Some reactions of the platinum(II) carbene complex cis-dichloro(dimethylaminomethylene)(triphenylphosphine)-platinum(II) and the X-ray crystal and molecular structures of ...

Article abstract of DOI:10.1016/S0022-328X(00)00732-4

Title full: Some reactions of the platinum(II) carbene complex cis-dichloro(dimethylaminomethylene)(triphenylphosphine)-platinum(II) and the X-ray crystal and molecular structures of the products trans-(CH ₂,P)-chloro(chloromethyl)(dimethylaminomethylene)(triphenylphosphine) platinum(II) and [1,2-bis(diphenylphosphino)ethane](dimethylaminomethylene)-(triphenylphosphine) platinum(II) bis(hexafluorophosphate). The reaction of the title complex 1 with excess diazomethane results in the exclusive insertion of a methylene group into the Pt-Cl bond trans to the phosphine ligand, to give the chloromethyl complex 6. The reactions of 1 with the diphosphines, Ph₂P(CH₂)_nPPh₂(n = 2, dppe, n = 3, dppp), and with the organometallic reagents Ph₄Sn, Ph₂Hg, or PhSnMe₃, can also all be interpreted as proceeding via initial displacement of the chlorine trans to PPh₃. The chelating phosphine ligands give equilibrium mixtures of the products [(LL)Pt(CHNMe₂)(PPh₃)]²⁺2Cl^- and [(LL)Pt(CHNMe₂)Cl]⁺Cl^- (LL = dppe, dppp), and treatment of the mixture [(LL) = dppe] with excess aqueous KPF₆ gave [(dppe)Pt(CHNMe₂)(PPh₃)]²⁺2PF₆ ^- (9b).