Supporting Information - Wiley-VCH · 2006. 11. 27. · ppm (f1) 10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0...

Supporting Information

© Copyright Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2006

SUPPORTING INFORMATION

Asymmetric Catalysis in the [2+2+2] Cycloaddition of Arynes and Alkynes: Enantioselective

Synthesis of a Pentahelicene. Caeiro, J.; Peña, D.; Cobas, A.; Pérez, D.; Guitián, E.

I. NMR SPECTRA

ppm (f1)

0.01.02.03.04.05.06.07.08.09.010.0

ppm (f1)

0102030405060708090100110120130140150160170180190200210

ppm (f1)

0102030405060708090100110120130140150160170180190200210

Br

OHMeO

6

NOESY spectrum of 6

ppm (t1)

0.01.02.03.04.05.06.07.08.09.010.0

Br

OTMSMeO

ppm (f1)

0.01.02.03.04.05.06.07.08.09.010.0

ppm (f1)

0102030405060708090100110120130140150160170180190200210

ppm (f1)

0102030405060708090100110120130140150160170180190200210

TMS

OTfMeO

4

ppm (t1)

0.01.02.03.04.05.06.07.08.09.010.0

ppm (t1)

0102030405060708090100110120130140150160170180190200210

ppm (f1)

0102030405060708090100110120130140150160170180190200210

MeO

1

CO2Me

CO2Me

MeO

NOESY spectrum of 1

COSY spectrum of 1

.

min0 2 4 6 8 10 12 14

mAU

0

100

200

300

400

500

DAD1 B, Sig=243,16 Ref=380,100 (GR\JCNA0004.D)

Area: 15074.3

9.2

45

Area: 15195.2 10

.29

5

nm200 225 250 275 300 325 350 375

mAU

0

100

200

300

400

500

600

DAD1, 9.242 (704 mAU,Apx) of JCNA0004.D DAD1, 10.302 (643 mAU,Apx) of JCNA0004.D

HPLC chromatogram of racemic 1 and UV spectra of both enantiomers. Column OL-86;

CH2Cl2/hexanes (25:75); ë = 243 nm.

min0 2 4 6 8 10

mAU

0

200

400

600

800

1000

DAD1 B, Sig=243,16 Ref=380,100 (GR\JC241001.D)

Area: 25684.6

7.5

45

Area: 1450.72 8.3

22

nm200 225 250 275 300 325 350 375

mAU

0

200

400

600

800

1000

1200

1400

DAD1, 7.549 (1448 mAU,Apx) of JC241001.D DAD1, 8.295 (188 mAU,Apx) of JC241001.D

HPLC chromatogram of a sample of (M)-1 (> 90% ee;experiment in Table 2, entry 4) and UV

spectra of both enantiomers. Column OL-86; CH2Cl2/hexanes (35:65); ë = 243 nm.

CD spectrum of a sample of 1, enriched in enantiomer (M) (61% ee), in CH2Cl2.

ppm (t1)

0.01.02.03.04.05.06.07.08.09.010.0

ppm (t1)

0102030405060708090100110120130140150160170180190200210

ppm (t1)

0102030405060708090100110120130140150160170180190200210

MeO

OMe

CO2Me

CO2Me

7

ppm (f1)

0.01.02.03.04.05.06.07.08.09.010.0

ppm (f1)

0102030405060708090100110120130140150160170180190200210

ppm (f1)

0102030405060708090100110120130140150160170180190200210

OMe

OMe

CO2Me

CO2Me

8

NOESY spectrum of 8

COSY spectrum of 8

ppm (f1)

0.01.02.03.04.05.06.07.08.09.010.0

ppm (t1)

-40-30-20-100102030405060708090

P

P

Pd

CO2Me

CO2Me

10

Ph2

Ph2

II. GEOMETRY AND ENERGY INFORMATION

Calculated geometry for transition state TS-1 – BLYP/6-31G(d,p)

6 0.062367 -3.285866 -1.456828 6 1.206825 -2.712910 -0.969528 6 1.175340 -1.408338 -0.357161 6 -0.065446 -0.675674 -0.192553 6 -1.282348 -1.526024 -0.307868 6 -1.211706 -2.742191 -1.100132 6 2.430136 -0.786694 -0.005251 6 0.017990 0.800163 -0.148364 6 1.340327 1.380244 -0.282387 6 2.513460 0.598907 0.017395 6 1.530651 2.690796 -0.843988 1 2.546055 3.061030 -0.976971 6 0.464902 3.419233 -1.301126 6 -0.863513 3.020534 -0.954752 1 0.101756 -4.210320 -2.039552 1 2.178534 -3.171821 -1.138653 1 0.613657 4.360054 -1.837849 6 -1.945672 3.915198 -1.201411 6 -3.189252 3.733405 -0.623450 6 -3.359137 2.659116 0.287456 6 -2.335139 1.718290 0.475688 6 -1.087848 1.797958 -0.209495 1 -1.754339 4.796916 -1.819404 1 -4.013192 4.431565 -0.781620 6 -2.393766 -3.477000 -1.382057 6 -3.623018 -3.154687 -0.813438 1 -2.311262 -4.356828 -2.026254 1 -4.508068 -3.748716 -1.040343 6 -3.653677 -2.097889 0.125362 6 -2.510327 -1.319891 0.363566 8 -4.562855 2.662884 0.957323 8 -4.760569 -1.759431 0.888720 6 -4.805891 1.647779 1.950167 1 -4.821896 0.637710 1.508905

1 -4.055451 1.686903 2.760216 1 -5.794163 1.881648 2.368412 6 -5.953488 -2.547394 0.733423 1 -6.360594 -2.475357 -0.290672 1 -5.773618 -3.608766 0.979384 1 -6.680479 -2.127989 1.441028 6 3.816628 1.316170 0.270872 8 3.950852 2.312355 0.971978 8 4.854852 0.737670 -0.422375 6 3.626018 -1.644757 0.338074 8 4.093878 -2.567903 -0.320200 8 4.113669 -1.283469 1.571586 1 -2.461150 0.980173 1.251542 1 -2.583657 -0.613824 1.176025 6 6.153948 1.353548 -0.192210 1 6.434889 1.280510 0.868809 1 6.854679 0.792471 -0.821970 1 6.133548 2.414727 -0.479913 6 5.281715 -2.036631 2.006042 1 6.119397 -1.886817 1.309067 1 5.525373 -1.642009 2.999709 1 5.050895 -3.110483 2.057582

Calculated geometry for ground state GS-1 – BLYP/6-31G(d,p)

6 0.028045 -3.481873 0.846311 6 -1.130455 -2.742105 0.864793 6 -1.142990 -1.369794 0.426164 6 0.093373 -0.724358 0.078917 6 1.255159 -1.583051 -0.178144 6 1.224986 -2.954156 0.264688 6 -2.385092 -0.646352 0.261753 6 0.093358 0.724327 -0.078949 6 -1.143017 1.369734 -0.426206 6 -2.385103 0.646264 -0.261807 6 -1.130512 2.742049 -0.864828 1 -2.056384 3.183556 -1.229242 6 0.027969 3.481847 -0.846328 6 1.224915 2.954155 -0.264692 1 0.028577 -4.514421 1.207062 1 -2.056321 -3.183632 1.229197 1 0.028481 4.514396 -1.207073 6 2.362972 3.786595 -0.038211 6 3.463993 3.330351 0.664298 6 3.455745 2.006701 1.194617 6 2.375880 1.154093 0.954404 6 1.255118 1.583048 0.178131 1 2.337423 4.816564 -0.405020 1 4.329564 3.966615 0.858904 6 2.363067 -3.786568 0.038226 6 3.464085 -3.330301 -0.664272 1 2.337539 -4.816536 0.405041 1 4.329675 -3.966544 -0.858863 6 3.455810 -2.006655 -1.194600 6 2.375919 -1.154073 -0.954407 8 4.567256 1.682357 1.943191 8 4.567320 -1.682287 -1.943163 6 4.630465 0.364944 2.520345 1 5.591005 0.320431 3.049928 1 3.807926 0.197270 3.237866 1 4.599331 -0.419636 1.744538 6 4.630502 -0.364876 -2.520326 1 3.807967 -0.197229 -3.237857 1 4.599338 0.419708 -1.744524 1 5.591047 -0.320341 -3.049897 1 2.370533 0.152980 1.375080 1 2.370552 -0.152964 -1.375092 6 -3.680741 -1.358001 0.572262 8 -3.955757 -1.902593 1.635578 8 -4.512276 -1.370937 -0.520653 6 -3.680766 1.357901 -0.572297 8 -3.955783 1.902520 -1.635599 8 -4.512230 1.370934 0.520669 6 -5.796526 -2.022165 -0.298869 1 -6.358539 -1.507622 0.494192 1 -6.322968 -1.955130 -1.258341 1 -5.649989 -3.071886 -0.006034 6 -5.796450 2.022243 0.298943 1 -5.649859 3.071945 0.006068 1 -6.358548 1.507715 -0.494067 1 -6.322838 1.955273 1.258450

