R=1.700

113 H 1.157725000000 2.713059000000 -2.523644000000 R=1.350

114 C 1.003032000000 4.759734000000 -3.185519000000 R=1.700

115 H 1.806020000000 4.656064000000 -3.917211000000 R=1.350

116 C 0.329289000000 5.984894000000 -3.071480000000 R=1.700

117 C 0.644935000000 7.122567000000 -4.038919000000 R=1.700

118 H -0.020735000000 7.959996000000 -3.796061000000 R=1.350

119 C 0.332219000000 6.712756000000 -5.489318000000 R=1.700

120 H -0.712728000000 6.383554000000 -5.588447000000 R=1.350

121 H 0.488461000000 7.569456000000 -6.162525000000 R=1.350

122 H 0.984808000000 5.891938000000 -5.825216000000 R=1.350

123 C 2.084223000000 7.631530000000 -3.895730000000 R=1.700

124 H 2.273971000000 8.443161000000 -4.613952000000 R=1.350

125 H 2.246418000000 8.020809000000 -2.882147000000 R=1.350

126 H 2.818999000000 6.834754000000 -4.086197000000 R=1.350

127 C -2.216873000000 5.115020000000 -0.287477000000 R=1.700

128 H -2.351663000000 6.188856000000 -0.081891000000 R=1.350

129 C -3.530886000000 4.572104000000 -0.883953000000 R=1.700

130 H -3.828269000000 5.128572000000 -1.782030000000 R=1.350

131 H -3.421376000000 3.509628000000 -1.152536000000 R=1.350

132 H -4.342911000000 4.655510000000 -0.145511000000 R=1.350

133 C -1.920867000000 4.407234000000 1.044294000000 R=1.700

134 H -0.943496000000 4.706935000000 1.446750000000 R=1.350

135 H -2.693806000000 4.659128000000 1.784742000000 R=1.350

136 Ge 1.042175000000 6.532138000000 -0.109706000000 R=2.033

END

GUIBONDS

1 133 1 1.0

2 133 135 1.0

3 2 10 1.5

4 2 3 1.0

5 3 4 1.5

6 3 20 1.0

7 4 5 1.0

8 4 6 1.5

9 6 7 1.0

10 6 8 1.5

11 8 9 1.0

12 8 10 1.5

13 10 11 1.0

14 11 12 1.5

15 11 19 1.5



39

16 12 13 1.5

17 12 49 1.0

18 13 14 1.0

19 13 15 1.5

20 15 16 1.0

21 15 17 1.5

22 17 18 1.0

23 17 19 1.5

24 19 59 1.0

25 20 21 1.5

26 20 28 1.5

27 21 22 1.5

28 21 39 1.0

29 22 23 1.0

30 22 24 1.5

31 24 25 1.0

32 24 26 1.5

33 26 27 1.0

34 26 28 1.5

35 28 29 1.0

36 29 30 1.0

37 29 35 1.0

38 29 31 1.0

39 31 33 1.0

40 31 32 1.0

41 31 34 1.0

42 35 38 1.0

43 35 36 1.0

44 35 37 1.0

45 39 40 1.0

46 39 45 1.0

47 39 41 1.0

48 41 43 1.0

49 41 44 1.0

50 41 42 1.0

51 45 46 1.0

52 45 48 1.0

53 45 47 1.0

54 49 50 1.0

55 49 51 1.0

56 49 55 1.0

57 51 54 1.0

58 51 52 1.0

59 51 53 1.0

60 55 57 1.0

61 55 56 1.0

62 55 58 1.0

63 59 60 1.0

64 59 61 1.0

65 59 65 1.0

66 61 64 1.0

67 61 63 1.0

68 61 62 1.0

69 65 67 1.0

70 65 66 1.0

71 65 68 1.0

72 69 70 1.5

73 70 78 1.5

74 70 71 1.0

75 71 72 1.5

76 71 108 1.0

77 72 73 1.0

78 72 74 1.5

79 74 75 1.0

80 74 76 1.5

81 76 77 1.0

82 76 78 1.5

83 78 79 1.0

84 79 80 1.5

85 79 87 1.5

86 80 81 1.5

87 80 98 1.0

88 81 82 1.0

89 81 83 1.5

90 83 84 1.0

91 83 85 1.5

92 85 86 1.0

93 85 87 1.5

94 87 88 1.0

95 88 89 1.0

96 88 90 1.0

97 88 94 1.0

98 90 93 1.0

99 90 92 1.0

100 90 91 1.0

101 94 96 1.0

102 94 95 1.0

103 94 97 1.0

104 98 99 1.0

105 98 100 1.0

106 98 104 1.0

107 100 103 1.0

108 100 101 1.0

109 100 102 1.0

110 104 106 1.0

111 104 105 1.0

112 104 107 1.0

113 108 109 1.5

114 108 116 1.5



40

115 109 110 1.5

116 109 127 1.0

117 110 111 1.0

118 110 112 1.5

119 112 113 1.0

120 112 114 1.5

121 114 115 1.0

122 114 116 1.5

123 116 117 1.0

124 117 118 1.0

125 117 123 1.0

126 117 119 1.0

127 119 121 1.0

128 119 120 1.0

129 119 122 1.0

130 123 126 1.0

131 123 124 1.0

132 123 125 1.0

133 127 128 1.0

134 127 133 1.0

135 127 129 1.0

136 129 131 1.0

137 129 132 1.0

138 129 130 1.0

139 133 134 1.0

140 136 69 2.0

141 2 69 1.0

END

SOLVATION

Surf Esurf


Charged method=CONJ

C-Mat POT

SCF VAR ALL

CSMRSP

END

BASIS

type TZP

core Large

createoutput None

END

XC


DISPERSION Grimme3

END



41

GEOMETRY

optim Delocalized

END

SAVE TAPE21 TAPE13

FULLSCF

BeckeGrid

Quality Good

End

NOPRINT LOGFILE

eor

--------------------------------------

#! /bin/sh

# ==============================

# {2,6-(2,6-iPr2C6H3)2C6H3}GeGe{2,6-(2,6-iPr2C6H3)2C6H3}

# ==============================

"$ADFBIN/adf" <<eor

ATOMS

1 Ge 0.048438000000 11.279910000000 0.506549000000 R=2.033

2 C 1.273555000000 11.896889000000 1.957073000000 R=1.700

3 C 1.110123000000 13.224760000000 2.409550000000 R=1.700

4 C 1.931761000000 13.729405000000 3.415481000000 R=1.700

5 H 1.815024000000 14.624431000000 3.709328000000 R=1.350

6 C 2.913953000000 12.945155000000 3.992505000000 R=1.700

7 H 3.474931000000 13.301278000000 4.671301000000 R=1.350

8 C 3.069709000000 11.630002000000 3.567740000000 R=1.700

9 H 3.732393000000 11.083714000000 3.972119000000 R=1.350



42

10 C 2.267581000000 11.100741000000 2.557191000000 R=1.700

11 C 2.495778000000 9.691634000000 2.117136000000 R=1.700

12 C 3.535699000000 9.436645000000 1.207244000000 R=1.700

13 C 3.706807000000 8.120877000000 0.778816000000 R=1.700

14 H 4.380044000000 7.924558000000 0.136970000000 R=1.350

15 C 2.921629000000 7.100716000000 1.264580000000 R=1.700

16 H 3.062353000000 6.211639000000 0.958787000000 R=1.350

17 C 1.925365000000 7.355705000000 2.194699000000 R=1.700

18 H 1.405644000000 6.638330000000 2.538716000000 R=1.350

19 C 1.681176000000 8.653421000000 2.624720000000 R=1.700

20 C 0.026386000000 14.113017000000 1.875210000000 R=1.700

21 C 0.334220000000 15.096663000000 0.918971000000 R=1.700

22 C -0.714816000000 15.955174000000 0.519210000000 R=1.700

23 H -0.553302000000 16.620443000000 -0.138562000000 R=1.350

24 C -1.974938000000 15.836808000000 1.079830000000 R=1.700

25 H -2.665766000000 16.429663000000 0.810669000000 R=1.350

26 C -2.233999000000 14.880650000000 2.009950000000 R=1.700

27 H -3.108728000000 14.815211000000 2.376264000000 R=1.350

28 C -1.261721000000 14.004703000000 2.433600000000 R=1.700

29 C -1.567157000000 13.033980000000 3.562803000000 R=1.700

30 H -0.833152000000 12.355582000000 3.593064000000 R=1.350

31 C -1.579950000000 13.771048000000 4.905424000000 R=1.700

32 H -0.705221000000 14.187482000000 5.056727000000 R=1.350

33 H -1.770248000000 13.135114000000 5.625310000000 R=1.350

34 H -2.272378000000 14.466473000000 4.889497000000 R=1.350

35 C -2.883249000000 12.291989000000 3.370090000000 R=1.700

36 H -2.963206000000 11.588359000000 4.046974000000 R=1.350

37 H -2.902439000000 11.889914000000 2.476602000000 R=1.350

38 H -3.628449000000 12.919717000000 3.460872000000 R=1.350

39 C 1.738265000000 15.262416000000 0.369499000000 R=1.700

40 H 2.265981000000 14.456216000000 0.635475000000 R=1.350

41 C 2.421098000000 16.497359000000 0.993826000000 R=1.700

42 H 2.462676000000 16.390686000000 1.966947000000 R=1.350



43

43 H 1.906175000000 17.301508000000 0.775630000000 R=1.350

44 H 3.329409000000 16.583518000000 0.637068000000 R=1.350

45 C 1.773446000000 15.356780000000 -1.157871000000 R=1.700

46 H 1.280911000000 14.603917000000 -1.543297000000 R=1.350

47 H 2.704146000000 15.330112000000 -1.465256000000 R=1.350

48 H 1.359269000000 16.197854000000 -1.441366000000 R=1.350

49 C 4.440812000000 10.538452000000 0.681663000000 R=1.700

50 H 4.308083000000 11.333985000000 1.270951000000 R=1.350

51 C 5.923215000000 10.166738000000 0.753333000000 R=1.700

52 H 6.169482000000 9.982112000000 1.683452000000 R=1.350

53 H 6.463724000000 10.911397000000 0.414094000000 R=1.350

54 H 6.087926000000 9.370795000000 0.207047000000 R=1.350

55 C 4.065014000000 10.964733000000 -0.740592000000 R=1.700

56 H 3.131116000000 11.260135000000 -0.756518000000 R=1.350

