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Electronic Supplementary Information
An efficient catalytic synthesis and characterization of new styryl-ferrocenes
and their trans-π-conjugated organosilicon materials
M. Majchrzaka*, S. Kosteraa, M. Grzelaka, B. Marciniec*a,b and M. Kubickia
aFaculty of Chemistry, Adam Mickiewicz University in Poznan, Umultowska 89b, 61-614 Poznan, PolandbCenter for Advanced Technology, Adam Mickiewicz University in Poznan, Umultowska 89c, 61-614 Poznan, Poland
Table of contents
I. Synthesis procedure of palladium complex
II. X-Ray structure determination
III. MS spectra
IV. GPC chromatograms
V. NMR Spectra
Procedure for the synthesis of Palladium(0) Complex
The title compound was synthesized according to the new procedure presented below.
Bis(tris(o-tolyl)phosphine)(dibenzylideneacetone)palladium(0) – [Pd(2-dba)(P(o-tolyl)3)2]32 (3):
Pd(dba)2 (0.3 g, 5.22 x 10-4 mol), tris(o-tolyl)phosphine (0.321 g, 1.054 x 10-3 mol) were placed in a
Schlenk flask (25 mL) and degassed for one minute. Afterwards, 4 mL toluene (0.125M) was
introduced into vigorously stirred solids of substrates and the final mixture was left for 8h at room
temperature to give a yellow-orange solution. The excess of the solvent was evaporated under
reduced pressure. The procedure was followed by the addition of hexane. As a result a yellow-orange
precipitate was observed. Next, the precipitate was filtered (‘canula’ system), washed with cold
hexane (4 x 10 mL) and dried in vacuum for 2h. The crude product was obtained with 93% (460 mg,
yellow-orange solid) yield. Elemental analyses calcd. for C60H58OP2Pd: C 74.80, H 6.07; found C 74.78,
H 6.06.
Electronic Supplementary Material (ESI) for RSC Advances.This journal is © The Royal Society of Chemistry 2016
2
X-Ray structure determination
Excalibur four-circle diffractometer with Eos CCD-detector, using MoKα radiation source (λ = 0.7107
Å). The data was corrected for Lorentz-polarization as well as for absorption effects.38 Accurate unit-
cell parameters were determined by a least-squares fit of 1984 reflections of highest intensity,
chosen from the whole experiment. The structures were solved with SIR9239 and refined with the
full-matrix least-squares procedure on F2 by SHELXL97.40 All non-hydrogen atoms were refined
anisotropically. The hydrogen atoms were placed geometrically, in idealized positions, and refined as
rigid groups with their Uiso’s as 1.2 times Ueq of the appropriate carrier atom. Crystallographic data
(excluding structure factors) for the structural analysis has been deposited with the Cambridge
Crystallographic Data Centre, No. CCDC 974168. Copies of this information may be obtained free of
charge from: The Director, CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK. Fax: +44(1223)336-033, e-
mail:[email protected], or www: www.ccdc.cam.ac.uk.
Notes and references38 Agilent Technologies 2010. CrysAlis PRO (Version 1.171.35.4).
39 A. Altomare, G. Cascarano, C. A. Giacovazzo, A. Gualardi, J. Appl. Cryst. 1993, 26, 343-350.
40 G. M. Sheldrick, Acta Cryst. 2008, A64, 112-122.
3
MS spectra
MS (m/z) spectra of 1d catalytic system (from Figure 1)
Figure 5. Sample of MS spectrum of 1[d] catalytic system.
10 (A) – 1,1’-bis(4-vinylphenyl)ferrocene
8 (B) – 1-(4-vinylphenyl)ferrocene
4
C – 1-(4-vinylphenyl)-1’-bromo-ferrocene
D - ferrocene
E – 4,4’-divinylbiphenyl
5
BrFc – 1-bromoferrocene
Br2Fc – 1,1’-dibromoferrocene
6
GPC chromatograms
GPC graphs of copolymers P1 and P2
6 8 10 12 14 16 18 20 22 24 26 28 30
0
1
2
3
4
5
GPC
sig
nal in
t. (%
)
Retention time (min.)
Figure 6. GPC chromatogram of copolymer P1.
6 8 10 12 14 16 18 20 22 24 26 28 30
0
1
2
3
4
5
6
7
8
GPC
sig
nal in
t. (%
)
Retention time (min.)
Figure 7. GPC chromatogram of copolymer P2.