III. CRYSTALOGRAPHIC INFORMATION

IIIa. X-Ray difracction study of pentahelicene 1 - This structure has been deposited at

the Cambridge Crystallographic Database with deposition number CCDC 605852

Mercury view of the packing of (M,P)-1 (unit cell)

Mercury view of the packing of (M,P)-1 along three axis

1

Table 1. Crystal data and structure refinement for.1

Empirical formula C28 H22 O6

Formula weight 454.46

Temperature 293(2) K

Wavelength 0.71073 Å

Crystal system Monoclinic

Space group P 2/c

Unit cell dimensions a = 15.679(4) Å α= 90°

b = 13.123(3) Å β= 109.821(5)°

c = 11.376(3) Å γ = 90°

Volume 2201.8(10) Å3

Z 4

Density (calculated) 1.371 Mg/m3

Absorption coefficient 0.096 mm-1

F(000) 952

Crystal size 0.31 x 0.16 x 0.05 mm3

Theta range for data collection 1.55 to 22.05°.

Index ranges -16<=h<=15, 0<=k<=13, 0<=l<=11

Reflections collected 34321

Independent reflections 2707 [R(int) = 0.0882]

Completeness to theta = 22.05° 99.5 %

Absorption correction SADABS Bruker

Max. and min. transmission 1.0000 and 0.8782

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 2707 / 0 / 312

Goodness-of-fit on F2 1.072

Final R indices [I>2sigma(I)] R1 = 0.0415, wR2 = 0.0958

R indices (all data) R1 = 0.1228, wR2 = 0.1355

Extinction coefficient 0.0061(9)

Largest diff. peak and hole 0.177 and -0.161 e.Å-3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 1.

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

C(101) 5455(3) 2085(3) 2593(4) 50(1)

C(102) 5913(3) 3015(3) 2560(4) 47(1)

C(103) 6819(3) 3023(4) 2557(4) 55(1)

C(104) 7185(3) 3862(4) 2258(4) 61(1)

C(105) 6664(3) 4753(3) 1860(4) 48(1)

C(106) 6987(3) 5575(4) 1333(4) 65(1)

C(107) 6476(3) 6415(4) 891(4) 63(1)

C(108) 5596(3) 6461(4) 925(4) 51(1)

C(109) 5244(3) 5661(3) 1384(3) 44(1)

C(110) 5779(3) 4806(3) 1903(3) 41(1)

C(111) 5428(2) 3935(3) 2389(3) 42(1)

C(112) 5972(3) 1108(3) 2746(5) 60(1)

O(113) 6598(3) 882(2) 3654(3) 90(1)

O(114) 5657(2) 533(2) 1731(3) 67(1)

C(115) 6113(4) -430(4) 1754(5) 97(2)

O(116) 5137(2) 7340(2) 458(3) 66(1)

C(117) 4272(3) 7484(3) 578(4) 71(1)

C(201) 9723(3) 5705(3) 1892(3) 45(1)

C(202) 9380(3) 4773(3) 1260(4) 45(1)

C(203) 8770(3) 4756(3) 8(4) 57(1)

C(204) 8378(3) 3890(4) -531(4) 64(1)

C(205) 8484(3) 2982(3) 168(4) 50(1)

C(206) 7961(3) 2100(4) -321(5) 67(1)

C(207) 7969(3) 1273(4) 392(5) 66(1)

C(208) 8503(3) 1294(3) 1660(5) 56(1)

C(209) 9034(3) 2126(3) 2162(4) 47(1)

C(210) 9073(3) 2961(3) 1419(4) 42(1)

C(211) 9626(2) 3845(3) 1924(3) 38(1)

C(212) 9394(3) 6681(3) 1227(5) 56(1)

O(213) 9465(2) 6958(2) 273(3) 83(1)

O(214) 8971(2) 7219(2) 1854(3) 70(1)

C(215) 8606(4) 8195(3) 1314(5) 100(2)

O(216) 8437(2) 445(2) 2325(4) 76(1)

C(217) 9019(4) 380(4) 3574(5) 99(2)

________________________________________________________________________________

Table 3. Bond lengths [Å] and angles [°] for 1.

_____________________________________________________

C(101)-C(101)#1 1.370(8)

C(101)-C(102) 1.424(5)

C(101)-C(112) 1.494(6)

C(102)-C(111) 1.404(5)

C(102)-C(103) 1.420(6)

C(103)-C(104) 1.337(5)

C(103)-H(103) 0.9300

C(104)-C(105) 1.410(6)

C(104)-H(104) 0.9300

C(105)-C(110) 1.406(5)

C(105)-C(106) 1.410(6)

C(106)-C(107) 1.354(6)

C(106)-H(106) 0.9300

C(107)-C(108) 1.395(6)

C(107)-H(107) 0.9300

C(108)-C(109) 1.369(5)

C(108)-O(116) 1.369(5)

C(109)-C(110) 1.405(5)

C(109)-H(109) 0.9300

C(110)-C(111) 1.457(5)

C(111)-C(111)#1 1.449(7)

C(112)-O(113) 1.196(5)

C(112)-O(114) 1.327(5)

O(114)-C(115) 1.448(5)

C(115)-H(11A) 0.9600

C(115)-H(11B) 0.9600

C(115)-H(11C) 0.9600

O(116)-C(117) 1.420(5)

C(117)-H(11D) 0.9600

C(117)-H(11E) 0.9600

C(117)-H(11F) 0.9600

C(201)-C(201)#2 1.362(7)

C(201)-C(202) 1.428(5)

C(201)-C(212) 1.488(5)

C(202)-C(211) 1.417(5)

C(202)-C(203) 1.421(5)

C(203)-C(204) 1.338(5)

C(203)-H(203) 0.9300

C(204)-C(205) 1.411(6)

C(204)-H(204) 0.9300

C(205)-C(210) 1.410(5)

C(205)-C(206) 1.418(6)

C(206)-C(207) 1.352(6)

C(206)-H(206) 0.9300

C(207)-C(208) 1.401(6)

C(207)-H(207) 0.9300

C(208)-O(216) 1.369(5)

C(208)-C(209) 1.375(5)

C(209)-C(210) 1.398(5)

C(209)-H(209) 0.9300

C(210)-C(211) 1.446(5)

C(211)-C(211)#2 1.432(7)

C(212)-O(213) 1.186(5)

C(212)-O(214) 1.329(5)

O(214)-C(215) 1.451(5)

C(215)-H(21A) 0.9600

C(215)-H(21B) 0.9600

C(215)-H(21C) 0.9600

O(216)-C(217) 1.407(5)

C(217)-H(21D) 0.9600

C(217)-H(21E) 0.9600

C(217)-H(21F) 0.9600

C(101)#1-C(101)-C(102) 120.3(2)

C(101)#1-C(101)-C(112) 120.9(2)

C(102)-C(101)-C(112) 118.7(4)

C(111)-C(102)-C(103) 119.2(4)

C(111)-C(102)-C(101) 119.1(4)

C(103)-C(102)-C(101) 121.3(4)