57 H 4.178553000000 10.205715000000 -1.348991000000 R=1.350

58 H 4.645502000000 11.701186000000 -1.024087000000 R=1.350

59 C 0.617268000000 8.942873000000 3.679068000000 R=1.700

60 H 0.326225000000 9.891851000000 3.556432000000 R=1.350

61 C 1.205752000000 8.829226000000 5.067876000000 R=1.700

62 H 1.958947000000 9.450800000000 5.155473000000 R=1.350

63 H 1.519183000000 7.912250000000 5.215994000000 R=1.350

64 H 0.521320000000 9.052828000000 5.732019000000 R=1.350

65 C -0.631660000000 8.062002000000 3.554839000000 R=1.700

66 H -1.320890000000 8.384072000000 4.172795000000 R=1.350

67 H -0.401384000000 7.136821000000 3.774628000000 R=1.350

68 H -0.970678000000 8.105081000000 2.635869000000 R=1.350

69 Ge -0.048438000000 9.234090000000 -0.506549000000 R=2.033

70 C -1.273555000000 8.617111000000 -1.957073000000 R=1.700

71 C -1.110123000000 7.289240000000 -2.409550000000 R=1.700

72 C -1.931761000000 6.784595000000 -3.415481000000 R=1.700

73 H -1.815024000000 5.889569000000 -3.709328000000 R=1.350

74 C -2.913953000000 7.568845000000 -3.992505000000 R=1.700

75 H -3.474931000000 7.212722000000 -4.671301000000 R=1.350



44

76 C -3.069709000000 8.883998000000 -3.567740000000 R=1.700

77 H -3.732393000000 9.430286000000 -3.972119000000 R=1.350

78 C -2.267581000000 9.413259000000 -2.557191000000 R=1.700

79 C -2.495778000000 10.822366000000 -2.117136000000 R=1.700

80 C -3.535699000000 11.077355000000 -1.207244000000 R=1.700

81 C -3.706807000000 12.393123000000 -0.778816000000 R=1.700

82 H -4.380044000000 12.589442000000 -0.136970000000 R=1.350

83 C -2.921629000000 13.413284000000 -1.264580000000 R=1.700

84 H -3.062353000000 14.302361000000 -0.958787000000 R=1.350

85 C -1.925365000000 13.158295000000 -2.194699000000 R=1.700

86 H -1.405644000000 13.875670000000 -2.538716000000 R=1.350

87 C -1.681176000000 11.860579000000 -2.624720000000 R=1.700

88 C -0.617268000000 11.571127000000 -3.679068000000 R=1.700

89 H -0.326225000000 10.622149000000 -3.556432000000 R=1.350

90 C -1.205752000000 11.684774000000 -5.067876000000 R=1.700

91 H -1.958946000000 11.063200000000 -5.155473000000 R=1.350

92 H -1.519183000000 12.601750000000 -5.215994000000 R=1.350

93 H -0.521320000000 11.461172000000 -5.732019000000 R=1.350

94 C 0.631660000000 12.451998000000 -3.554839000000 R=1.700

95 H 1.320890000000 12.129928000000 -4.172795000000 R=1.350

96 H 0.401384000000 13.377179000000 -3.774628000000 R=1.350

97 H 0.970678000000 12.408919000000 -2.635869000000 R=1.350

98 C -4.440812000000 9.975548000000 -0.681663000000 R=1.700

99 H -4.308083000000 9.180015000000 -1.270951000000 R=1.350

100 C -5.923215000000 10.347262000000 -0.753333000000 R=1.700

101 H -6.169482000000 10.531888000000 -1.683452000000 R=1.350

102 H -6.463724000000 9.602603000000 -0.414094000000 R=1.350

103 H -6.087926000000 11.143205000000 -0.207047000000 R=1.350

104 C -4.065014000000 9.549267000000 0.740592000000 R=1.700

105 H -3.131116000000 9.253865000000 0.756518000000 R=1.350

106 H -4.178553000000 10.308285000000 1.348991000000 R=1.350

107 H -4.645502000000 8.812814000000 1.024087000000 R=1.350

108 C -0.026386000000 6.400983000000 -1.875210000000 R=1.700



45

109 C -0.334220000000 5.417337000000 -0.918971000000 R=1.700

110 C 0.714816000000 4.558826000000 -0.519210000000 R=1.700

111 H 0.553302000000 3.893557000000 0.138562000000 R=1.350

112 C 1.974938000000 4.677192000000 -1.079830000000 R=1.700

113 H 2.665766000000 4.084337000000 -0.810669000000 R=1.350

114 C 2.233999000000 5.633350000000 -2.009950000000 R=1.700

115 H 3.108728000000 5.698789000000 -2.376264000000 R=1.350

116 C 1.261721000000 6.509297000000 -2.433600000000 R=1.700

117 C 1.567157000000 7.480020000000 -3.562803000000 R=1.700

118 H 0.833152000000 8.158418000000 -3.593064000000 R=1.350

119 C 1.579950000000 6.742952000000 -4.905424000000 R=1.700

120 H 0.705221000000 6.326518000000 -5.056727000000 R=1.350

121 H 1.770248000000 7.378886000000 -5.625310000000 R=1.350

122 H 2.272378000000 6.047527000000 -4.889497000000 R=1.350

123 C 2.883249000000 8.222011000000 -3.370090000000 R=1.700

124 H 2.963206000000 8.925641000000 -4.046974000000 R=1.350

125 H 2.902439000000 8.624086000000 -2.476602000000 R=1.350

126 H 3.628449000000 7.594283000000 -3.460872000000 R=1.350

127 C -1.738265000000 5.251584000000 -0.369499000000 R=1.700

128 H -2.265981000000 6.057784000000 -0.635475000000 R=1.350

129 C -2.421098000000 4.016641000000 -0.993826000000 R=1.700

130 H -2.462676000000 4.123314000000 -1.966947000000 R=1.350

131 H -1.906175000000 3.212492000000 -0.775630000000 R=1.350

132 H -3.329409000000 3.930482000000 -0.637068000000 R=1.350

133 C -1.773446000000 5.157220000000 1.157871000000 R=1.700

134 H -1.280911000000 5.910083000000 1.543297000000 R=1.350

135 H -2.704146000000 5.183888000000 1.465256000000 R=1.350

136 H -1.359269000000 4.316146000000 1.441366000000 R=1.350

END

GUIBONDS

1 1 2 1.5

2 1 69 2.0

3 2 10 1.5

4 2 3 1.0

5 3 4 1.5

6 3 20 1.0



46

7 4 5 1.0

8 4 6 1.5

9 6 7 1.0

10 6 8 1.5

11 8 9 1.0

12 8 10 1.5

13 10 11 1.0

14 11 12 1.5

15 11 19 1.5

16 12 13 1.5

17 12 49 1.0

18 13 14 1.0

19 13 15 1.5

20 15 16 1.0

21 15 17 1.5

22 17 18 1.0

23 17 19 1.5

24 19 59 1.0

25 20 21 1.5

26 20 28 1.5

27 21 22 1.5

28 21 39 1.0

29 22 23 1.0

30 22 24 1.5

31 24 25 1.0

32 24 26 1.5

33 26 27 1.0

34 26 28 1.5

35 28 29 1.0

36 29 30 1.0

37 29 35 1.0

38 29 31 1.0

39 31 33 1.0

40 31 32 1.0

41 31 34 1.0

42 35 38 1.0

43 35 36 1.0

44 35 37 1.0

45 39 40 1.0

46 39 45 1.0

47 39 41 1.0

48 41 43 1.0

49 41 44 1.0

50 41 42 1.0

51 45 46 1.0

52 45 48 1.0

53 45 47 1.0

54 49 50 1.0

55 49 51 1.0

56 49 55 1.0

57 51 54 1.0

58 51 52 1.0

59 51 53 1.0

60 55 57 1.0

61 55 56 1.0

62 55 58 1.0

63 59 60 1.0

64 59 61 1.0

65 59 65 1.0

66 61 64 1.0

67 61 63 1.0

68 61 62 1.0

69 65 67 1.0

70 65 66 1.0

71 65 68 1.0

72 69 70 1.5

73 70 78 1.5

74 70 71 1.0

75 71 72 1.5

76 71 108 1.0

77 72 73 1.0

78 72 74 1.5

79 74 75 1.0

80 74 76 1.5

81 76 77 1.0

82 76 78 1.5

83 78 79 1.0

84 79 80 1.5

85 79 87 1.5

86 80 81 1.5

87 80 98 1.0

88 81 82 1.0

89 81 83 1.5

90 83 84 1.0

91 83 85 1.5

92 85 86 1.0

93 85 87 1.5

94 87 88 1.0

95 88 89 1.0

96 88 90 1.0

97 88 94 1.0

98 90 93 1.0

99 90 92 1.0

100 90 91 1.0

101 94 96 1.0

102 94 95 1.0

103 94 97 1.0

104 98 99 1.0

105 98 100 1.0



47

106 98 104 1.0

107 100 103 1.0

108 100 101 1.0

109 100 102 1.0

110 104 106 1.0

111 104 105 1.0

112 104 107 1.0

113 108 109 1.5

114 108 116 1.5

115 109 110 1.5

116 109 127 1.0

117 110 111 1.0

118 110 112 1.5

119 112 113 1.0

120 112 114 1.5

121 114 115 1.0

122 114 116 1.5

123 116 117 1.0

124 117 118 1.0

125 117 123 1.0

126 117 119 1.0

127 119 121 1.0

128 119 120 1.0

129 119 122 1.0

130 123 126 1.0

131 123 124 1.0

132 123 125 1.0

133 127 128 1.0

134 127 133 1.0

135 127 129 1.0

136 129 131 1.0

137 129 132 1.0

138 129 130 1.0

139 133 134 1.0

140 133 136 1.0

141 133 135 1.0

END

SOLVATION

Surf Esurf


Charged method=CONJ

C-Mat POT

SCF VAR ALL

CSMRSP

END

BASIS

type TZP

core Large

createoutput None

END

XC


DISPERSION Grimme3

END



48

GEOMETRY

optim Delocalized

END

SAVE TAPE21 TAPE13

FULLSCF

BeckeGrid

Quality Good

End

NOPRINT LOGFILE

eor

------------------------------------

#! /bin/sh



49

Supplementary Figure 20. DFT calculated energies for potential products arising from the reaction of 5 with one equivalent of H2.

