Abstract
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 differing phosphine ligands. The iridabenzenes could be isolated from the reaction mixture either by direct means or after heating of the crude solution. In the case of the reactions using PMe3 and PEt3, a σ-vinyl/η2-cyclopropene Ir(I) complex, best described as an iridabenzvalene, could be isolated and fully characterized. The metallabenzvalene intermediate could be cleanly converted to the corresponding iridabenzene by heating in solution. The PEt3-substituted iridabenzene and iridabenzvalene were characterized by X-ray crystallography. Plausible mechanisms for the formation of both iridacycles from the lithiated vinylcyclopropene as well as the isomerization of the benzvalene into the benzene are postulated.
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