C(104)-C(103)-C(102) 121.5(4)

C(104)-C(103)-H(103) 119.3

C(102)-C(103)-H(103) 119.3

C(103)-C(104)-C(105) 120.8(4)

C(103)-C(104)-H(104) 119.6

C(105)-C(104)-H(104) 119.6

C(110)-C(105)-C(106) 118.5(4)

C(110)-C(105)-C(104) 120.1(4)

C(106)-C(105)-C(104) 121.3(4)

C(107)-C(106)-C(105) 121.8(4)

C(107)-C(106)-H(106) 119.1

C(105)-C(106)-H(106) 119.1

C(106)-C(107)-C(108) 119.5(4)

C(106)-C(107)-H(107) 120.3

C(108)-C(107)-H(107) 120.3

C(109)-C(108)-O(116) 124.6(4)

C(109)-C(108)-C(107) 120.5(4)

O(116)-C(108)-C(107) 114.9(4)

C(108)-C(109)-C(110) 120.7(4)

C(108)-C(109)-H(109) 119.6

C(110)-C(109)-H(109) 119.6

C(109)-C(110)-C(105) 118.8(4)

C(109)-C(110)-C(111) 122.5(3)

C(105)-C(110)-C(111) 118.5(4)

C(102)-C(111)-C(111)#1 117.8(2)

C(102)-C(111)-C(110) 118.1(3)

C(111)#1-C(111)-C(110) 123.9(2)

O(113)-C(112)-O(114) 124.4(4)

O(113)-C(112)-C(101) 124.6(5)

O(114)-C(112)-C(101) 111.1(4)

C(112)-O(114)-C(115) 116.4(4)

O(114)-C(115)-H(11A) 109.5

O(114)-C(115)-H(11B) 109.5

H(11A)-C(115)-H(11B) 109.5

O(114)-C(115)-H(11C) 109.5

H(11A)-C(115)-H(11C) 109.5

H(11B)-C(115)-H(11C) 109.5

C(108)-O(116)-C(117) 117.9(3)

O(116)-C(117)-H(11D) 109.5

O(116)-C(117)-H(11E) 109.5

H(11D)-C(117)-H(11E) 109.5

O(116)-C(117)-H(11F) 109.5

H(11D)-C(117)-H(11F) 109.5

H(11E)-C(117)-H(11F) 109.5

C(201)#2-C(201)-C(202) 120.9(2)

C(201)#2-C(201)-C(212) 120.5(2)

C(202)-C(201)-C(212) 118.3(3)

C(211)-C(202)-C(203) 119.3(4)

C(211)-C(202)-C(201) 118.7(3)

C(203)-C(202)-C(201) 121.9(4)

C(204)-C(203)-C(202) 121.4(4)

C(204)-C(203)-H(203) 119.3

C(202)-C(203)-H(203) 119.3

C(203)-C(204)-C(205) 120.8(4)

C(203)-C(204)-H(204) 119.6

C(205)-C(204)-H(204) 119.6

C(210)-C(205)-C(204) 119.8(4)

C(210)-C(205)-C(206) 118.3(4)

C(204)-C(205)-C(206) 121.7(4)

C(207)-C(206)-C(205) 122.2(4)

C(207)-C(206)-H(206) 118.9

C(205)-C(206)-H(206) 118.9

C(206)-C(207)-C(208) 118.9(4)

C(206)-C(207)-H(207) 120.5

C(208)-C(207)-H(207) 120.5

O(216)-C(208)-C(209) 124.4(4)

O(216)-C(208)-C(207) 115.0(4)

C(209)-C(208)-C(207) 120.6(5)

C(208)-C(209)-C(210) 121.0(4)

C(208)-C(209)-H(209) 119.5

C(210)-C(209)-H(209) 119.5

C(209)-C(210)-C(205) 118.6(4)

C(209)-C(210)-C(211) 122.1(4)

C(205)-C(210)-C(211) 119.0(4)

C(202)-C(211)-C(211)#2 118.6(2)

C(202)-C(211)-C(210) 117.4(3)

C(211)#2-C(211)-C(210) 123.9(2)

O(213)-C(212)-O(214) 123.2(4)

O(213)-C(212)-C(201) 127.2(4)

O(214)-C(212)-C(201) 109.5(4)

C(212)-O(214)-C(215) 116.0(4)

O(214)-C(215)-H(21A) 109.5

O(214)-C(215)-H(21B) 109.5

H(21A)-C(215)-H(21B) 109.5

O(214)-C(215)-H(21C) 109.5

H(21A)-C(215)-H(21C) 109.5

H(21B)-C(215)-H(21C) 109.5

C(208)-O(216)-C(217) 117.5(4)

O(216)-C(217)-H(21D) 109.5

O(216)-C(217)-H(21E) 109.5

H(21D)-C(217)-H(21E) 109.5

O(216)-C(217)-H(21F) 109.5

H(21D)-C(217)-H(21F) 109.5

H(21E)-C(217)-H(21F) 109.5

_____________________________________________________________

Symmetry transformations used to generate equivalent atoms:

#1 -x+1,y,-z+1/2 #2 -x+2,y,-z+1/2

Table 4. Anisotropic displacement parameters (Å2x 103)for gt01jc01. The anisotropic displacement factor

exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ]

______________________________________________________________________________

U11 U22 U33 U23 U13 U12

______________________________________________________________________________

C(101) 55(3) 46(3) 40(3) -1(2) 6(3) 1(2)

C(102) 39(3) 53(3) 44(3) -8(2) 9(2) 0(2)

C(103) 44(3) 61(3) 58(3) -13(2) 15(2) 4(3)

C(104) 37(3) 78(4) 69(3) -24(3) 17(2) -4(3)

C(105) 38(3) 59(3) 51(3) -14(2) 19(2) -12(2)

C(106) 51(3) 86(4) 67(3) -17(3) 30(3) -13(3)

C(107) 60(3) 80(4) 58(3) -9(3) 31(3) -29(3)

C(108) 58(3) 57(3) 38(3) -5(2) 17(2) -12(3)

C(109) 43(3) 53(3) 38(3) -5(2) 17(2) -6(2)

C(110) 36(3) 49(3) 36(3) -9(2) 10(2) -7(2)

C(111) 37(2) 51(3) 38(2) -6(2) 11(2) -1(2)

C(112) 60(3) 56(3) 60(4) 2(3) 16(3) 4(3)

O(113) 92(3) 77(3) 82(3) 5(2) 4(2) 32(2)

O(114) 76(2) 48(2) 74(2) -13(2) 21(2) 4(2)

C(115) 106(4) 49(3) 139(5) -23(3) 48(4) 7(3)

O(116) 77(2) 55(2) 68(2) 10(2) 27(2) -7(2)

C(117) 73(4) 64(3) 69(3) 14(3) 16(3) 3(3)

C(201) 53(3) 36(2) 53(3) 1(2) 28(2) 3(2)

C(202) 46(3) 49(3) 43(3) 1(2) 20(2) 8(2)

C(203) 63(3) 55(3) 51(3) 6(2) 15(3) 18(3)

C(204) 63(3) 68(3) 44(3) -3(3) -1(2) 14(3)

C(205) 42(3) 53(3) 50(3) -11(2) 8(2) 10(2)

C(206) 56(3) 74(4) 61(3) -21(3) 8(3) -2(3)

C(207) 50(3) 60(3) 82(4) -26(3) 13(3) -8(3)

C(208) 48(3) 51(3) 72(4) -9(3) 24(3) -1(3)

C(209) 43(3) 47(3) 53(3) -10(2) 18(2) -6(2)

C(210) 35(2) 43(3) 48(3) -5(2) 15(2) 4(2)

C(211) 35(2) 43(2) 40(3) -3(2) 17(2) 4(2)

C(212) 63(3) 51(3) 63(3) 1(3) 34(3) 3(2)

O(213) 116(3) 67(2) 84(3) 28(2) 59(2) 27(2)

O(214) 90(2) 43(2) 95(2) 10(2) 56(2) 16(2)

C(215) 124(5) 50(3) 142(5) 22(3) 67(4) 36(3)