# ==============================

# {(HCDippN)2B}Ge(H)Ge(H){B(DippNCH)2} # ==============================

"$ADFBIN/adf" <<eor

ATOMS

1 Ge 5.358767071000 5.306168979000 8.466430924000 R=2.033

2 H 5.814970781000 1.462424293000 5.414180891000 R=1.350

3 H 6.301069082000 4.040541102000 8.477758840000 R=1.350

4 N 4.440358176000 4.636684920000 11.413555060000 R=1.608

5 N 3.469229230000 6.581109168000 10.705101310000 R=1.608

6 B 4.400146361000 5.552648323000 10.289837850000 R=1.792

7 C 3.592874661000 5.120851081000 12.416144890000 R=1.700

8 H 3.469088353000 4.601669295000 13.360271940000 R=1.350

9 C 3.013449839000 6.279457881000 11.992534420000 R=1.700

10 H 2.304249946000 6.915523326000 12.510840220000 R=1.350



50

11 C 5.205741823000 3.428952846000 11.597302070000 R=1.700

12 C 4.647672424000 2.191709400000 11.204780790000 R=1.700

13 C 5.412214418000 1.031133911000 11.397879330000 R=1.700

14 H 5.001488645000 0.064519301230 11.098794270000 R=1.350

15 C 6.684378964000 1.090170528000 11.964243850000 R=1.700

16 H 7.263381407000 0.176124564700 12.105819350000 R=1.350

17 C 7.214179252000 2.320218131000 12.350425760000 R=1.700

18 H 8.211104139000 2.360550278000 12.794211240000 R=1.350

19 C 6.491236875000 3.510247099000 12.178643970000 R=1.700

20 C 3.255392437000 2.086161744000 10.590398870000 R=1.700

21 H 2.851486400000 3.104906227000 10.516756380000 R=1.350

22 C 2.302405565000 1.271037037000 11.485277420000 R=1.700

23 H 2.646275214000 0.230502778500 11.590204100000 R=1.350

24 H 1.292252248000 1.247926063000 11.048669880000 R=1.350

25 H 2.230078784000 1.703494898000 12.493521040000 R=1.350

26 C 3.303506123000 1.500858379000 9.167231677000 R=1.700

27 H 3.955203960000 2.096946401000 8.513041278000 R=1.350

28 H 2.295316235000 1.482768101000 8.726066159000 R=1.350

29 H 3.685121432000 0.468246337400 9.172372354000 R=1.350

30 C 7.101824489000 4.836288871000 12.620962440000 R=1.700

31 H 6.383254291000 5.628297275000 12.370625490000 R=1.350

32 C 7.326786750000 4.875048156000 14.144610490000 R=1.700

33 H 6.391290986000 4.697549535000 14.694522230000 R=1.350

34 H 7.721878781000 5.856588447000 14.448089500000 R=1.350

35 H 8.052401902000 4.109580710000 14.460358040000 R=1.350

36 C 8.407905405000 5.141139885000 11.865621070000 R=1.700

37 H 9.182876069000 4.391321555000 12.087680660000 R=1.350

38 H 8.800099018000 6.125503081000 12.163327050000 R=1.350

39 H 8.245346005000 5.149168892000 10.778997960000 R=1.350

40 C 3.002945291000 7.747786861000 9.998930188000 R=1.700

41 C 1.876136572000 7.634595593000 9.153749994000 R=1.700

42 C 1.433024962000 8.787685634000 8.488502669000 R=1.700

43 H 0.566494619300 8.723339865000 7.827232562000 R=1.350



51

44 C 2.077063566000 10.011487590000 8.658019284000 R=1.700

45 H 1.717996953000 10.896173090000 8.130094928000 R=1.350

46 C 3.183478546000 10.102746310000 9.500894808000 R=1.700

47 H 3.683214557000 11.064887810000 9.627022306000 R=1.350

48 C 3.669782747000 8.980156092000 10.187012480000 R=1.700

49 C 1.129146351000 6.317968053000 8.962727906000 R=1.700

50 H 1.665495918000 5.550430282000 9.536962505000 R=1.350

51 C -0.304909652700 6.398565929000 9.520854937000 R=1.700

52 H -0.307441709700 6.676521365000 10.584706540000 R=1.350

53 H -0.810772169100 5.426152233000 9.419116495000 R=1.350

54 H -0.902372152500 7.146335740000 8.976738078000 R=1.350

55 C 1.119394461000 5.871991901000 7.489663038000 R=1.700

56 H 0.582262415200 6.593618842000 6.855375076000 R=1.350

57 H 0.614798805700 4.898772616000 7.388978440000 R=1.350

58 H 2.142525792000 5.772316147000 7.100088112000 R=1.350

59 C 4.864236035000 9.118256348000 11.126855830000 R=1.700

60 H 5.193328198000 8.102813981000 11.387255480000 R=1.350

61 C 4.460355684000 9.829298860000 12.434171490000 R=1.700

62 H 4.115950434000 10.855683040000 12.232245150000 R=1.350

63 H 5.318606892000 9.888379434000 13.121087550000 R=1.350

64 H 3.647528880000 9.296868108000 12.948410590000 R=1.350

65 C 6.054736425000 9.834863546000 10.467616600000 R=1.700

66 H 6.360541227000 9.325907390000 9.542870378000 R=1.350

67 H 6.914873797000 9.848172774000 11.153962510000 R=1.350

68 H 5.814705058000 10.879964720000 10.220074140000 R=1.350

69 Ge 6.235140027000 7.034048427000 7.151713328000 R=2.033

70 H 4.720096810000 2.475281928000 4.453132515000 R=1.350

71 H 5.292683693000 8.299515527000 7.140283637000 R=1.350

72 N 7.146987468000 7.697896644000 4.200429155000 R=1.608

73 N 8.132549542000 5.763955173000 4.917762174000 R=1.608

74 B 7.193875692000 6.787241885000 5.328242550000 R=1.792

75 C 7.998659255000 7.215828356000 3.200388330000 R=1.700

76 H 8.119155012000 7.732027745000 2.254193548000 R=1.350



52

77 C 8.585845298000 6.062903827000 3.628784286000 R=1.700

78 H 9.299083818000 5.429257205000 3.113075602000 R=1.350

79 C 6.375069001000 8.900737229000 4.011792890000 R=1.700

80 C 6.928303258000 10.142511680000 4.396706206000 R=1.700

81 C 6.158303218000 11.298672750000 4.199018257000 R=1.700

82 H 6.565270182000 12.268630780000 4.492361172000 R=1.350

83 C 4.885360081000 11.230985640000 3.635391777000 R=1.700

84 H 4.301898473000 12.141637430000 3.490151786000 R=1.350

85 C 4.360433828000 9.996626931000 3.256448270000 R=1.700

86 H 3.362974017000 9.949580190000 2.814555429000 R=1.350

87 C 5.088971222000 8.810694335000 3.432972853000 R=1.700

88 C 8.321191601000 10.257321290000 5.008086405000 R=1.700

89 H 8.729967042000 9.240787511000 5.085552644000 R=1.350

90 C 9.269054745000 11.072773830000 4.108108666000 R=1.700

91 H 8.920536049000 12.111369960000 3.999342346000 R=1.350

92 H 10.279829380000 11.102128300000 4.542899223000 R=1.350

93 H 9.341596303000 10.636353450000 3.101585773000 R=1.350

94 C 8.272772845000 10.848729240000 6.428730892000 R=1.700

95 H 7.624474055000 10.252935570000 7.086519765000 R=1.350

96 H 9.281535602000 10.873060950000 6.868264226000 R=1.350

97 H 7.886812795000 11.879714410000 6.419488776000 R=1.350

98 C 4.483586921000 7.480020105000 2.997577703000 R=1.700

99 H 5.205168734000 6.692107851000 3.252080627000 R=1.350

100 C 4.259021811000 7.432789049000 1.474089137000 R=1.700

101 H 5.193899572000 7.611284636000 0.923445562600 R=1.350

102 H 3.867883132000 6.448196020000 1.175403164000 R=1.350

103 H 3.530437687000 8.193821392000 1.154463992000 R=1.350

