Bi- and triferrocene complexes containing silylenevinylenephenylene bridges. Model compounds for poly{ferrocene(phenylene)bis(silylenevinylene)}s

Rajsapan Jain, Hojae Choi, Roger A. Lalancette, John B. Sheridan

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19 Scopus citations

Abstract

A series of conjugated ferrocene-based organosilicon complexes with one, two, or three ferrocene units have been prepared via hydrosilylation of alkynes with ferrocenylsilanes using Karstedt's catalyst (platmum- divinyltetramethyldisiloxane) and Rh(PPh 3) 3I. Reaction of 1,1′-bis(dimethylsilyl)ferrocene (1) with 2 equiv of RC≡CR 1 (R = H, R 1 = Ph, SiMe 3, Fc {Fc = (η-C 5H 5)Fe(η-C 5H 4)}; R = SiMe 3, R 1 = Ph, Fc) gave Fe[(η 5-C 5H 4)(Me) 2SiC(R)=CHR 1] 2 complexes (type 1) with varying regiochemical distributions. Addition of 2 equiv of dimethylsilylferrocene (2) to dialkynes R-C≡C-X-C≡C-R [R = H, X = C 6H 4 (1,4- and 1,3-), SiMe 2; R = Me, X = Fc′ {Fc′ = (η-C 5H 4)Fe(η-C 5H 4)}; R = SiMe3, X = C 6H 4 (1,4- and 1,3-); R = Ph, X = nothing] resulted in Fc(Me) 2Si(R)C=C(H)-X-(H) C≡C(R)Si(Me) 2Fc complexes (type 2), again with varying regiochemical distributions. The platinum-promoted hydrosilylations resulted in β-(E) and α-regioisomers, whereas the rhodium-catalyzed reactions gave primarily β-(Z) species with minor amounts of the β-(E) isomer. X-ray crystallographic studies of the predominant adducts obtained from 1 and Me 3SiC≡CPh as well as 2 and Me 3Si-C≡C-C 6H 4-C≡C-SiMe 3 (1,4-) using Karstedt's catalyst are described. Cyclic voltammetry shows single redox waves for most systems indicative of no interaction between the Fe-Fe centers. One complex, Fc(Me) 2Si(C=CH 2)-Fc′-Si(C=CH 2)(Me) 2Fc, shows two reversible waves for the two different types of ferrocene center.

Original languageEnglish (US)
Pages (from-to)1468-1476
Number of pages9
JournalOrganometallics
Volume24
Issue number7
DOIs
StatePublished - Mar 28 2005

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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