O(216) 80(2) 52(2) 96(3) -6(2) 31(2) -22(2)

C(217) 136(5) 73(4) 90(5) 9(3) 40(4) -31(4)

______________________________________________________________________________

Table 5. Hydrogen coordinates ( x 104) and isotropic displacement parameters (Å2x 103) for 1.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

H(103) 7164 2432 2768 66

H(104) 7790 3857 2314 74

H(106) 7567 5540 1287 78

H(107) 6710 6956 569 76

H(109) 4643 5684 1353 53

H(11A) 6739 -308 1862 145

H(11B) 5830 -784 981 145

H(11C) 6072 -837 2434 145

H(11D) 3865 6965 116 106

H(11E) 4040 8142 257 106

H(11F) 4328 7442 1444 106

H(203) 8640 5360 -446 69

H(204) 8032 3886 -1376 76

H(206) 7600 2090 -1161 80

H(207) 7625 701 47 80

H(209) 9373 2134 3010 57

H(21A) 9095 8645 1341 149

H(21B) 8259 8486 1781 149

H(21C) 8223 8098 462 149

H(21D) 9634 483 3610 148

H(21E) 8963 -281 3901 148

H(21F) 8858 894 4061 148

________________________________________________________________________________

Table 6. Torsion angles [°] for 1.

________________________________________________________________

C(101)#1-C(101)-C(102)-C(111) 2.7(7)

C(112)-C(101)-C(102)-C(111) 178.6(4)

C(101)#1-C(101)-C(102)-C(103) -170.2(5)

C(112)-C(101)-C(102)-C(103) 5.7(6)

C(111)-C(102)-C(103)-C(104) -7.5(6)

C(101)-C(102)-C(103)-C(104) 165.4(4)

C(102)-C(103)-C(104)-C(105) -3.9(6)

C(103)-C(104)-C(105)-C(110) 7.0(6)

C(103)-C(104)-C(105)-C(106) -168.5(4)

C(110)-C(105)-C(106)-C(107) 1.2(6)

C(104)-C(105)-C(106)-C(107) 176.8(4)

C(105)-C(106)-C(107)-C(108) -1.8(7)

C(106)-C(107)-C(108)-C(109) -0.9(6)

C(106)-C(107)-C(108)-O(116) 180.0(4)

O(116)-C(108)-C(109)-C(110) -176.9(3)

C(107)-C(108)-C(109)-C(110) 4.0(6)

C(108)-C(109)-C(110)-C(105) -4.6(6)

C(108)-C(109)-C(110)-C(111) -179.3(3)

C(106)-C(105)-C(110)-C(109) 2.0(5)

C(104)-C(105)-C(110)-C(109) -173.7(4)

C(106)-C(105)-C(110)-C(111) 176.9(4)

C(104)-C(105)-C(110)-C(111) 1.3(5)

C(103)-C(102)-C(111)-C(111)#1 -169.5(4)

C(101)-C(102)-C(111)-C(111)#1 17.5(6)

C(103)-C(102)-C(111)-C(110) 15.4(5)

C(101)-C(102)-C(111)-C(110) -157.7(3)

C(109)-C(110)-C(111)-C(102) 162.5(4)

C(105)-C(110)-C(111)-C(102) -12.3(5)

C(109)-C(110)-C(111)-C(111)#1 -12.4(6)

C(105)-C(110)-C(111)-C(111)#1 172.9(4)

C(101)#1-C(101)-C(112)-O(113) -119.7(6)

C(102)-C(101)-C(112)-O(113) 64.5(6)

C(101)#1-C(101)-C(112)-O(114) 61.8(6)

C(102)-C(101)-C(112)-O(114) -114.1(4)

O(113)-C(112)-O(114)-C(115) 0.4(7)

C(101)-C(112)-O(114)-C(115) 179.0(4)

C(109)-C(108)-O(116)-C(117) 7.1(6)

C(107)-C(108)-O(116)-C(117) -173.7(4)

C(201)#2-C(201)-C(202)-C(211) 0.1(7)

C(212)-C(201)-C(202)-C(211) -174.3(4)

C(201)#2-C(201)-C(202)-C(203) 177.2(5)

C(212)-C(201)-C(202)-C(203) 2.8(6)

C(211)-C(202)-C(203)-C(204) 4.3(6)

C(201)-C(202)-C(203)-C(204) -172.8(4)

C(202)-C(203)-C(204)-C(205) 6.7(7)

C(203)-C(204)-C(205)-C(210) -5.7(6)

C(203)-C(204)-C(205)-C(206) 169.4(4)

C(210)-C(205)-C(206)-C(207) 4.2(7)

C(204)-C(205)-C(206)-C(207) -171.0(4)

C(205)-C(206)-C(207)-C(208) 0.8(7)

C(206)-C(207)-C(208)-O(216) 177.0(4)

C(206)-C(207)-C(208)-C(209) -2.2(6)

O(216)-C(208)-C(209)-C(210) 179.3(4)

C(207)-C(208)-C(209)-C(210) -1.6(6)

C(208)-C(209)-C(210)-C(205) 6.6(6)

C(208)-C(209)-C(210)-C(211) 180.0(4)

C(204)-C(205)-C(210)-C(209) 167.6(4)

C(206)-C(205)-C(210)-C(209) -7.7(6)

C(204)-C(205)-C(210)-C(211) -6.1(6)

C(206)-C(205)-C(210)-C(211) 178.7(3)

C(203)-C(202)-C(211)-C(211)#2 167.3(4)

C(201)-C(202)-C(211)-C(211)#2 -15.5(6)

C(203)-C(202)-C(211)-C(210) -15.5(5)

C(201)-C(202)-C(211)-C(210) 161.6(3)

C(209)-C(210)-C(211)-C(202) -157.0(3)

C(205)-C(210)-C(211)-C(202) 16.4(5)

C(209)-C(210)-C(211)-C(211)#2 20.0(6)

C(205)-C(210)-C(211)-C(211)#2 -166.6(4)

C(201)#2-C(201)-C(212)-O(213) 125.5(6)

C(202)-C(201)-C(212)-O(213) -60.1(6)

C(201)#2-C(201)-C(212)-O(214) -56.0(6)

C(202)-C(201)-C(212)-O(214) 118.4(4)

O(213)-C(212)-O(214)-C(215) -1.1(7)

C(201)-C(212)-O(214)-C(215) -179.7(4)

C(209)-C(208)-O(216)-C(217) -6.5(6)

C(207)-C(208)-O(216)-C(217) 174.3(4)

________________________________________________________________

Symmetry transformations used to generate equivalent atoms:

#1 -x+1,y,-z+1/2 #2 -x+2,y,-z+1/2

IIIa. X-Ray difracction study of ppalladium complex 10 - This structure has been

deposited at the Cambridge Crystallographic Database with deposition number CCDC

605851

Mercury view of the structure of complex 10

Mercury view of the packing of 10 (unit cell)

Mercury view of the packing mode of 10 along three axis

Table 1. Crystal data and structure refinement for 10.

Empirical formula C50 H38 O4 P2 Pd

Formula weight 871.14

Temperature 293(2) K

Wavelength 0.71073 Å

Crystal system triclinic

Space group P-1

Unit cell dimensions a = 11.147(4) Å α= 103.430(5)°.

b = 13.957(5) Å β= 103.367(5)°.

c = 14.524(5) Å γ = 110.489(5)°.

Volume 1934.1(12) Å3

Z 2

Density (calculated) 1.496 Mg/m3

Absorption coefficient 0.611 mm-1

F(000) 892

Crystal size 0.34x 0.13 x 0.13 mm3

Theta range for data collection 1.53 to 26.42°.

Index ranges -13<=h<=13, -17<=k<=16, 0<=l<=18

Reflections collected 7856

Independent reflections 7856 [R(int) = 0.0609]

Completeness to theta = 26.42° 98.8 %

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 7856 / 0 / 516

Goodness-of-fit on F2 1.031

Final R indices [I>2sigma(I)] R1 = 0.0496, wR2 = 0.1241

R indices (all data) R1 = 0.0791, wR2 = 0.1440

Largest diff. peak and hole 2.579 and -2.641 e.Å-3

Table 2. Atomic coordinates ( x 104) and equivalent isotropic displacement parameters (Å2x 103) for 10.

