Synthesis, Spectroscopy, and Structure of a Family of Iridabenzenes Generated by the Reaction of Vaska-Type Complexes with a Nucleophilic 3-Vinyl-1-cyclopropene
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- 作者：Robert D. Gilbertson ; Thomas L. S. Lau ; Seren Lanza ; He-Ping Wu ; Timothy J. R. Weakley ; and Michael M. Haley
- 刊名：Organometallics
- 出版年：2003
- 出版时间：August 4, 2003
- 年：2003
- 卷：22
- 期：16
- 页码：3279 - 3289
- 全文大小：174K
- 年卷期：v.22,no.16(August 4, 2003)
- ISSN：1520-6041
文摘
Seven new iridabenzenes were prepared by the addition of (Z)-1,2-diphenyl-3-(2-lithioethenyl)-1-cyclopropene to the Vaska-type complexes [IrCl(CO)(PR3)2], containing differingphosphine ligands. The iridabenzenes could be isolated from the reaction mixture either bydirect means or after heating of the crude solution. In the case of the reactions using PMe3and PEt3, a 
-vinyl/
2-cyclopropene Ir(I) complex, best described as an iridabenzvalene, couldbe isolated and fully characterized. The metallabenzvalene intermediate could be cleanlyconverted to the corresponding iridabenzene by heating in solution. The PEt3-substitutediridabenzene and iridabenzvalene were characterized by X-ray crystallography. Plausiblemechanisms for the formation of both iridacycles from the lithiated vinylcyclopropene aswell as the isomerization of the benzvalene into the benzene are postulated.
-vinyl/2-cyclopropene Ir(I) complex, best described as an iridabenzvalene, couldbe isolated and fully characterized. The metallabenzvalene intermediate could be cleanlyconverted to the corresponding iridabenzene by heating in solution. The PEt3-substitutediridabenzene and iridabenzvalene were characterized by X-ray crystallography. Plausiblemechanisms for the formation of both iridacycles from the lithiated vinylcyclopropene aswell as the isomerization of the benzvalene into the benzene are postulated.