Metal coordination of phosphoniocarbynes

Abstract

Heterobi- and tetrametallic phosphoniocarbyne bridged complexes [WAu(μ-CPMe₂Ph)Cl(CO)₂(Tp*)]⁺ (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate), [W₂Cu₂(μ-CPMe₂Ph)₂(μ-Cl)₂(CO)₄(Tp*)₂]²⁺ and [WPt(μ-CPMe₂Ph)(COD)(CO)₂(Tp*)]⁺ (COD = 1,5-cyclo-octadiene) arise from the reactions of the mononuclear terminal phosphoniocarbyne [W(CPMe₂Ph)(CO)₂(Tp*)]PF₆ with [AuCl(THT)] (THT = tetrahydrothiophene), [CuCl(SMe₂)] and [Pt(nbe)₃] (nbe = norbornene) in the presence of COD. The COD ligand in [WPt(μ-CPMe₂Ph)(COD)(CO)₂(Tp*)]⁺ is labile and readily replaced by isonitriles to provide [WPt(μ-CPMe₂Ph)(CNR)₂(CO)₂(Tp*)]⁺ (R = ^tBu, C₆H₂Me₃-2,4,6) with retention of the tungstaplatinacyclopropene core, the bonding within which was computationally interrogated.