U(eq) is defined as one third of the trace of the orthogonalized Uij tensor.

________________________________________________________________________________

x y z U(eq)

________________________________________________________________________________

Pd(1) 2040(1) 2150(1) 2747(1) 12(1)

P(2) 3669(1) 2802(1) 2038(1) 12(1)

C(3) 2732(4) 2723(4) 780(3) 13(1)

C(4) 2262(4) 3497(4) 630(3) 12(1)

C(5) 2568(4) 4485(4) 1492(3) 12(1)

C(6) 1943(4) 4395(4) 2205(3) 12(1)

P(7) 802(1) 3066(1) 2203(1) 11(1)

C(8) 2286(5) 1744(4) -37(3) 16(1)

C(9) 1470(5) 1567(4) -969(3) 15(1)

C(10) 1057(5) 2369(4) -1167(3) 16(1)

C(11) 1443(4) 3340(4) -364(3) 12(1)

C(12) 3556(4) 5522(4) 1589(3) 13(1)

C(13) 3962(5) 6436(4) 2459(3) 15(1)

C(14) 3330(5) 6309(4) 3199(3) 16(1)

C(15) 2332(5) 5325(4) 3060(3) 15(1)

C(16) 233(5) 2197(4) -2138(3) 21(1)

C(17) -206(5) 2964(4) -2320(3) 20(1)

C(18) 163(5) 3924(4) -1530(3) 19(1)

C(19) 963(5) 4119(4) -574(3) 16(1)

C(20) 4202(5) 5669(4) 860(3) 15(1)

C(21) 5205(5) 6662(4) 1012(4) 18(1)

C(22) 5617(5) 7558(4) 1881(4) 20(1)

C(23) 5014(5) 7447(4) 2593(4) 18(1)

C(24) 4682(4) 2031(4) 1835(3) 14(1)

C(25) 5030(5) 1609(4) 2590(4) 18(1)

C(26) 5849(5) 1054(4) 2540(4) 25(1)

C(27) 6297(5) 890(4) 1738(4) 26(1)

C(28) 5967(5) 1314(4) 994(4) 22(1)

C(29) 5176(5) 1896(4) 1046(3) 19(1)

C(30) 5001(5) 4200(4) 2642(3) 15(1)

C(31) 5875(5) 4661(4) 2164(4) 19(1)

C(32) 6903(5) 5706(4) 2648(4) 23(1)

C(33) 7054(5) 6296(4) 3606(4) 27(1)

C(34) 6195(5) 5832(4) 4094(4) 25(1)

C(35) 5172(5) 4791(4) 3613(3) 19(1)

C(36) 1098(5) 1190(4) 3453(3) 15(1)

C(37) 2225(5) 1150(4) 3564(3) 16(1)

C(38) -202(5) 781(4) 3656(3) 16(1)

O(38) -1299(4) 238(3) 3017(3) 29(1)

O(39) 6(4) 1105(3) 4644(3) 25(1)

C(40) -1227(6) 775(6) 4882(4) 36(1)

C(41) 3136(5) 709(4) 3998(3) 16(1)

O(41) 4103(4) 1189(3) 4770(3) 28(1)

O(42) 2767(3) -319(3) 3424(2) 20(1)

C(43) 3633(5) -826(4) 3770(4) 25(1)

C(44) -492(4) 2412(4) 952(3) 13(1)

C(45) -1115(5) 2966(4) 478(3) 17(1)

C(46) -2082(5) 2448(4) -475(4) 21(1)

C(47) -2420(5) 1363(4) -987(4) 23(1)

C(48) -1789(5) 814(4) -539(4) 22(1)

C(49) -846(5) 1323(4) 429(3) 17(1)

C(50) -75(5) 3395(4) 3074(3) 15(1)

C(51) -1186(5) 3633(4) 2825(4) 20(1)

C(52) -1842(5) 3798(4) 3509(4) 23(1)

C(53) -1407(5) 3722(4) 4449(4) 22(1)

C(54) -284(5) 3512(4) 4719(4) 22(1)

C(55) 377(5) 3343(4) 4036(3) 19(1)

________________________________________________________________________________

Table 3. Bond lengths [Å] and angles [°] for 10.

_____________________________________________________

Pd(1)-C(36) 2.025(4)

Pd(1)-C(37) 2.064(4)

Pd(1)-P(2) 2.3081(13)

Pd(1)-P(7) 2.3167(12)

P(2)-C(30) 1.832(5)

P(2)-C(24) 1.839(5)

P(2)-C(3) 1.839(4)

C(3)-C(4) 1.393(6)

C(3)-C(8) 1.421(6)

C(4)-C(11) 1.439(6)

C(4)-C(5) 1.503(6)

C(5)-C(6) 1.380(6)

C(5)-C(12) 1.430(6)

C(6)-C(15) 1.423(6)

C(6)-P(7) 1.844(4)

P(7)-C(44) 1.819(5)

P(7)-C(50) 1.839(5)

C(8)-C(9) 1.356(6)

C(9)-C(10) 1.414(6)

C(10)-C(16) 1.407(6)

C(10)-C(11) 1.417(6)

C(11)-C(19) 1.430(6)

C(12)-C(13) 1.419(6)

C(12)-C(20) 1.426(6)

C(13)-C(23) 1.419(7)

C(13)-C(14) 1.426(6)

C(14)-C(15) 1.364(7)

C(16)-C(17) 1.375(7)

C(17)-C(18) 1.401(7)

C(18)-C(19) 1.371(6)

C(20)-C(21) 1.371(6)

C(21)-C(22) 1.402(7)

C(22)-C(23) 1.366(7)

C(24)-C(29) 1.384(6)

C(24)-C(25) 1.400(6)

C(25)-C(26) 1.393(7)

C(26)-C(27) 1.372(7)

C(27)-C(28) 1.385(7)

C(28)-C(29) 1.395(7)

C(30)-C(35) 1.389(6)

C(30)-C(31) 1.389(7)

C(31)-C(32) 1.383(7)

C(32)-C(33) 1.381(8)

C(33)-C(34) 1.390(8)

C(34)-C(35) 1.377(7)

C(36)-C(37) 1.251(7)

C(36)-C(38) 1.487(6)

C(37)-C(41) 1.460(6)

C(38)-O(38) 1.196(6)

C(38)-O(39) 1.337(6)

O(39)-C(40) 1.439(6)

C(41)-O(41) 1.206(6)

C(41)-O(42) 1.340(6)

O(42)-C(43) 1.451(5)

C(44)-C(49) 1.396(6)

C(44)-C(45) 1.399(6)

C(45)-C(46) 1.379(7)

C(46)-C(47) 1.392(7)

C(47)-C(48) 1.379(7)

C(48)-C(49) 1.385(7)

C(50)-C(51) 1.383(6)

C(50)-C(55) 1.399(6)

C(51)-C(52) 1.387(7)

C(52)-C(53) 1.380(7)

C(53)-C(54) 1.375(7)

C(54)-C(55) 1.390(7)

C(36)-Pd(1)-C(37) 35.61(19)

C(36)-Pd(1)-P(2) 154.36(13)

C(37)-Pd(1)-P(2) 119.33(14)

C(36)-Pd(1)-P(7) 110.80(14)

C(37)-Pd(1)-P(7) 146.04(14)

P(2)-Pd(1)-P(7) 94.57(5)

C(30)-P(2)-C(24) 101.5(2)

C(30)-P(2)-C(3) 105.7(2)

C(24)-P(2)-C(3) 106.0(2)

C(30)-P(2)-Pd(1) 120.11(15)

C(24)-P(2)-Pd(1) 116.51(15)

C(3)-P(2)-Pd(1) 105.94(14)

C(4)-C(3)-C(8) 119.0(4)

C(4)-C(3)-P(2) 122.5(3)