104 C 3.178547520000 7.174010590000 3.754208244000 R=1.700

105 H 2.400670416000 7.919593826000 3.528094009000 R=1.350

106 H 2.790267686000 6.186571615000 3.461602308000 R=1.350

107 H 3.341010863000 7.172186616000 4.840860786000 R=1.350

108 C 8.606150346000 4.602898093000 5.628292761000 R=1.700

109 C 9.724656582000 4.728584197000 6.482753785000 R=1.700



53

110 C 10.174691810000 3.580548005000 7.152040925000 R=1.700

111 H 11.034963110000 3.654577675000 7.820410411000 R=1.350

112 C 9.545872056000 2.349515929000 6.977424861000 R=1.700

113 H 9.910134171000 1.469027833000 7.508778754000 R=1.350

114 C 8.447775620000 2.245974048000 6.125202636000 R=1.700

115 H 7.959633852000 1.278387147000 5.994903075000 R=1.350

116 C 7.954951824000 3.363099496000 5.434814119000 R=1.700

117 C 10.456864940000 6.052859496000 6.677991077000 R=1.700

118 H 9.912409867000 6.815970921000 6.105479866000 R=1.350

119 C 11.891843950000 5.988823481000 6.119893329000 R=1.700

120 H 11.897376090000 5.714280200000 5.055170658000 R=1.350

121 H 12.387716610000 6.966034825000 6.224802357000 R=1.350

122 H 12.496585380000 5.245354864000 6.661877800000 R=1.350

123 C 10.461848710000 6.495566354000 8.151998262000 R=1.700

124 H 11.007427750000 5.778997903000 8.784791912000 R=1.350

125 H 10.955362950000 7.474218151000 8.254552625000 R=1.350

126 H 9.437723142000 6.582842999000 8.541952864000 R=1.350

127 C 6.769008452000 3.210916598000 4.486416393000 R=1.700

128 H 6.441061645000 4.222130212000 4.208896099000 R=1.350

129 C 7.184216697000 2.481732127000 3.192815611000 R=1.700

130 H 7.526432299000 1.458108789000 3.411558640000 R=1.350

131 H 6.332100896000 2.413341904000 2.499143778000 R=1.350

132 H 8.001880707000 3.006702084000 2.678495448000 R=1.350

133 C 5.574062385000 2.502434575000 5.146785419000 R=1.700

134 H 5.258919234000 3.025762904000 6.060288938000 R=1.350

END

GUIBONDS

1 133 2 1.0

2 1 3 1.0

3 1 6 3

4 1 69 3.0

5 4 7 1.0

6 4 6 1.0

7 4 11 1.0

8 5 9 1.0

9 5 6 1.0

10 5 40 1.0

11 7 8 1.0

12 7 9 2.0

13 9 10 1.0

14 11 19 1.5

15 11 12 1.5



54

16 12 13 1.5

17 12 20 1.0

18 13 14 1.0

19 13 15 1.5

20 15 16 1.0

21 15 17 1.5

22 17 18 1.0

23 17 19 1.5

24 19 30 1.0

25 20 21 1.0

26 20 22 1.0

27 20 26 1.0

28 22 23 1.0

29 22 24 1.0

30 22 25 1.0

31 26 29 1.0

32 26 28 1.0

33 26 27 1.0

34 30 31 1.0

35 30 36 1.0

36 30 32 1.0

37 32 33 1.0

38 32 35 1.0

39 32 34 1.0

40 36 37 1.0

41 36 39 1.0

42 36 38 1.0

43 40 41 1.5

44 40 48 1.5

45 41 42 1.5

46 41 49 1.0

47 42 43 1.0

48 42 44 1.5

49 44 45 1.0

50 44 46 1.5

51 46 47 1.0

52 46 48 1.5

53 48 59 1.0

54 49 50 1.0

55 49 51 1.0

56 49 55 1.0

57 51 54 1.0

58 51 53 1.0

59 51 52 1.0

60 55 58 1.0

61 55 56 1.0

62 55 57 1.0

63 59 60 1.0

64 59 61 1.0

65 59 65 1.0

66 61 62 1.0

67 61 63 1.0

68 61 64 1.0

69 65 66 1.0

70 65 67 1.0

71 65 68 1.0

72 133 70 1.0

73 69 71 1.0

74 69 74 3

75 72 75 1.0

76 72 74 1.0

77 72 79 1.0

78 73 77 1.0

79 73 74 1.0

80 73 108 1.0

81 75 76 1.0

82 75 77 2.0

83 77 78 1.0

84 79 87 1.5

85 79 80 1.5

86 80 81 1.5

87 80 88 1.0

88 81 82 1.0

89 81 83 1.5

90 83 84 1.0

91 83 85 1.5

92 85 86 1.0

93 85 87 1.5

94 87 98 1.0

95 88 89 1.0

96 88 90 1.0

97 88 94 1.0

98 90 91 1.0

99 90 92 1.0

100 90 93 1.0

101 94 97 1.0

102 94 96 1.0

103 94 95 1.0

104 98 99 1.0

105 98 104 1.0

106 98 100 1.0

107 100 101 1.0

108 100 103 1.0

109 100 102 1.0

110 104 105 1.0

111 104 107 1.0

112 104 106 1.0

113 108 109 1.5

114 108 116 1.5



55

115 109 110 1.5

116 109 117 1.0

117 110 111 1.0

118 110 112 1.5

119 112 113 1.0

120 112 114 1.5

121 114 115 1.0

122 114 116 1.5

123 116 127 1.0

124 117 118 1.0

125 117 119 1.0

126 117 123 1.0

127 119 122 1.0

128 119 121 1.0

129 119 120 1.0

130 123 126 1.0

131 123 124 1.0

132 123 125 1.0

133 127 128 1.0

134 127 129 1.0

135 127 133 1.0

136 129 130 1.0

137 129 131 1.0

138 129 132 1.0

139 133 134 1.0

END

SOLVATION

Surf Esurf


Charged method=CONJ

C-Mat POT

SCF VAR ALL

CSMRSP

END

BASIS

type TZP

core Large

createoutput None

END

XC


DISPERSION Grimme3

END

GEOMETRY



56

optim Delocalized

END

SAVE TAPE21 TAPE13

SCF

iterations 150

END

FULLSCF

BeckeGrid

Quality Good

End

NOPRINT LOGFILE

eor

----------------------------------------------------

#! /bin/sh

# ==============================

# {(HCDippN)2B}2GeGeH2 # ==============================

"$ADFBIN/adf" <<eor

ATOMS

1 Ge 1.193856905000 7.092908025000 11.722543410000 R=2.033

2 Ge 0.593851930300 8.467810398000 13.520236660000 R=2.033

3 N 3.847098415000 6.228502430000 13.162199800000 R=1.608

4 N 3.845209383000 5.417633975000 11.022837060000 R=1.608

5 N -1.661075457000 5.647293418000 11.762438590000 R=1.608



57

6 N -1.272386465000 6.684798726000 9.767712124000 R=1.608

7 B 3.022118572000 6.136874311000 11.974365360000 R=1.792

8 B -0.635966475600 6.352400971000 11.020227570000 R=1.792

9 C 5.065530281000 5.581387948000 12.913630100000 R=1.700

10 H 5.842069595000 5.527482652000 13.668192580000 R=1.350

11 C 5.065412204000 5.100143275000 11.644457280000 R=1.700

12 H 5.841292610000 4.557923451000 11.116224590000 R=1.350

13 C 3.726394353000 7.105747060000 14.295606290000 R=1.700

14 C 4.345705871000 8.371554844000 14.223653410000 R=1.700

15 C 4.254393380000 9.216687792000 15.340645810000 R=1.700

16 H 4.720972071000 10.202905720000 15.306324280000 R=1.350

17 C 3.558882797000 8.822888834000 16.480669090000 R=1.700

18 H 3.490336534000 9.493630348000 17.338186150000 R=1.350

19 C 2.932746812000 7.575424334000 16.520356790000 R=1.700

20 H 2.372794535000 7.291075117000 17.410211270000 R=1.350

21 C 2.999865233000 6.691903620000 15.433551840000 R=1.700

22 C 5.068273305000 8.851416680000 12.970213470000 R=1.700

23 H 5.072225873000 8.029210930000 12.244071240000 R=1.350

24 C 4.326170448000 10.034939530000 12.324385040000 R=1.700

25 H 3.295438087000 9.756249342000 12.061689730000 R=1.350

26 H 4.841697036000 10.354749190000 11.406801150000 R=1.350

27 H 4.283013019000 10.896964350000 13.007415970000 R=1.350

28 C 6.537829207000 9.202839691000 13.255974770000 R=1.700

29 H 6.622053124000 10.049366550000 13.954360110000 R=1.350

30 H 7.048676744000 9.484278304000 12.322714780000 R=1.350

31 H 7.070623003000 8.346171807000 13.694233140000 R=1.350

32 C 2.309748473000 5.334246846000 15.466797390000 R=1.700

