64023-21-8Relevant articles and documents
Synthesis and reactions of new organothallium(I) compounds derived from the reactions of cyclopentadienylthallium(I) with electrophilic olefins
Freeman, Michael B.,Sneddon, Larry G.
, p. 1125 - 1132 (1980)
The reactions of cyclopentadienylthallium (TlCp) with several electrophilic olefins were investigated Reaction of TlCp with tetracyanoethylene yields (tricyanovinyl)cyclopentadienide, Tl+[C5H4C(CN)C(CN)2]- (I), in 90% yield. Similarly the reaction of TlCp with 1,1-dicyano-2,2-bis(trifluoromethyl)ethylene yields Tl+[C5H4C(CF3) 2CH(CN)2]- (III). Protonation of I and III with anhydrous HCl results in the formation of the tricyanovinylcyclopentadiene, C10H5N3, and both the linear and cross-conjugated isomers of 1,1-dicyano-2,2-bis(trifluoromethyl)-2-cyclopentadienylethane, C11H6N2F6, respectively Compound I was found useful as a general reagent for production of tricyanovinyl-substituted metallocenes, including [η5-C5H4(CN)C(CN)2]Mn(CO) 3, [η5-C5H4C(CN)C(CN)2]CuP(C 6H5)3, and [η5-C5H4C(CN)C(CN) 2]Fe(η-C5H5). It has also been found that [η5-C5H4C(CN)C(CN) 2]Fe(η-C5H5) can be reacted with TlCp followed by addition of either (η-C5H5)Fe(CO)2I or Mn(CO)5Br to yield [(η5-C5H4)Fe(η-C5H 5)]2C2(CN)2 and [(η5-C5H4)Fe(η-C5H 5)]C2(CN)2[(η5-C 5H4)Mn(CO)3], respectively. These latter two compounds are unusual examples of bridged metallocenes containing strongly electron-withdrawing groups on the bridging unit. The reaction of III with (η-C5H5)Fe(CO)2I was also investigated and found to yield [(η5-C5H4C(CF3) 2CH(CN)2]Fe(η-C5H5).