C(8)-C(3)-P(2) 117.6(3)

C(3)-C(4)-C(11) 119.6(4)

C(3)-C(4)-C(5) 121.3(4)

C(11)-C(4)-C(5) 119.0(4)

C(6)-C(5)-C(12) 120.0(4)

C(6)-C(5)-C(4) 120.8(4)

C(12)-C(5)-C(4) 119.1(4)

C(5)-C(6)-C(15) 119.8(4)

C(5)-C(6)-P(7) 122.3(3)

C(15)-C(6)-P(7) 117.3(3)

C(44)-P(7)-C(50) 105.9(2)

C(44)-P(7)-C(6) 105.1(2)

C(50)-P(7)-C(6) 105.0(2)

C(44)-P(7)-Pd(1) 118.18(15)

C(50)-P(7)-Pd(1) 111.03(15)

C(6)-P(7)-Pd(1) 110.70(14)

C(9)-C(8)-C(3) 121.8(4)

C(8)-C(9)-C(10) 120.7(4)

C(16)-C(10)-C(11) 120.0(4)

C(16)-C(10)-C(9) 120.9(4)

C(11)-C(10)-C(9) 119.0(4)

C(10)-C(11)-C(19) 118.1(4)

C(10)-C(11)-C(4) 119.5(4)

C(19)-C(11)-C(4) 122.4(4)

C(13)-C(12)-C(20) 118.1(4)

C(13)-C(12)-C(5) 119.4(4)

C(20)-C(12)-C(5) 122.4(4)

C(23)-C(13)-C(12) 119.6(4)

C(23)-C(13)-C(14) 121.3(4)

C(12)-C(13)-C(14) 119.1(4)

C(15)-C(14)-C(13) 120.3(4)

C(14)-C(15)-C(6) 121.2(4)

C(17)-C(16)-C(10) 120.7(4)

C(16)-C(17)-C(18) 119.7(4)

C(19)-C(18)-C(17) 121.2(4)

C(18)-C(19)-C(11) 120.3(4)

C(21)-C(20)-C(12) 120.5(4)

C(20)-C(21)-C(22) 121.2(4)

C(23)-C(22)-C(21) 119.9(4)

C(22)-C(23)-C(13) 120.8(4)

C(29)-C(24)-C(25) 118.9(4)

C(29)-C(24)-P(2) 125.6(4)

C(25)-C(24)-P(2) 115.4(3)

C(26)-C(25)-C(24) 120.4(4)

C(27)-C(26)-C(25) 120.4(5)

C(26)-C(27)-C(28) 119.5(5)

C(27)-C(28)-C(29) 120.8(5)

C(24)-C(29)-C(28) 119.9(5)

C(35)-C(30)-C(31) 119.5(4)

C(35)-C(30)-P(2) 119.2(4)

C(31)-C(30)-P(2) 121.2(4)

C(32)-C(31)-C(30) 120.2(4)

C(33)-C(32)-C(31) 120.0(5)

C(32)-C(33)-C(34) 120.0(5)

C(35)-C(34)-C(33) 120.0(5)

C(34)-C(35)-C(30) 120.3(5)

C(37)-C(36)-C(38) 145.0(4)

C(37)-C(36)-Pd(1) 73.9(3)

C(38)-C(36)-Pd(1) 141.1(3)

C(36)-C(37)-C(41) 145.9(5)

C(36)-C(37)-Pd(1) 70.5(3)

C(41)-C(37)-Pd(1) 143.5(3)

O(38)-C(38)-O(39) 124.2(4)

O(38)-C(38)-C(36) 124.3(4)

O(39)-C(38)-C(36) 111.5(4)

C(38)-O(39)-C(40) 113.8(4)

O(41)-C(41)-O(42) 123.2(4)

O(41)-C(41)-C(37) 125.6(4)

O(42)-C(41)-C(37) 111.2(4)

C(41)-O(42)-C(43) 115.8(4)

C(49)-C(44)-C(45) 118.5(4)

C(49)-C(44)-P(7) 118.8(3)

C(45)-C(44)-P(7) 122.7(4)

C(46)-C(45)-C(44) 121.2(5)

C(45)-C(46)-C(47) 119.5(5)

C(48)-C(47)-C(46) 119.9(4)

C(47)-C(48)-C(49) 120.7(5)

C(48)-C(49)-C(44) 120.2(4)

C(51)-C(50)-C(55) 118.2(4)

C(51)-C(50)-P(7) 124.5(4)

C(55)-C(50)-P(7) 117.3(3)

C(50)-C(51)-C(52) 120.6(4)

C(53)-C(52)-C(51) 120.8(4)

C(54)-C(53)-C(52) 119.5(4)

C(53)-C(54)-C(55) 120.0(5)

C(54)-C(55)-C(50) 120.9(4)

_____________________________________________________________

Symmetry transformations used to generate equivalent atoms:

Table 4. Anisotropic displacement parameters (Å2x 103)for 10. The anisotropic displacement factor

exponent takes the form: -2π2[ h2a*2U11 + ... + 2 h k a* b* U12 ]

______________________________________________________________________________

U11 U22 U33 U23 U13 U12

______________________________________________________________________________

Pd(1) 12(1) 14(1) 17(1) 9(1) 7(1) 10(1)

P(2) 12(1) 13(1) 16(1) 7(1) 6(1) 9(1)

C(3) 10(2) 17(2) 18(2) 9(2) 8(2) 10(2)

C(4) 11(2) 13(2) 17(2) 6(2) 8(2) 8(2)

C(5) 15(2) 13(2) 14(2) 5(2) 5(2) 12(2)

C(6) 10(2) 13(2) 18(2) 9(2) 6(2) 7(2)

P(7) 11(1) 13(1) 15(1) 7(1) 6(1) 9(1)

C(8) 16(2) 14(2) 22(2) 8(2) 10(2) 8(2)

C(9) 16(2) 8(2) 19(2) 2(2) 7(2) 3(2)

C(10) 13(2) 17(2) 21(2) 8(2) 10(2) 8(2)

C(11) 11(2) 14(2) 15(2) 8(2) 7(2) 7(2)

C(12) 11(2) 14(2) 18(2) 9(2) 4(2) 10(2)

C(13) 13(2) 18(2) 19(2) 7(2) 6(2) 12(2)

C(14) 18(2) 17(2) 18(2) 5(2) 7(2) 12(2)

C(15) 16(2) 19(2) 15(2) 7(2) 9(2) 11(2)

C(16) 21(3) 22(3) 16(2) 4(2) 5(2) 8(2)

C(17) 18(2) 23(3) 16(2) 10(2) 3(2) 8(2)

C(18) 18(2) 22(3) 23(2) 13(2) 7(2) 12(2)

C(19) 16(2) 15(2) 19(2) 7(2) 5(2) 7(2)

C(20) 18(2) 13(2) 16(2) 6(2) 7(2) 8(2)

C(21) 16(2) 20(2) 25(2) 15(2) 11(2) 9(2)

C(22) 14(2) 14(2) 29(3) 10(2) 6(2) 3(2)

C(23) 17(2) 14(2) 22(2) 3(2) 4(2) 9(2)

C(24) 13(2) 12(2) 20(2) 6(2) 7(2) 8(2)

C(25) 17(2) 24(3) 25(2) 13(2) 13(2) 14(2)

C(26) 19(3) 31(3) 40(3) 22(3) 14(2) 18(2)

C(27) 18(3) 23(3) 47(3) 14(2) 14(2) 16(2)

C(28) 16(2) 23(3) 30(3) 4(2) 12(2) 10(2)

C(29) 16(2) 23(3) 19(2) 6(2) 7(2) 11(2)

C(30) 16(2) 16(2) 19(2) 11(2) 6(2) 10(2)

C(31) 18(2) 24(3) 18(2) 7(2) 4(2) 14(2)

C(32) 13(2) 30(3) 27(3) 16(2) 4(2) 9(2)

C(33) 19(3) 21(3) 38(3) 12(2) 0(2) 10(2)

C(34) 23(3) 23(3) 24(3) 5(2) 2(2) 10(2)

