TY - JOUR
T1 - Molecular structures and charge-transfer complexes of cis-dibenzo[c,h]-1,6-disilabicyclo[4.4.0]deca-3,8-dienes and bi(benzo[c]silacyclopent-3-ene-1-yl)s
AU - Kyushin, Soichiro
AU - Ikarugi, Masanobu
AU - Tsunakawa, Satoshi
AU - Izumi, Yukiko
AU - Miyake, Michihiro
AU - Sato, Mitsuo
AU - Matsumoto, Hideyuki
AU - Goto, Midori
N1 - Funding Information:
This work was supportedi n part by Grants-in-Aid for Scientific Research (Priority Area of Organic Unusual Valency No. 03233105 and Reactive OrganometallicsN o. 05236206a, nd Encouragemento f Young ScientistsN o. 04740288f)r om the Ministry of Education, Science and Culture. We also thank Shin-etsu ChemicalC o., Ltd. and Toshiba Silicone Co., Ltd. for financial support.
PY - 1994/6/28
Y1 - 1994/6/28
N2 - The reaction of the di-Grignard reagent of α,α′-dichloro-o-xylene with Cl2RSiSiRCl2(R iPr and Me) produced cis-dibenzo[c,h-1,6-dialkyl-1,6-disilabicyclo[4.4.O]deca-3,8-diene (1) and bi(benzo[c]-1-alkylsilacyclopent-3-ene-1-yl) (2). The structures of 1a (R iPr) and 2a (R iPr) were determined by X-ray crystallography. Crystal data for 1a: orthorhombic, Pbca, a = 14.816(1), b = 16.263(1), c = 17.257(1) Å, V = 4158.1(3) Å3, Z = 8, R = 0.040, Rw = 0.050 for 2008 reflections. Crystal data for 2a: triclinic, P1, a = 8.179(2), b = 10.389(3), c = 6.605(2) Å, α = 100.39(2)°, β = 98.29(2), γ = 106.75(2)°, V = 517.0(3) Å3, Z = 1, R = 0.042, Rw = 0.051 for 1167 reflections. Compounds 1 and 2 have relatively low oxidation potentials (1.24-1.59 V vs. SCE, in acetonitrile) and form charge-transfer complexes with tetracyanoethylene (TCNE). In the case of 2a, the charge-transfer complex was isolated as red crystals and the structure was determined by X-ray crystallography. Crystal data for the 2a-TCNE complex: triclinic, P1, a = 6.8399(8), b = 8.2836(6), c = 12.868(1) Å, α = 84.142(6)°, β = 88.737(6)°, γ = 66.801(8)°, V = 666.5(1) Å3, Z = 1, R = 0.038, Rw = 0.042 for 1554 reflections.
AB - The reaction of the di-Grignard reagent of α,α′-dichloro-o-xylene with Cl2RSiSiRCl2(R iPr and Me) produced cis-dibenzo[c,h-1,6-dialkyl-1,6-disilabicyclo[4.4.O]deca-3,8-diene (1) and bi(benzo[c]-1-alkylsilacyclopent-3-ene-1-yl) (2). The structures of 1a (R iPr) and 2a (R iPr) were determined by X-ray crystallography. Crystal data for 1a: orthorhombic, Pbca, a = 14.816(1), b = 16.263(1), c = 17.257(1) Å, V = 4158.1(3) Å3, Z = 8, R = 0.040, Rw = 0.050 for 2008 reflections. Crystal data for 2a: triclinic, P1, a = 8.179(2), b = 10.389(3), c = 6.605(2) Å, α = 100.39(2)°, β = 98.29(2), γ = 106.75(2)°, V = 517.0(3) Å3, Z = 1, R = 0.042, Rw = 0.051 for 1167 reflections. Compounds 1 and 2 have relatively low oxidation potentials (1.24-1.59 V vs. SCE, in acetonitrile) and form charge-transfer complexes with tetracyanoethylene (TCNE). In the case of 2a, the charge-transfer complex was isolated as red crystals and the structure was determined by X-ray crystallography. Crystal data for the 2a-TCNE complex: triclinic, P1, a = 6.8399(8), b = 8.2836(6), c = 12.868(1) Å, α = 84.142(6)°, β = 88.737(6)°, γ = 66.801(8)°, V = 666.5(1) Å3, Z = 1, R = 0.038, Rw = 0.042 for 1554 reflections.
KW - Charge transfer
KW - Silicon
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U2 - 10.1016/0022-328X(94)80101-0
DO - 10.1016/0022-328X(94)80101-0
M3 - Article
AN - SCOPUS:0000798131
SN - 0022-328X
VL - 473
SP - 19
EP - 27
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 1-2
ER -