Chemistry of vinylidene complexes. XXI. Synthesis, spectroscopic and structural study of the RePt and MnPt μ–vinylidene complexes

Reaction of Cp(CO)2ReCCHPh (1) with Pt(PPh3)4 and subsequent treatment of Cp(CO)2RePt(μ–CCHPh)(PPh3)2 (2) with diphosphines P–P = dppe, dppp afforded new complexes Cp(CO)2RePt(μ–CCHPh)(P–P) (4, 5). The structures of Cp(CO)2RePt(μ–CCHPh)(dppp) (5) and Cp(CO)2MnPt(μ–CCHPh)(dppp) (10) have been determined by single crystal XRD. The influence of the nature of M = Re, Mn and L2 = (PPh3)2, dppm, dppe, dppp at the Pt atom on the structural, IR and 1H, 13C and 31P NMR spectroscopic characteristics of complexes Cp(CO)2MPt(μ–CCHPh)(L2) (2–5, 7–10) is considered.

The series of dinuclear μ–vinylidene complexes Cp(CO)2RePt(–CCHPh)(L2) (2–5) were formed by consecutive reactions of Cp(CO)2ReCCHPh (1) with Pt(PPh3)4 and Cp(CO)2RePt(μ–CCHPh)(PPh3)2 (2) with diphosphines L2 = dppm, dppe, dppp. The structures of Cp(CO)2MPt(–CCHPh)(dppp) (M = Mn, Re) were determined by single crystal XRD. The rotation of the [Cp(CO)2Re] and [PtP2] fragments around the Re–Pt bond was discovered by VT NMR investigation.Figure optionsDownload as PowerPoint slideHighlights
► The series of dinuclear μ–vinylidene complexes Cp(CO)2RePt(μ–CCHPh)(L2) (L2 = (PPh3)2, dppm, dppe, dppp) were synthesized and characterized.
► Dependence of the structural and spectroscopic parameters of complexes Cp(CO)2MPt(μ–CCHPh)(L2) on the metal M = Mn, Re and ligands L2 were investigated.
► The rotation of the Re- and Pt-containing fragments around the Re–Pt bond was shown by VT NMR study of Cp(CO)2RePt(μ–CCHPh)(L2).