C(35) 20(2) 23(3) 18(2) 11(2) 7(2) 13(2)

C(36) 23(2) 13(2) 18(2) 11(2) 12(2) 12(2)

C(37) 23(3) 18(2) 14(2) 10(2) 8(2) 13(2)

C(38) 18(2) 15(2) 23(2) 9(2) 12(2) 12(2)

O(38) 19(2) 33(2) 27(2) 2(2) 9(2) 8(2)

O(39) 21(2) 37(2) 22(2) 12(2) 12(2) 13(2)

C(40) 28(3) 58(4) 31(3) 20(3) 21(3) 21(3)

C(41) 18(2) 17(2) 23(2) 15(2) 13(2) 13(2)

O(41) 29(2) 28(2) 24(2) 6(2) 0(2) 17(2)

O(42) 20(2) 17(2) 27(2) 9(2) 4(2) 16(1)

C(43) 26(3) 23(3) 36(3) 16(2) 9(2) 18(2)

C(44) 12(2) 14(2) 17(2) 9(2) 8(2) 6(2)

C(45) 18(2) 19(2) 21(2) 11(2) 9(2) 11(2)

C(46) 17(2) 29(3) 22(2) 14(2) 8(2) 11(2)

C(47) 15(2) 27(3) 16(2) 7(2) 1(2) 1(2)

C(48) 25(3) 14(2) 22(2) 2(2) 9(2) 4(2)

C(49) 18(2) 16(2) 23(2) 11(2) 11(2) 9(2)

C(50) 16(2) 13(2) 19(2) 6(2) 8(2) 8(2)

C(51) 15(2) 28(3) 20(2) 9(2) 7(2) 14(2)

C(52) 13(2) 28(3) 30(3) 5(2) 8(2) 15(2)

C(53) 25(3) 23(3) 23(2) 4(2) 16(2) 13(2)

C(54) 32(3) 22(3) 19(2) 9(2) 11(2) 19(2)

C(55) 21(2) 20(2) 21(2) 7(2) 8(2) 15(2)

______________________________________________________________________________

Table 5. Torsion angles [°] for 10.

________________________________________________________________

C(36)-Pd(1)-P(2)-C(30) -111.6(3)

C(37)-Pd(1)-P(2)-C(30) -101.4(2)

P(7)-Pd(1)-P(2)-C(30) 76.61(17)

C(36)-Pd(1)-P(2)-C(24) 11.5(4)

C(37)-Pd(1)-P(2)-C(24) 21.7(2)

P(7)-Pd(1)-P(2)-C(24) -160.30(17)

C(36)-Pd(1)-P(2)-C(3) 129.0(3)

C(37)-Pd(1)-P(2)-C(3) 139.2(2)

P(7)-Pd(1)-P(2)-C(3) -42.76(16)

C(30)-P(2)-C(3)-C(4) -48.8(4)

C(24)-P(2)-C(3)-C(4) -155.9(4)

Pd(1)-P(2)-C(3)-C(4) 79.7(4)

C(30)-P(2)-C(3)-C(8) 141.8(3)

C(24)-P(2)-C(3)-C(8) 34.6(4)

Pd(1)-P(2)-C(3)-C(8) -89.7(3)

C(8)-C(3)-C(4)-C(11) -5.8(6)

P(2)-C(3)-C(4)-C(11) -175.1(3)

C(8)-C(3)-C(4)-C(5) 172.9(4)

P(2)-C(3)-C(4)-C(5) 3.6(6)

C(3)-C(4)-C(5)-C(6) -71.7(6)

C(11)-C(4)-C(5)-C(6) 107.0(5)

C(3)-C(4)-C(5)-C(12) 106.0(5)

C(11)-C(4)-C(5)-C(12) -75.3(5)

C(12)-C(5)-C(6)-C(15) -2.9(6)

C(4)-C(5)-C(6)-C(15) 174.7(4)

C(12)-C(5)-C(6)-P(7) -173.3(3)

C(4)-C(5)-C(6)-P(7) 4.4(6)

C(5)-C(6)-P(7)-C(44) -54.9(4)

C(15)-C(6)-P(7)-C(44) 134.5(3)

C(5)-C(6)-P(7)-C(50) -166.4(4)

C(15)-C(6)-P(7)-C(50) 23.0(4)

C(5)-C(6)-P(7)-Pd(1) 73.7(4)

C(15)-C(6)-P(7)-Pd(1) -96.9(3)

C(36)-Pd(1)-P(7)-C(44) -89.4(2)

C(37)-Pd(1)-P(7)-C(44) -96.3(3)

P(2)-Pd(1)-P(7)-C(44) 86.84(16)

C(36)-Pd(1)-P(7)-C(50) 33.2(2)

C(37)-Pd(1)-P(7)-C(50) 26.3(3)

P(2)-Pd(1)-P(7)-C(50) -150.57(16)

C(36)-Pd(1)-P(7)-C(6) 149.4(2)

C(37)-Pd(1)-P(7)-C(6) 142.5(3)

P(2)-Pd(1)-P(7)-C(6) -34.36(16)

C(4)-C(3)-C(8)-C(9) 3.2(7)

P(2)-C(3)-C(8)-C(9) 173.1(4)

C(3)-C(8)-C(9)-C(10) 1.6(7)

C(8)-C(9)-C(10)-C(16) 178.7(4)

C(8)-C(9)-C(10)-C(11) -3.6(7)

C(16)-C(10)-C(11)-C(19) 0.5(6)

C(9)-C(10)-C(11)-C(19) -177.3(4)

C(16)-C(10)-C(11)-C(4) 178.7(4)

C(9)-C(10)-C(11)-C(4) 1.0(6)

C(3)-C(4)-C(11)-C(10) 3.7(6)

C(5)-C(4)-C(11)-C(10) -175.0(4)

C(3)-C(4)-C(11)-C(19) -178.1(4)

C(5)-C(4)-C(11)-C(19) 3.2(6)

C(6)-C(5)-C(12)-C(13) 4.6(6)

C(4)-C(5)-C(12)-C(13) -173.0(4)

C(6)-C(5)-C(12)-C(20) -178.1(4)

C(4)-C(5)-C(12)-C(20) 4.3(6)

C(20)-C(12)-C(13)-C(23) -2.0(6)

C(5)-C(12)-C(13)-C(23) 175.4(4)

C(20)-C(12)-C(13)-C(14) -180.0(4)

C(5)-C(12)-C(13)-C(14) -2.6(6)

C(23)-C(13)-C(14)-C(15) -179.1(4)

C(12)-C(13)-C(14)-C(15) -1.2(7)

C(13)-C(14)-C(15)-C(6) 3.0(7)

C(5)-C(6)-C(15)-C(14) -1.0(7)

P(7)-C(6)-C(15)-C(14) 169.9(4)

C(11)-C(10)-C(16)-C(17) 0.0(7)

C(9)-C(10)-C(16)-C(17) 177.7(5)

C(10)-C(16)-C(17)-C(18) -0.4(7)

C(16)-C(17)-C(18)-C(19) 0.3(7)

C(17)-C(18)-C(19)-C(11) 0.2(7)

C(10)-C(11)-C(19)-C(18) -0.5(7)

C(4)-C(11)-C(19)-C(18) -178.7(4)

C(13)-C(12)-C(20)-C(21) 1.3(6)

C(5)-C(12)-C(20)-C(21) -176.0(4)

C(12)-C(20)-C(21)-C(22) -0.2(7)

C(20)-C(21)-C(22)-C(23) -0.1(7)

C(21)-C(22)-C(23)-C(13) -0.7(7)

C(12)-C(13)-C(23)-C(22) 1.8(7)

C(14)-C(13)-C(23)-C(22) 179.7(4)

C(30)-P(2)-C(24)-C(29) -81.5(4)

C(3)-P(2)-C(24)-C(29) 28.7(5)

Pd(1)-P(2)-C(24)-C(29) 146.2(4)

C(30)-P(2)-C(24)-C(25) 94.6(4)

