The First Example of a Dinuclear Platinum(III) Complex with Three Bridging Ligands

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AbstractThe first triply bridged dinuclear platinum(III) compound with acetamidate ligands, X[Pt2Cl4{N(H)C(CH3)O}3] (X = K+ or AsPh4+), has been isolated in the solid state and characterized by one‐ and two‐dimensional NMR spectroscopy and X‐ray crystallography. Owing to the asymmetry of the bridging acetamidate ligands, three isomers can be formed (HHH, HHT, and HTH), although only two are found in the crude reaction product: HHT and HTH. The HTH species is thermodynamically less stable and slowly (half life of around two days at room temperature) isomerizes into the HHT form. The more stable and less symmetric HHT isomer crystallizes from chloroform/pentane (AsPh4+ counter ion). The two [Pt2Cl4{N(H)C(CH3)O}3]– anions of the unit cell are linked by two strong N–H···O H‐bonds while contiguous anions of adjacent cells are linked together by two, slightly weaker N–H···Cl H‐bonds. The result is a chain of anions running along the a direction. The crystal packing allows for the formation of one‐dimensional pore channels, also running along the a direction, which are filled with disordered pentane molecules. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)