33 H 1.852409991000 5.188063223000 14.474299420000 R=1.350

34 C 3.323656858000 4.196053915000 15.694821380000 R=1.700

35 H 4.083432594000 4.164951663000 14.903167430000 R=1.350

36 H 2.806441442000 3.224503272000 15.709074510000 R=1.350

37 H 3.833827971000 4.324916474000 16.662611070000 R=1.350

38 C 1.185905448000 5.253105859000 16.503293880000 R=1.700



58

39 H 1.571539190000 5.336161284000 17.531161310000 R=1.350

40 H 0.676556118600 4.285305972000 16.416924810000 R=1.350

41 H 0.433272056700 6.038300671000 16.340696130000 R=1.350

42 C 3.771540327000 5.286950321000 9.591391297000 R=1.700

43 C 4.010495710000 6.423650707000 8.784486774000 R=1.700

44 C 4.118372193000 6.233207415000 7.398651794000 R=1.700

45 H 4.302965987000 7.095672802000 6.756462872000 R=1.350

46 C 4.031457537000 4.962019555000 6.832553516000 R=1.700

47 H 4.142351586000 4.834999850000 5.755166611000 R=1.350

48 C 3.775955942000 3.858405650000 7.644712143000 R=1.700

49 H 3.672813732000 2.869820418000 7.194063883000 R=1.350

50 C 3.610802036000 4.004133831000 9.029873273000 R=1.700

51 C 4.253272773000 7.804408826000 9.378172581000 R=1.700

52 H 3.882918445000 7.795911306000 10.410965000000 R=1.350

53 C 3.487136278000 8.913974632000 8.647277228000 R=1.700

54 H 3.845150661000 9.052717479000 7.615617995000 R=1.350

55 H 3.620194338000 9.868941961000 9.176925922000 R=1.350

56 H 2.411829625000 8.689428522000 8.605076800000 R=1.350

57 C 5.764450982000 8.095848389000 9.437267058000 R=1.700

58 H 6.287847077000 7.330732270000 10.029295810000 R=1.350

59 H 5.951075359000 9.074289433000 9.904348386000 R=1.350

60 H 6.198000998000 8.108225720000 8.424844427000 R=1.350

61 C 3.257227252000 2.800450522000 9.889742803000 R=1.700

62 H 3.051245321000 3.176912744000 10.901548310000 R=1.350

63 C 4.419259906000 1.797279438000 9.985593131000 R=1.700

64 H 4.672029463000 1.394582250000 8.992298164000 R=1.350

65 H 4.145565741000 0.952682764800 10.635861580000 R=1.350

66 H 5.321525018000 2.269923307000 10.398328970000 R=1.350

67 C 1.981801121000 2.116130502000 9.370402146000 R=1.700

68 H 1.139847190000 2.821406110000 9.348201861000 R=1.350

69 H 1.710032179000 1.267530731000 10.014723130000 R=1.350

70 H 2.120875051000 1.726163630000 8.351630336000 R=1.350

71 C -2.810917490000 5.563505555000 10.960058600000 R=1.700



59

72 H -3.699549043000 5.046707027000 11.300551530000 R=1.350

73 C -2.582311894000 6.187093506000 9.776902286000 R=1.700

74 H -3.246435110000 6.308911194000 8.930287161000 R=1.350

75 C -1.699996212000 5.131189510000 13.103896240000 R=1.700

76 C -1.017183633000 3.931417125000 13.403583670000 R=1.700

77 C -1.190415388000 3.376692550000 14.678851650000 R=1.700

78 H -0.684233503700 2.445556703000 14.932348220000 R=1.350

79 C -2.004739823000 3.989235693000 15.631325350000 R=1.700

80 H -2.130674033000 3.535508095000 16.615126220000 R=1.350

81 C -2.629542563000 5.196902259000 15.333198930000 R=1.700

82 H -3.238320929000 5.689283040000 16.093028210000 R=1.350

83 C -2.481882921000 5.798625012000 14.073449960000 R=1.700

84 C -0.184686857200 3.210887006000 12.350159550000 R=1.700

85 H 0.270347796500 3.975227573000 11.702076190000 R=1.350

86 C 0.959863354500 2.384291229000 12.949908000000 R=1.700

87 H 1.600024780000 3.000685020000 13.595803880000 R=1.350

88 H 1.584023562000 1.970454301000 12.148203190000 R=1.350

89 H 0.587708231600 1.534272782000 13.540761440000 R=1.350

90 C -1.103750999000 2.338020777000 11.472217880000 R=1.700

91 H -0.525606269100 1.814595707000 10.698326560000 R=1.350

92 H -1.867648641000 2.952063900000 10.974400880000 R=1.350

93 H -1.615157825000 1.584187474000 12.091703840000 R=1.350

94 C -3.154394457000 7.139000745000 13.795741890000 R=1.700

95 H -2.682114429000 7.563438281000 12.897343090000 R=1.350

96 C -2.953655770000 8.131813229000 14.955088040000 R=1.700

97 H -3.555928389000 7.850194226000 15.831801180000 R=1.350

98 H -3.266163467000 9.139752712000 14.646173120000 R=1.350

99 H -1.901118901000 8.177823385000 15.265705220000 R=1.350

100 C -4.662349101000 6.977924896000 13.516901540000 R=1.700

101 H -4.852714203000 6.349393865000 12.638120650000 R=1.350

102 H -5.126626829000 7.960035927000 13.338674000000 R=1.350

103 H -5.162467202000 6.516393655000 14.382958830000 R=1.350

104 C -0.738060096900 7.378817131000 8.629087283000 R=1.700



60

105 C -0.429776014300 6.644100541000 7.464287236000 R=1.700

106 C 0.102730064400 7.340058352000 6.368369463000 R=1.700

107 H 0.358899344000 6.792631895000 5.459927803000 R=1.350

108 C 0.314559094700 8.716457723000 6.424135775000 R=1.700

109 H 0.740521436300 9.238976638000 5.566504911000 R=1.350

110 C -0.020742499710 9.427259771000 7.577062919000 R=1.700

111 H 0.140870504800 10.505048560000 7.607958887000 R=1.350

112 C -0.557722252400 8.778872812000 8.698356894000 R=1.700

113 C -0.710438087400 5.149544369000 7.364426598000 R=1.700

114 H -0.887597069300 4.776865489000 8.383464812000 R=1.350

115 C -1.982515136000 4.889663649000 6.533465161000 R=1.700

116 H -2.853542912000 5.424522795000 6.935687732000 R=1.350

117 H -2.217035370000 3.814459412000 6.515664356000 R=1.350

118 H -1.834506260000 5.224831441000 5.494568618000 R=1.350

119 C 0.473211102200 4.365569393000 6.785927650000 R=1.700

120 H 0.656524803700 4.623196851000 5.731612525000 R=1.350

121 H 0.272666244500 3.284723866000 6.833089084000 R=1.350

122 H 1.391328847000 4.570388630000 7.347918183000 R=1.350

123 C -1.011087652000 9.575465038000 9.914489652000 R=1.700

124 H -0.990789553300 8.901446971000 10.778634400000 R=1.350

125 C -0.093293394580 10.758294020000 10.247198650000 R=1.700

126 H -0.147223596100 11.550103830000 9.484457729000 R=1.350

127 H 0.951093197100 10.427776640000 10.338585450000 R=1.350

128 H -0.392406987900 11.201063100000 11.208506580000 R=1.350

129 C -2.472863332000 10.028920980000 9.734820435000 R=1.700

130 H -2.819369729000 10.570525880000 10.628473890000 R=1.350

131 H -3.133364879000 9.163058244000 9.579524537000 R=1.350

132 H -2.568466938000 10.697785500000 8.864940887000 R=1.350

133 H -0.736520170300 9.295248215000 13.273949300000 R=1.350

134 H 1.613994817000 9.415291316000 14.260288370000 R=1.350

END

GUIBONDS



61

1 1 7 3

2 1 8 3

3 1 2 3

4 3 9 1.0

5 3 13 1.0

6 3 7 1.0

7 4 11 1.0

8 4 7 1.0

9 4 42 1.0