C(3)-P(2)-C(24)-C(25) -155.3(4)

Pd(1)-P(2)-C(24)-C(25) -37.7(4)

C(29)-C(24)-C(25)-C(26) -0.7(7)

P(2)-C(24)-C(25)-C(26) -177.0(4)

C(24)-C(25)-C(26)-C(27) -1.6(8)

C(25)-C(26)-C(27)-C(28) 2.2(8)

C(26)-C(27)-C(28)-C(29) -0.6(8)

C(25)-C(24)-C(29)-C(28) 2.2(7)

P(2)-C(24)-C(29)-C(28) 178.2(4)

C(27)-C(28)-C(29)-C(24) -1.6(7)

C(24)-P(2)-C(30)-C(35) -118.5(4)

C(3)-P(2)-C(30)-C(35) 131.1(4)

Pd(1)-P(2)-C(30)-C(35) 11.6(4)

C(24)-P(2)-C(30)-C(31) 58.9(4)

C(3)-P(2)-C(30)-C(31) -51.5(4)

Pd(1)-P(2)-C(30)-C(31) -171.0(3)

C(35)-C(30)-C(31)-C(32) -0.5(7)

P(2)-C(30)-C(31)-C(32) -177.9(4)

C(30)-C(31)-C(32)-C(33) -0.5(7)

C(31)-C(32)-C(33)-C(34) 1.5(7)

C(32)-C(33)-C(34)-C(35) -1.5(8)

C(33)-C(34)-C(35)-C(30) 0.5(7)

C(31)-C(30)-C(35)-C(34) 0.5(7)

P(2)-C(30)-C(35)-C(34) 178.0(4)

P(2)-Pd(1)-C(36)-C(37) 15.4(5)

P(7)-Pd(1)-C(36)-C(37) -173.4(3)

C(37)-Pd(1)-C(36)-C(38) -178.1(7)

P(2)-Pd(1)-C(36)-C(38) -162.7(4)

P(7)-Pd(1)-C(36)-C(38) 8.5(6)

C(38)-C(36)-C(37)-C(41) -3.0(14)

Pd(1)-C(36)-C(37)-C(41) 179.1(8)

C(38)-C(36)-C(37)-Pd(1) 177.9(8)

P(2)-Pd(1)-C(37)-C(36) -172.4(2)

P(7)-Pd(1)-C(37)-C(36) 11.1(4)

C(36)-Pd(1)-C(37)-C(41) -179.1(8)

P(2)-Pd(1)-C(37)-C(41) 8.4(6)

P(7)-Pd(1)-C(37)-C(41) -168.0(4)

C(37)-C(36)-C(38)-O(38) -116.0(8)

Pd(1)-C(36)-C(38)-O(38) 60.8(8)

C(37)-C(36)-C(38)-O(39) 64.6(9)

Pd(1)-C(36)-C(38)-O(39) -118.6(5)

O(38)-C(38)-O(39)-C(40) -2.2(7)

C(36)-C(38)-O(39)-C(40) 177.2(4)

C(36)-C(37)-C(41)-O(41) -100.0(9)

Pd(1)-C(37)-C(41)-O(41) 78.5(7)

C(36)-C(37)-C(41)-O(42) 80.1(9)

Pd(1)-C(37)-C(41)-O(42) -101.4(6)

O(41)-C(41)-O(42)-C(43) -1.7(7)

C(37)-C(41)-O(42)-C(43) 178.1(4)

C(50)-P(7)-C(44)-C(49) -115.2(4)

C(6)-P(7)-C(44)-C(49) 134.0(4)

Pd(1)-P(7)-C(44)-C(49) 10.0(4)

C(50)-P(7)-C(44)-C(45) 67.1(4)

C(6)-P(7)-C(44)-C(45) -43.7(4)

Pd(1)-P(7)-C(44)-C(45) -167.7(3)

C(49)-C(44)-C(45)-C(46) 1.6(7)

P(7)-C(44)-C(45)-C(46) 179.3(4)

C(44)-C(45)-C(46)-C(47) -1.8(7)

C(45)-C(46)-C(47)-C(48) 0.1(7)

C(46)-C(47)-C(48)-C(49) 1.7(7)

C(47)-C(48)-C(49)-C(44) -1.9(7)

C(45)-C(44)-C(49)-C(48) 0.2(7)

P(7)-C(44)-C(49)-C(48) -177.5(4)

C(44)-P(7)-C(50)-C(51) -30.2(5)

C(6)-P(7)-C(50)-C(51) 80.6(4)

Pd(1)-P(7)-C(50)-C(51) -159.7(4)

C(44)-P(7)-C(50)-C(55) 146.3(4)

C(6)-P(7)-C(50)-C(55) -102.8(4)

Pd(1)-P(7)-C(50)-C(55) 16.9(4)

C(55)-C(50)-C(51)-C(52) -1.0(7)

P(7)-C(50)-C(51)-C(52) 175.6(4)

C(50)-C(51)-C(52)-C(53) -0.4(8)

C(51)-C(52)-C(53)-C(54) 2.0(8)

C(52)-C(53)-C(54)-C(55) -2.1(8)

C(53)-C(54)-C(55)-C(50) 0.7(8)

C(51)-C(50)-C(55)-C(54) 0.9(7)

P(7)-C(50)-C(55)-C(54) -175.9(4)

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Symmetry transformations used to generate equivalent atoms:

IV. KINETICS OF THE RACEMIZATION PROCESS

A sample of non-racemic 1 dissolved in 1:3 CH2Cl2/hexane (1 mL) was prepared andheated to 45 ºC by immersion in a thermostatic bath. Once the constant temperature was reached, an aliquot was taken, cooled to room temperature, and quickly analyzed byHPLC [OL-86 (CH2Cl2/hexane 35:65)] to determine the initial enantiomeric excess.This process was repeated at four different intervals of time. Representation ofln(ee0/eet) against time resulted in a first order plot, from which the enantiomerizationreaction rate k was determined, from the kinetic ecuation: ln(ee0/eet) = 2k x t]. The same procedure was repeated at constant temperatures 60, 65 and 75 ºC.

45 ºC

t (min) ee (%) ln(eeo/eet)

0 68

61 61 0,10863

123 57 0,17646

175 54 0,23052

240 51 0,28768

300 47 0,36936

60 ºC

t (min) ee (%) ln(eeo/eet)

0 68

30 57 0,17646

62 47 0,36936

90 40 0,53063

120 36 0,63599

150 30 0,81831

65 ºC

t (min) ee (%) ln(eeo/eet)

0 73

31 55 0,28313

59 43 0,52926

91 32 0,82472

120 24 1,11241

153 17 1,45725

75 ºC

t (min) ee (%) ln(eeo/eet)

0 65

16 53 0,2041

30 39 0,51083

46 29 0,80709

60 24 0,99633

70 15 1,46634

0

0,2

0,4

0,6

0,8

1

1,2

1,4

1,6

0 50 100 150 200 250 300 350

t/min

ln(e

eo

/ee

t) 45

60

65

75

T = 45 ºC y = 1,063E-03x + 4,333E-02 k = 8,858E-06 s-1

T = 60 ºC y = 5,205E-03x + 3,563E-02 k = 43,375E-06 s-1

T = 65 ºC y = 9,617E-03x - 3,191E-02 k = 80,142E-06 s-1

T = 75 ºC y = 2,152E-02x - 1,587E-01 k = 179,33E-06 s-1

Eyring Plot

T (K) k (s-1

) ln (k/T) 1/T (K-1

)

318,15 0,000008858 -17,3967 0,003143

333,15 0,000043375 -15,8542 0,003002

338,15 0,000080142 -15,2552 0,002957

348,15 0,00017933 -14,4785 0,002872

-18

-17

-16

-15

-14

-13

-12

2,8E-03 2,9E-03 3,0E-03 3,1E-03 3,2E-03

1/T

ln (

k/T

)

y = -10894x + 16,866

ΔΔH� = 21.65 kcal/mol

ΔΔS� = -13.70 cal/mol K

ΔΔG� (298K) = 25.73 kcal/mol