Metal coordination of phosphoniocarbynes

Heterobi- and tetrametallic phosphoniocarbyne bridged complexes [WAu(μ-CPMe 2 Ph)Cl(CO) 2 (Tp*)] + (Tp* = hydrotris(3,5-dimethylpyrazol-1-yl)borate), [W 2 Cu 2 (μ-CPMe 2 Ph) 2 (μ-Cl) 2 (CO) 4 (Tp*) 2 ] 2+ and [WPt(μ-CPMe 2 Ph)(COD)(CO) 2 (Tp*)] + (COD = 1,5-cyclo-octadiene) arise from the reactions of the mononuclear terminal phosphoniocarbyne [W(&z.tbd;CPMe 2 Ph)(CO) 2 (Tp*)]PF 6 with [AuCl(THT)] (THT = tetrahydrothiophene), [CuCl(SMe 2 )] and [Pt(nbe) 3 ] (nbe = norbornene) in the presence of COD. The COD ligand in [WPt(μ-CPMe 2 Ph)(COD)(CO) 2 (Tp*)] + is labile and readily replaced by isonitriles to provide [WPt(μ-CPMe 2 Ph)(CNR) 2 (CO) 2 (Tp*)] + (R = t Bu, C 6 H 2 Me 3 -2,4,6) with retention of the tungstaplatinacyclopropene core, the bonding within which was computationally interrogated. Heterobi- and tetrametallic phosphoniocarbyne bridged complexes arise from the reactions of the terminal phosphoniocarbyne [W(&z.tbd;CPMe 2 Ph)(CO) 2 (Tp*)]PF 6 with unsaturated metal centres.