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Heteronuclear Hexaplatinum Cluster Complexes:  Structure as a Function of Electron Count

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posted on 1998-09-24, 00:00 authored by Greg J. Spivak, Jagadese J. Vittal, Richard J. Puddephatt
The 84-electron hexaplatinum cluster complex [Pt6(μ-CO)6(μ-dppm)3], 1, dppm = Ph2PCH2PPh2, reacts in a 1:2 molar ratio with either 0-electron metalloligands LM+ (L = Ph3P, M = Cu, Ag, Au; L = iPr3P, M = Au) or InX3 (X = Cl, Br) or 2-electron metalloligands Tl+ and Hg to give the corresponding 84-electron clusters [Pt63-ML)2(μ-CO)6(μ-dppm)3]2+ or [Pt63-InX3)2(μ-CO)6(μ-dppm)3] or 88-electron clusters [Pt63-Tl)2(μ-CO)6(μ-dppm)3]2+ and [Pt63-Hg)2(μ-CO)6(μ-dppm)3], respectively. The mercury cluster is oxidized by CH2I2 to give the known 86-electron cluster [Pt63-HgI)2(μ-CO)6(μ-dppm)3]. Reaction of 1 with [Ir(CO)4]- occurs in a 1:1 ratio only to give the 98-electron anionic cluster [Pt63-Ir(CO)2}(μ-CO)6(μ-dppm)3]-, which reacts with [Ph3PAu]+ to give [Pt63-Ir(CO)2}(μ3-AuPPh3)(μ-CO)6(μ-dppm)3]. The new cluster complexes are characterized by NMR and IR spectroscopies, and [Pt63-AuPiPr3)2(μ-CO)6(μ-dppm)3]2+ is also characterizedby an X-ray structure determination.