Unprecedented co-ordination mode of the tetrathio-molybdate or -tungstate anions in heterometallic gold complexes. Crystal structures of [MoS4(AuAsPh3)2] and [WS4(AuCH2PPh3)2]·CH 2Cl2

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Abstract
Treatment of the tetrathiometalates [NH 4 ] 2 [MS 4 ] (M = Mo or W) with [AuCl(AsPh 3 )] (molar ratio 1∶2) gave the trinuclear species [MS 4 (AuAsPh 3 ) 2 ] (M = Mo 1 or W 2). Stepwise substitution of the arsine ligand afforded the complexes [MS 4 (AuAsPh 3 )(AuPPh 3 )] (M = Mo 3 or W 4) or [MS 4 (AuPPh 3 )(AuPPh 2 Me)] (M = Mo 5 or W 6). The reaction with gold(I) complexes [AuCl(ylide)] follows a different pathway depending on the ylide ligand; with the less sterically demanding CH 2 PPh 2 Me the species [MS 4 (AuCH 2 PPh 2 Me) 2 ] (M = Mo 7 or W 8) with three-co-ordinate gold were formed, but the ylide CH 2 PPh 3 led to [MS 4 (AuCH 2 PPh 3 ) 2 ] (M = Mo 9 or W 10) with one three- and one two-co-ordinate gold centre. The crystal structures of complexes 1 and 10 were determined by X-ray diffraction.

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