Synthesis of platinum–manganese and –rhenium complexes with bridging thiocarbonyl ligands; crystal structure of [MnPt(µ-CS)(CO)2(PMePh2)2(η-C5H5)]
Abstract
Addition of the compounds [M(CO)2(CS)(η-C5H5)](M = Mn or Re) to the species [Pt(C2H4)(PR3)2] in light petroleum at 0 °C affords the dimetal complexes [MPt(µ-CS)(CO)2(PR3)2(η-C5H5)](M = Mn, PR3= PMe2Ph or PMePh2; M = Re, PR3= PMe2Ph). The structure of [MnPt(µ-CS)(CO)2(PMePh2)2(η-C5H5)] has been established by X-ray diffraction. Crystals are monoclinic, space group P21/c, Z= 4, in a unit cell with a= 16.655(4), b= 9.684(3), c= 21.409(5)Å, β= 114.57(2)°. The structure was refined to R 0.043 (R′ 0.043) for 4 358 independent absorption-corrected intensities with 2.9 ⩽ 2θ⩽ 50°(Mo-KαX-radiation) collected at room temperature. The Pt–Mn bond [2.641(1)Å] is bridged by the CS ligand [C–Mn 1.878(8), C–Pt 2.015(8)Å] and strongly semi-bridged by a CO group [Mn–C–O 154.0(8)°; C–Mn 1.798(8), C–Pt 2.220(9)Å]. Variable-temperature n.m.r. studies revealed that the compounds [MPt(µ-CS)(CO)2(PR3)2(η-C5H5)] undergo dynamic behaviour in solution, and possible mechanisms for site exchange of PR3 and CO ligands are discussed. Treatment of [MnPt(µ-CS)(CO)2(PMe2Ph)2(η-C5H5)] with [OMe3][BF4] gave the salt [MnPt(µ-CSMe)(CO)2(PMe2Ph)2(η-C5H5)][BF4] containing the µ-CSMe thiocarbyne ligand.
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