SCHEDULED MAINTENANCE
Bimetallic systems. Part 7. Platinum and palladium dicyanides containing terminal or bridging Ph2PCH2PPh2 and heterobimetallics with silver, gold, mercury, rhodium, iridium, or molybdenum
Abstract
Treatment of [M (Ph2PCH2PPh2-PP′)2]Cl2, i.e.[M (dppm-PP′)2] Cl2, with NaCN gives [M(CN)2(dppm-P)2](M = Pt or Pd). These complexes are fluxional at 20 °C due to rapid ‘end over end’ motion of the dppm ligands. The complex [MCl2(dppm-PP′)] with NaCN gives the binuclear ‘face to face’ complexes [M2(CN)4(µ-dppm)2]. The platinum complex [Pt(CN)2(dppm-P)2] is quaternized by methyl iodide to give [Pt(CN)2(Ph2PCH2PMePh2)2]I2. With AgNO3, followed by Nal, [Pt(CN)2(dppm-P)2] gives [(NC)2Pt(µ-dppm)2Agl], with [AuCl(PPh3)] it gives [(NC)2 Pt(µ-dppm)2Au]Cl, and with HgCl2 it gives [(NC)2Pt(µ-dppm)2HgCl2]. The complex [M(CN)2(dppm-P)2](M = Pt or Pd), when treated with [Rh2Cl2(CO)4], [IrCl(CO)2(NH2C6H4-p)] or trans-[IrCl(CO)(PPh3)2], give heterobimetallics of type [(NC)2M(µ-dppm)2M′(CO) Cl](M′= Rh or Ir). Treatment of [Pd(CN)2(dppm-P)2] with [Mo(CO)3(C7H8)](C7H8= cyclohepta-1,3,5-triene) gives [(NC)2Pd(µ-dppm)2Mo(CO)3]. I.r. and 31P and 1H n.m.r. data are given.
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