Stable Carbeneiridium(I) Complexes with 16- and 18-Electron Configurations at the Metal Center

Abstract

Using the mixed phosphine−stibine compound [IrCl(C2H4)(PiPr3)(SbiPr3)] (2) as the starting material, the square-planar carbeneiridium(I) complexes [IrCl(CR2)(PiPr3)(SbiPr3)] (3a,b) and trans-[IrCl(CR2)(PiPr3)2] (4a,b) were prepared. The cyclopentadienyl derivative [C5H5Ir(CPh2)(PiPr3)] (5), obtained from 3a and NaC5H5, reacts with HCl by attack of the IrCPh2 bond; in contrast, upon treatment of 4a with HCl or HBF4, hydridoiridium(III) complexes 8 and 9 with an intact IrCPh2 unit are formed.