10 5 71 1.0

11 5 75 1.0

12 5 8 1.0

13 6 73 1.0

14 6 8 1.0

15 6 104 1.0

16 9 10 1.0

17 9 11 2.0

18 11 12 1.0

19 13 14 1.5

20 13 21 1.5

21 14 15 1.5

22 14 22 1.0

23 15 16 1.0

24 15 17 1.5

25 17 18 1.0

26 17 19 1.5

27 19 20 1.0

28 19 21 1.5

29 21 32 1.0

30 22 23 1.0

31 22 24 1.0

32 22 28 1.0

33 24 27 1.0

34 24 26 1.0

35 24 25 1.0

36 28 31 1.0

37 28 30 1.0

38 28 29 1.0

39 32 33 1.0

40 32 38 1.0

41 32 34 1.0

42 34 36 1.0

43 34 37 1.0

44 34 35 1.0

45 38 41 1.0

46 38 39 1.0

47 38 40 1.0

48 42 43 1.5

49 42 50 1.5

50 43 44 1.5

51 43 51 1.0

52 44 45 1.0

53 44 46 1.5

54 46 47 1.0

55 46 48 1.5

56 48 49 1.0

57 48 50 1.5

58 50 61 1.0

59 51 52 1.0

60 51 57 1.0

61 51 53 1.0

62 53 56 1.0

63 53 54 1.0

64 53 55 1.0

65 57 60 1.0

66 57 59 1.0

67 57 58 1.0

68 61 62 1.0

69 61 67 1.0

70 61 63 1.0

71 63 64 1.0

72 63 65 1.0

73 63 66 1.0

74 67 68 1.0

75 67 70 1.0

76 67 69 1.0

77 71 72 1.0

78 71 73 2.0

79 73 74 1.0

80 75 83 1.5

81 75 76 1.5

82 76 77 1.5

83 76 84 1.0

84 77 78 1.0

85 77 79 1.5

86 79 80 1.0

87 79 81 1.5

88 81 82 1.0

89 81 83 1.5

90 83 94 1.0

91 84 85 1.0

92 84 86 1.0

93 84 90 1.0

94 86 87 1.0

95 86 88 1.0

96 86 89 1.0

97 90 92 1.0

98 90 91 1.0



62

99 90 93 1.0

100 94 95 1.0

101 94 96 1.0

102 94 100 1.0

103 96 97 1.0

104 96 98 1.0

105 96 99 1.0

106 100 101 1.0

107 100 102 1.0

108 100 103 1.0

109 104 112 1.5

110 104 105 1.5

111 105 106 1.5

112 105 113 1.0

113 106 107 1.0

114 106 108 1.5

115 108 109 1.0

116 108 110 1.5

117 110 111 1.0

118 110 112 1.5

119 112 123 1.0

120 113 114 1.0

121 113 119 1.0

122 113 115 1.0

123 115 116 1.0

124 115 117 1.0

125 115 118 1.0

126 119 121 1.0

127 119 120 1.0

128 119 122 1.0

129 123 124 1.0

130 123 129 1.0

131 123 125 1.0

132 125 128 1.0

133 125 126 1.0

134 125 127 1.0

135 129 131 1.0

136 129 130 1.0

137 129 132 1.0

138 133 2 1.0

139 134 2 1.0

END

SOLVATION

Surf Esurf


Charged method=CONJ

C-Mat POT

SCF VAR ALL

CSMRSP

END

BASIS

type TZP

core Large

createoutput None

END

XC




63

DISPERSION Grimme3

END

GEOMETRY

optim Delocalized

iterations 100

END

SAVE TAPE21 TAPE13

SCF

iterations 100

END

FULLSCF

BeckeGrid

Quality Good

End

NOPRINT LOGFILE

eor

---------------------------

#! /bin/sh

# ==============================

# Attempted optimization of [{(HCDippN)2B}2Ge(H)Ge(H) # ==============================



64

"$ADFBIN/adf" <<eor

ATOMS

1 Ge 1.213370678000 7.110292610000 11.596694400000 R=2.033

2 Ge 0.579670929600 8.423687431000 13.545154340000 R=2.033

3 N 3.875691341000 6.243628185000 13.152219280000 R=1.608

4 N 3.886411940000 5.486483850000 10.995627680000 R=1.608

5 N -1.692494503000 5.715242020000 11.794463590000 R=1.608

6 N -1.269259796000 6.697441480000 9.777278963000 R=1.608

7 B 3.048494508000 6.158907313000 11.965686210000 R=1.792

8 B -0.642294459500 6.364330892000 11.035787050000 R=1.792

9 C 5.108095113000 5.632168022000 12.884856040000 R=1.700

10 H 5.889559202000 5.580130465000 13.634449060000 R=1.350

11 C 5.114300333000 5.179628017000 11.604697080000 R=1.700

12 H 5.900443198000 4.667239266000 11.062408610000 R=1.350

13 C 3.732648448000 7.089227272000 14.306165120000 R=1.700

14 C 4.317651495000 8.372556050000 14.265969970000 R=1.700

15 C 4.200124248000 9.187749111000 15.402715900000 R=1.700

16 H 4.641134417000 10.186250180000 15.393847640000 R=1.350

17 C 3.511744650000 8.748045753000 16.530400840000 R=1.700

18 H 3.422621014000 9.395682835000 17.403593180000 R=1.350

19 C 2.918019529000 7.483909721000 16.537895120000 R=1.700

20 H 2.362280217000 7.163569753000 17.418287010000 R=1.350

21 C 3.013010871000 6.629452123000 15.430466880000 R=1.700

22 C 5.030618950000 8.897779694000 13.025416270000 R=1.700

23 H 5.034331368000 8.098021913000 12.275079190000 R=1.350

24 C 4.279623955000 10.094309020000 12.415293340000 R=1.700

25 H 3.250537400000 9.815648332000 12.146449030000 R=1.350

26 H 4.792728834000 10.442896110000 11.506472280000 R=1.350

27 H 4.231004376000 10.937290010000 13.121521490000 R=1.350

28 C 6.499021531000 9.248838802000 13.317700180000 R=1.700

29 H 6.578720858000 10.072788580000 14.043335220000 R=1.350

30 H 7.006321645000 9.563619439000 12.393366360000 R=1.350

31 H 7.037631241000 8.381890581000 13.727518290000 R=1.350



65

32 C 2.361750306000 5.252512356000 15.425145170000 R=1.700

33 H 1.917770826000 5.119397935000 14.424758970000 R=1.350

34 C 3.406531893000 4.138785170000 15.633606930000 R=1.700

35 H 4.175053130000 4.151649039000 14.850047330000 R=1.350

36 H 2.918950702000 3.151937221000 15.615907470000 R=1.350

37 H 3.901660537000 4.255995431000 16.610586150000 R=1.350

38 C 1.230734785000 5.113927897000 16.447276810000 R=1.700

39 H 1.603168544000 5.185219661000 17.480917030000 R=1.350

40 H 0.752082027800 4.133083906000 16.334240930000 R=1.350

41 H 0.455483795400 5.878918876000 16.293969470000 R=1.350

42 C 3.775509603000 5.360172362000 9.567266523000 R=1.700

43 C 3.964999107000 6.507880658000 8.761293409000 R=1.700

44 C 3.989377830000 6.332578940000 7.370010874000 R=1.700

45 H 4.123099200000 7.201178227000 6.724654284000 R=1.350

46 C 3.875400162000 5.065736789000 6.798073900000 R=1.700

47 H 3.917469770000 4.950281617000 5.714424889000 R=1.350

48 C 3.682226747000 3.950790654000 7.611367268000 R=1.700

49 H 3.566112354000 2.966080640000 7.155819019000 R=1.350

50 C 3.597905384000 4.080371711000 9.005708670000 R=1.700

51 C 4.240208096000 7.879241359000 9.367145434000 R=1.700

52 H 3.794213280000 7.898805701000 10.370754010000 R=1.350

53 C 3.608276207000 9.033379676000 8.580199761000 R=1.700

54 H 4.093226790000 9.178682968000 7.602591501000 R=1.350

55 H 3.720739657000 9.970457069000 9.145090350000 R=1.350

56 H 2.537451422000 8.858622644000 8.408747787000 R=1.350

57 C 5.758392664000 8.087708211000 9.533282184000 R=1.700

58 H 6.200658111000 7.303135766000 10.163771520000 R=1.350

59 H 5.963395714000 9.060596590000 10.004672600000 R=1.350

60 H 6.257957041000 8.069064074000 8.551598745000 R=1.350

61 C 3.318030341000 2.863135649000 9.875616291000 R=1.700

62 H 3.123855339000 3.231195690000 10.893154460000 R=1.350

63 C 4.529172239000 1.915867775000 9.937647281000 R=1.700

64 H 4.766645354000 1.521988377000 8.936984206000 R=1.350



66

