A convenient synthesis of cationic, heterobimetallic complexes of general formulae [(R3P)2M1(µ-Cl)2M2(chel)]BF4, [(R3P)2M1(µ-Cl)2Rh(cod)]BF4 and [(R3P)2M1(µ-Cl)2M3(chel)]BF4 (M1, M2 = PdII or PtII; M3 = RhIII or IrIII, chel = anion of 2-phenylpyridine, benzo[h]quinoline, C6H5CHRNMe2 or η3-allyl) has been elaborated. These complexes were formed in quantitative yields by metathesis reactions of the dicationic complexes [(R3P)2M1(µ-Cl)}2][BF4]2 with the corresponding neutral, homodimeric compounds [(cod)Rh(µ-Cl)}2] and [(chel)M3(µ-Cl)}2]. Reactions with half-sandwich complexes such as [(p-cym)RuCl(µ-Cl)}2], (cym = cymene), on the other hand, were shown to result in chloride transfer. The structures of [(Bu3P)2Pt(µ-Cl)2Pd(η3-C3H5)]BF4 and [(Bu3P)2Pt(µ-Cl)2Rh(bzq)2]BF4 (bzq = benzo[h]quinoline anion) were determined by X-ray diffraction analyses.
方便合成通式为 [(R3P)2M1(μ-Cl)2M2(chel)]BF4、[(R3P)2M1(μ-Cl)2Rh(cod)]BF4 和 [(R3P)2M1 的阳离子异双
金属配合物(μ-Cl)2M3(chel)]BF4(M1、M2 = PdII 或 PtII;M3 = RhIII 或 IrIII,chel =
2-苯基吡啶、苯并[h]
喹啉、C6H5CHRNMe2 或 η3-烯丙基的阴离子)已得到详细阐述。这些配合物是通过双阳离子配合物 [(R3P)2M1(μ-Cl)}2][BF4]2 与相应的中性同二聚化合物 [(cod)Rh(μ-Cl) 的复分解反应以定量产率形成的}2]和[(chel)M3(μ-Cl)}2]。另一方面,与半夹心配合物如 [(p-cym)RuCl(μ-Cl)}2] (cym =
伞花烃) 的反应会导致
氯离子转移。 [(Bu3P)2Pt(μ-Cl)2Pd(η3-
C3H5)]BF4 和 [(Bu3P)2Pt(μ-Cl)2Rh(bzq)2]BF4(bzq = 苯并[h]
喹啉阴离子)的结构为通过X射线衍射分析测定。