7
NMR Spectra
Compound 7 1H NMR
0.00.51.03.03.54.04.55.05.56.06.57.07.5f1 (ppm)
1HNMR in CDCl3 at 25oC Compound 7
Compound 7 13C NMR
102030405060708090100110120130140150160170f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 7
114118122126130134138f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 7
8
Compound 8 1H NMR
0.00.51.03.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
1HNMR in CDCl3 at 25oC Compound 8
Compound 8 13C NMR
-100102030405060708090100110120130140150160170180190200210220f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 8
110115120125130135140f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 8
9
Compound 9 1H NMR (presence in the Article)
Compound 9 13C NMR
253035404550556065707580859095105115125135145155165f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 9
115120125130135140f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 9
Compound 10 1H NMR
0.20.61.03.03.43.84.24.65.05.45.86.26.67.07.4f1 (ppm)
1HNMR in CDCl3 at 25oC Compound 10
10
Compound 10 13C NMR
-100102030405060708090100110120130140150160170180190200210220f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 10
114118122126130134138f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 10
Compound 11 1H NMR
-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
1HNMR in CDCl3 at 25oC Compound 11
11
Compound 11 13C NMR
0102030405060708090100110120130140150f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 11
126128130132134136138140142144f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 11
Compound 11 29Si NMR
-25-20-15-10-5051015202530354045505560f1 (ppm)
29SiNMR in CDl3 at 25oC compound 11
12
Compound 12 1H NMR
0.20.61.03.03.43.84.24.65.05.45.86.26.67.07.47.8f1 (ppm)
1H NMR in CDCl3 at 25oC Compound 12
Compound 12 13C NMR
0102030405060708090100110120130140150160170180190200210f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 12
126128130132134136138140142144f1 (ppm)
13CNMR in CDCl3 at 25oC Compound 12
13
Compound 12 29Si NMR
-14-12-10-8-6-4-201234567891113151719f1 (ppm)
29SiNMR in CDl3 at 25oC compound 12
Compound 13 1H NMR
0.61.03.03.43.84.24.65.05.45.86.26.67.07.47.8f1 (ppm)
1H NMR in CDCl3 at 25oC, Compound 13
14
Compound 13 13C NMR
0102030405060708090100110120130140150f1 (ppm)
13C NMR in CDl3 at 25oC, Compound 13
124128132136140144f1 (ppm)
13C NMR in CDl3 at 25oC, Compound 13
Compound 13 29Si NMR
-70-60-50-40-30-20-100102030405060708090100110120130140150160170f1 (ppm)
29Si NMR in CDl3 at 25oC Copomound 13
15
Compound 14 1H NMR
0.00.40.82.83.23.64.04.44.85.25.66.06.46.87.27.68.0f1 (ppm)
1H NMR in CDCl3 at 25oC Compound 14
7.26
Chl
orof
orm
-d
Compound 14 13C NMR
0102030405060708090100110120130140150f1 (ppm)
13C NMR in CDl3 at 25oC compound 14
126130134138142f1 (ppm)
13C NMR in CDl3 at 25oC compound 14
16
Compound 14 29Si NMR
-70-60-50-40-30-20-100102030405060708090100110f1 (ppm)
29SiNMR in CDl3 at 25oC Copomound 14
-10.
23
Polymer P1 1H NMR
0.40.82.83.23.64.04.44.85.25.66.06.46.87.27.68.08.4f1 (ppm)
Polymer P1 1H NMR in CDCl3 at 25oC
17
Polymer P1 13C NMR
0102030405060708090100110120130140150f1 (ppm)
Polymer P1 13C NMR in CDCl3 at 25oC
124128132136140144148f1 (ppm)
Polymer P1 13C NMR in CDCl3 at 25oC
Polymer P1 29Si NMR
-50-40-30-20-100102030405060708090100110120130140150160170f1 (ppm)
Polymer P1 29Si NMR in CDCl3 at 25oC-1
0.34
Polymer P2 1H NMR (presence in the Article)
18
0.40.82.83.23.64.04.44.85.25.66.06.46.87.27.68.08.4f1 (ppm)
Polymer P2 1H NMR in CDCl3 at 25oC
7.26
Chlo
rofo
rm-d
Polymer P2 13C NMR
0102030405060708090100110120130140ppm
Polymer P2 13C NMR in CDCl3 at 25oC
124128132136140144ppm
Polymer P2 13C NMR in CDCl3 at 25oC
Polymer P2 29Si NMR
19
-50-40-30-20-100102030405060708090100110120130140150f1 (ppm)
Polymer 2 29SiNMR in CDCl3 at 25oC
-10.
36