65 H 4.317668376000 1.061765344000 10.598866400000 R=1.350

66 H 5.421108740000 2.431830347000 10.319372170000 R=1.350

67 C 2.063392336000 2.115721013000 9.396426811000 R=1.700

68 H 1.190418461000 2.781768109000 9.388592953000 R=1.350

69 H 1.846216110000 1.263865445000 10.057066410000 R=1.350

70 H 2.192491582000 1.718809120000 8.379039723000 R=1.350

71 C -2.848442822000 5.665374499000 10.997950420000 R=1.700

72 H -3.756355236000 5.191627026000 11.349307800000 R=1.350

73 C -2.599087141000 6.256705857000 9.802901155000 R=1.700

74 H -3.262144227000 6.394259124000 8.957964751000 R=1.350

75 C -1.735533951000 5.176449167000 13.127248580000 R=1.700

76 C -1.055448176000 3.968729201000 13.406010130000 R=1.700

77 C -1.235791076000 3.388816371000 14.668454890000 R=1.700

78 H -0.732567966100 2.451838062000 14.905537380000 R=1.350

79 C -2.051166595000 3.984406238000 15.631185440000 R=1.700

80 H -2.179914022000 3.511620962000 16.605614170000 R=1.350

81 C -2.672169312000 5.198756892000 15.354639230000 R=1.700

82 H -3.283359647000 5.676801791000 16.121717890000 R=1.350

83 C -2.520487617000 5.824719738000 14.106946780000 R=1.700

84 C -0.210409110000 3.270952453000 12.346486150000 R=1.700

85 H 0.283112416800 4.050496566000 11.745970270000 R=1.350

86 C 0.897198664100 2.392561786000 12.942121190000 R=1.700

87 H 1.513460417000 2.956241050000 13.655855970000 R=1.350

88 H 1.553376651000 2.025899008000 12.142946100000 R=1.350

89 H 0.489703585800 1.510397610000 13.458373190000 R=1.350

90 C -1.117825960000 2.457106008000 11.402722840000 R=1.700

91 H -0.522297355900 1.944062984000 10.634841170000 R=1.350

92 H -1.844602305000 3.108551171000 10.897046670000 R=1.350

93 H -1.672995167000 1.696052322000 11.973804670000 R=1.350

94 C -3.194088997000 7.169701060000 13.854927270000 R=1.700

95 H -2.734992836000 7.603136994000 12.954306840000 R=1.350

96 C -2.971127898000 8.150297945000 15.020888440000 R=1.700

97 H -3.550555683000 7.855583015000 15.908732350000 R=1.350



67

98 H -3.297219833000 9.160194224000 14.732207850000 R=1.350

99 H -1.911701645000 8.199264273000 15.306278990000 R=1.350

100 C -4.706608111000 7.015712609000 13.599875560000 R=1.700

101 H -4.914852141000 6.372297583000 12.736044350000 R=1.350

102 H -5.165166418000 7.998392782000 13.410904970000 R=1.350

103 H -5.198850347000 6.573877380000 14.480537190000 R=1.350

104 C -0.711758290800 7.320865658000 8.609571918000 R=1.700

105 C -0.464920549200 6.527765472000 7.466985022000 R=1.700

106 C 0.083607123950 7.152415473000 6.337080609000 R=1.700

107 H 0.292817907600 6.558366574000 5.446034823000 R=1.350

108 C 0.367258268600 8.517345528000 6.335540011000 R=1.700

109 H 0.802358372500 8.984528298000 5.450972463000 R=1.350

110 C 0.091378339520 9.286633467000 7.466030950000 R=1.700

111 H 0.304957149200 10.355956740000 7.451402749000 R=1.350

112 C -0.455173878200 8.710343654000 8.622008435000 R=1.700

113 C -0.828594434300 5.047381314000 7.424839681000 R=1.700

114 H -1.013030685000 4.720888364000 8.458312506000 R=1.350

115 C -2.123768013000 4.830275244000 6.616994213000 R=1.700

116 H -2.959789955000 5.422970959000 7.012375244000 R=1.350

117 H -2.415807953000 3.769123437000 6.636239115000 R=1.350

118 H -1.971885138000 5.124275039000 5.566368168000 R=1.350

119 C 0.298978888000 4.175171575000 6.860314374000 R=1.700

120 H 0.486684942600 4.389042350000 5.796965842000 R=1.350

121 H 0.032187586990 3.110757410000 6.942147552000 R=1.350

122 H 1.234533782000 4.342169007000 7.405411353000 R=1.350

123 C -0.841832867500 9.582537991000 9.809201324000 R=1.700

124 H -0.907235440200 8.935561619000 10.691888890000 R=1.350

125 C 0.192167922900 10.671406710000 10.124794690000 R=1.700

126 H 0.240164129400 11.435403570000 9.333742207000 R=1.350

127 H 1.192768624000 10.235244880000 10.252715340000 R=1.350

128 H -0.076664509870 11.178698070000 11.063053180000 R=1.350

129 C -2.242632063000 10.184658430000 9.587435892000 R=1.700

130 H -2.549570564000 10.776139730000 10.463897860000 R=1.350



68

131 H -2.988257086000 9.391668229000 9.428327731000 R=1.350

132 H -2.248333151000 10.844992690000 8.705680831000 R=1.350

133 H 1.579848517000 9.377032822000 14.304750460000 R=1.350

134 H 1.289605645000 5.605271506000 11.035493260000 R=1.350

END

GUIBONDS

1 1 7 3

2 1 8 3

3 1 2 3

4 3 9 1.0

5 3 13 1.0

6 3 7 1.0

7 4 11 1.0

8 4 7 1.0

9 4 42 1.0

10 5 71 1.0

11 5 75 1.0

12 5 8 1.0

13 6 73 1.0

14 6 8 1.0

15 6 104 1.0

16 9 10 1.0

17 9 11 2.0

18 11 12 1.0

19 13 14 1.5

20 13 21 1.5

21 14 15 1.5

22 14 22 1.0

23 15 16 1.0

24 15 17 1.5

25 17 18 1.0

26 17 19 1.5

27 19 20 1.0

28 19 21 1.5

29 21 32 1.0

30 22 23 1.0

31 22 24 1.0

32 22 28 1.0

33 24 27 1.0

34 24 26 1.0

35 24 25 1.0

36 28 31 1.0

37 28 30 1.0

38 28 29 1.0

39 32 33 1.0

40 32 38 1.0

41 32 34 1.0

42 34 36 1.0

43 34 37 1.0

44 34 35 1.0

45 38 41 1.0

46 38 39 1.0

47 38 40 1.0

48 42 43 1.5

49 42 50 1.5

50 43 44 1.5

51 43 51 1.0

52 44 45 1.0

53 44 46 1.5

54 46 47 1.0

55 46 48 1.5

56 48 49 1.0

57 48 50 1.5

58 50 61 1.0

59 51 52 1.0

60 51 57 1.0

61 51 53 1.0

62 53 56 1.0

63 53 54 1.0

64 53 55 1.0

65 57 60 1.0

66 57 59 1.0

67 57 58 1.0

68 61 62 1.0

69 61 67 1.0

70 61 63 1.0

71 63 64 1.0

72 63 65 1.0

73 63 66 1.0

74 67 68 1.0

75 67 70 1.0

76 67 69 1.0

77 71 72 1.0

78 71 73 2.0



69

79 73 74 1.0

80 75 83 1.5

81 75 76 1.5

82 76 77 1.5

83 76 84 1.0

84 77 78 1.0

85 77 79 1.5

86 79 80 1.0

87 79 81 1.5

88 81 82 1.0

89 81 83 1.5

90 83 94 1.0

91 84 85 1.0

92 84 86 1.0

93 84 90 1.0

94 86 87 1.0

95 86 88 1.0

96 86 89 1.0

97 90 92 1.0

98 90 91 1.0

99 90 93 1.0

100 94 95 1.0

101 94 96 1.0

102 94 100 1.0

103 96 97 1.0

104 96 98 1.0

105 96 99 1.0

106 100 101 1.0

107 100 102 1.0

108 100 103 1.0

109 104 112 1.5

110 104 105 1.5

111 105 106 1.5

112 105 113 1.0

113 106 107 1.0

114 106 108 1.5

115 108 109 1.0

116 108 110 1.5

117 110 111 1.0

118 110 112 1.5

119 112 123 1.0

120 113 114 1.0

121 113 119 1.0

122 113 115 1.0

123 115 116 1.0

124 115 117 1.0

125 115 118 1.0

126 119 121 1.0

127 119 120 1.0

128 119 122 1.0

129 123 124 1.0

130 123 129 1.0

131 123 125 1.0

132 125 128 1.0

133 125 126 1.0

134 125 127 1.0

135 129 131 1.0

136 129 130 1.0

137 129 132 1.0

138 133 2 1.0

139 134 1 1.0

END



70

SOLVATION

Surf Esurf


