Bi- and Triferrocene Complexes Containing Silylenevinylenephenylene Bridges. Model Compounds for Poly{ferrocene(phenylene)bis(silylenevinylene)}s
详细信息 查看全文
- 作者：Rajsapan Jain ; Hojae Choi ; Roger A. Lalancette ; and John B. Sheridan
- 刊名：Organometallics
- 出版年：2005
- 出版时间：March 28, 2005
- 年：2005
- 卷：24
- 期：7
- 页码：1468 - 1476
- 全文大小：181K
- 年卷期：v.24,no.7(March 28, 2005)
- ISSN：1520-6041
文摘
A series of conjugated ferrocene-based organosilicon complexes with one, two, or threeferrocene units have been prepared via hydrosilylation of alkynes with ferrocenylsilanesusing Karstedt's catalyst (platinum-divinyltetramethyldisiloxane) and Rh(PPh3)3I. Reactionof 1,1'-bis(dimethylsilyl)ferrocene (1) with 2 equiv of RC
CR1 (R = H, R1 = Ph, SiMe3, Fc{Fc = (
-C5H5)Fe(-C5H4)}; R = SiMe3, R1 = Ph, Fc) gave Fe[(5-C5H4)(Me)2SiC(R)=CHR1]2complexes (type 1) with varying regiochemical distributions. Addition of 2 equiv ofdimethylsilylferrocene (2) to dialkynes R-CC-X-CC-R [R = H, X = C6H4 (1,4- and1,3-), SiMe2; R = Me, X = Fc' {Fc' = (-C5H4)Fe(-C5H4)}; R = SiMe3, X = C6H4 (1,4- and1,3-); R = Ph, X = nothing] resulted in Fc(Me)2Si(R)C=C(H)-X-(H)C=C(R)Si(Me)2Fccomplexes (type 2), again with varying regiochemical distributions. The platinum-promotedhydrosilylations resulted in 
-(E) and 
-regioisomers, whereas the rhodium-catalyzedreactions gave primarily -(Z) species with minor amounts of the -(E) isomer. X-raycrystallographic studies of the predominant adducts obtained from 1 and Me3SiCCPh aswell as 2 and Me3Si-CC-C6H4-CC-SiMe3 (1,4-) using Karstedt's catalyst are described.Cyclic voltammetry shows single redox waves for most systems indicative of no interactionbetween the Fe-Fe centers. One complex, Fc(Me)2Si(C=CH2)-Fc'-Si(C=CH2)(Me)2Fc, showstwo reversible waves for the two different types of ferrocene center.
CR1 (R = H, R1 = Ph, SiMe3, Fc{Fc = (-C5H5)Fe(-C5H4)}; R = SiMe3, R1 = Ph, Fc) gave Fe[(5-C5H4)(Me)2SiC(R)=CHR1]2complexes (type 1) with varying regiochemical distributions. Addition of 2 equiv ofdimethylsilylferrocene (2) to dialkynes R-CC-X-CC-R [R = H, X = C6H4 (1,4- and1,3-), SiMe2; R = Me, X = Fc' {Fc' = (-C5H4)Fe(-C5H4)}; R = SiMe3, X = C6H4 (1,4- and1,3-); R = Ph, X = nothing] resulted in Fc(Me)2Si(R)C=C(H)-X-(H)C=C(R)Si(Me)2Fccomplexes (type 2), again with varying regiochemical distributions. The platinum-promotedhydrosilylations resulted in -(E) and -regioisomers, whereas the rhodium-catalyzedreactions gave primarily -(Z) species with minor amounts of the -(E) isomer. X-raycrystallographic studies of the predominant adducts obtained from 1 and Me3SiCCPh aswell as 2 and Me3Si-CC-C6H4-CC-SiMe3 (1,4-) using Karstedt's catalyst are described.Cyclic voltammetry shows single redox waves for most systems indicative of no interactionbetween the Fe-Fe centers. One complex, Fc(Me)2Si(C=CH2)-Fc'-Si(C=CH2)(Me)2Fc, showstwo reversible waves for the two different types of ferrocene center.