Charged method=CONJ

C-Mat POT

SCF VAR ALL

CSMRSP

END

BASIS

type TZP

core Large

createoutput None

END

XC


DISPERSION Grimme3

END

GEOMETRY

optim Delocalized

iterations 150

END

SAVE TAPE21 TAPE13

SCF

iterations 150



71

END

FULLSCF

BeckeGrid

Quality Good

End

NOPRINT LOGFILE

eor

-----------------------------------------------



72

Supplementary Figure 21: Structure of Ge(-boryl)Ge(boryl) transition state describing 1,2 transfer of a single boryl ligand

Ge 1.364399 6.939009 11.189787

Ge 0.571936 8.259056 13.647021

N 3.681246 6.167101 13.439715

N 3.703004 5.000561 11.457259

N -0.989908 5.211904 13.172588

N -1.54381 6.666395 11.443579

B 2.885149 5.924211 12.243954

B -0.513466 6.494271 12.532604

C 4.870683 5.428364 13.337808

C 2.076038 2.707159 10.523988

C 4.88189 4.735833 12.16474

C -0.144747 1.477919 13.502815

C 3.58928 7.259705 14.374347

C 4.115897 8.517269 13.989754

C 4.086338 9.569035 14.914844

C 2.556513 1.249318 10.428328

C 3.512831 9.403512 16.172266

C -1.811863 8.144715 8.0221230

C 2.962836 8.173535 16.524166

C -2.390056 9.370073 12.18985



73

C 2.99744 7.075726 15.647794

C 4.682126 8.763653 12.601636

C -2.261119 9.430225 8.3188460

C 4.074086 10.018105 11.956291

C 0.566777 2.817151 10.248864

C -2.662746 6.506768 15.203451

C -3.83957 9.059286 12.549103

C 6.219171 8.824874 12.620806

C -2.486168 7.695483 16.159321

C -2.124803 4.769692 12.507542

C -2.427578 9.816357 9.647712

C 2.429798 5.733838 16.085813

C -2.448235 5.625531 11.48751

C 3.542769 4.762271 16.527517

C -2.038937 10.842742 12.399841

C -0.890276 4.739206 14.547027

C -0.146936 3.579257 14.850121

C 1.406915 5.868987 17.216283

C -0.212874 3.065229 16.15441

C -2.136525 8.936031 10.701326

C -1.00425 3.666314 17.129181

C 3.622520 4.700207 10.044148

C 4.340969 5.509929 9.126187

C 4.261396 5.211309 7.758444

C -4.124234 6.017788 15.200993

C 3.494434 4.145244 7.293694

C -1.735978 4.80807 16.81282

C 2.798091 3.358057 8.204656

C -1.097421 5.808516 8.662724

C 2.849522 3.614375 9.584058

C 5.175661 6.704045 9.562985

C -1.712959 5.358316 15.522403

C 4.691515 8.00454 8.903420



74

C 0.605528 2.793995 13.788534

C 0.113991 5.785944 7.717814

C 2.061857 2.506562 14.181781

C 6.672952 6.465854 9.302462

C -2.266771 5.006911 8.059054

C -1.687311 7.635586 10.379731

C -1.526997 7.220117 9.0364340

H 5.632812 5.461926 14.108003

H 2.263576 3.061394 11.545083

H 5.647238 4.073949 11.774824

H 0.384922 0.882593 12.745765

H -1.165679 1.665688 13.139504

H -0.217171 0.867981 14.416712

H 4.497985 10.539491 14.633642

H 3.632735 1.170132 10.64102

H 2.377349 0.834787 9.424362

H 2.01619 0.616499 11.147976

H 3.479691 10.236739 16.875259

H -1.687448 7.845986 6.980269

H 2.497825 8.062739 17.501993

H -1.75169 8.758324 12.796399

H 4.397943 7.90754 11.979414

H -2.488785 10.129049 7.51305

H 4.330543 10.927097 12.522009

H 2.978622 9.929496 11.912822

H 4.458019 10.141459 10.933421

H 0.224529 3.844537 10.431596

H -0.007468 2.142578 10.896764

H 0.333097 2.560595 9.2045600

H -2.431809 6.868268 14.194703

H -4.006729 9.320339 13.605458

H -4.061642 7.989576 12.420028

H -4.547206 9.635586 11.932186



75

H 6.644135 7.906977 13.053394

H 6.573615 9.682218 13.215006

H 6.60905 8.934177 11.596952

H -1.44028 8.034179 16.167618

H -2.784197 7.437184 17.187241

H -3.11459 8.53700 15.830119

H -2.664944 3.891116 12.842885

H -2.793636 10.818464 9.873062

H 1.915895 5.295314 15.215044

H -3.264074 5.553845 10.778177

H 4.252969 4.551674 15.719443

H 3.100493 3.806534 16.847359

H 4.097863 5.184433 17.380365

H -1.010556 11.067874 12.080883

H -2.123777 11.064299 13.473559

H -2.718298 11.522739 11.864531

H 0.965199 4.888029 17.428153

H 0.590381 6.55349 16.947076

H 1.877775 6.225881 18.145288

H 0.347089 2.161655 16.399518

H -1.050789 3.245655 18.134053

H 4.805419 5.832673 7.044775

H -4.796553 6.835009 14.898585

H -4.428096 5.676338 16.203191

H -4.261935 5.184749 14.496793

H 3.442526 3.928012 6.226254

H -2.365642 5.26937 17.574965

H 2.19907 2.522169 7.839809

H -0.788623 5.307625 9.587816

H 5.049971 6.822613 10.644105

H 5.288121 8.855673 9.262721

H 3.636161 8.194472 9.148757

H 4.789449 7.965006 7.807862



76

H 0.610877 3.399406 12.872853

H 0.953218 6.353048 8.145161

H -0.134181 6.203326 6.729675

H 0.455707 4.750038 7.572695

H 2.560155 1.922561 13.395289

H 2.122571 1.924159 15.113427

H 2.625119 3.437089 14.319316

H 7.01999 5.553331 9.80879

H 7.267553 7.313081 9.676901

H 6.874762 6.356101 8.225128

H -2.585654 5.446742 7.100933

H -3.140606 4.985637 8.725881

H -1.954019 3.968461 7.869944



77

Supplementary Figure 22: Electron density surface for the HOMO-11 of 5 (E = -6.37 eV).



78

5. TD-DFT

The electronic excitations of 5 were calculated using all-electron triple-zeta polarization basis set in a simulated hexane solvent environment. The calculation was performed at the spin-orbit coupled level, without symmetry restrictions and employing the noncollinear and Tamm-Dancoff approximations.

Supplementary Figure 23: Calculated UV/Vis spectrum for 5.



79

Supplementary Table 2: Assignment of key bands in the calculated UV/Vis spectrum of 5. All MOs belong to the a1/2 irreducible representation. The HOMO is MO 243.

Energy/eV (nm)

f Transition MOs

Initial MO Final MO

2.68 (461)

0.20 94% 243→245

Energy/eV (nm)

f Transition MOs

Initial MO Final MO

2.998 (413)

0.0033 80% 242→245



80

4. References for supporting information

1. Pangborn, A. B., Giardello, M. A., Grubbs, R. H., Rosen, R. K. & Timmers, F. J., Safe and convenient procedure for solvent purification. Organometallics 15, 1518-1520 (1996).

2. Ryan, S. J., Schimler, S. D., Bland, D. C. & Sanford, M S. Acyl azolium fluorides for room temperature nucleophilic aromatic fluorination of chloro- and nitroarenes. Org. Lett. 17, 1866-1869 (2015).

3. Segawa, Y., Yamashita, M. & Nozaki, K. Boryllithium: isolation, characterization, and reactivity as a boryl anion. Science 314, 113-115 (2006).

4. Rupar, P. A., Staroverov, V. N., Ragogna, P. J. & Baines, K. M. A germanium(II)-centered dication. J. Am. Chem. Soc. 129, 15138-15139 (2007).

5. Green, S. P., Jones, C. & Stasch, A. Stable magnesium(I) compounds with Mg-Mg bonds. Science 318, 1754-1757 (2007).

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