The Synthesis of Mono- and Bi-Metallic Platinum(II) and/or (IV) Complexes Containing the Ligand Bis(diphenylphosphino) Methylamine

Abstract

Complexes of the type [Pt R2 (dppma-PP′)] (R─Me, Et, Ph, CH2Ph, C6H4 Me-p, C6H4OMe-2, CH2CMe3, 1-naphthyl, C6H4Me-o, dppma = Ph2PNMe PPh2) have been prepared from [PtCl2, (dppma-PP′)] and the corresponding alkyl-lithium or Grignard reagents. Equilibrium constants, k, for the conversion of [PtR2 (dppma-PP′)] into cis-[PtR2(dppma-P)2] with dppma were studied using 31P NMR spectroscopy at room temperature. Equilibrium is rapidly established for R─C6H4-Me-o, at 20°C. Complex of the type cis-[PtR2 (dppma-P)2] was isolated R─C6H4 Me-o. The complexes [PtMe2(dppma-P)2] and [Pt(o-methoxyphenyl)2(dppma-P)2] were prepared, but unfortunately decomposed once isolated, the only evidence for its formation being from 31P-{1H} NMZR spectroscopy. The o-tolyl or 1-naphthyl complexes exist as syn-anti mixtures in solution, due to restricted rotation around the platinum aryl bonds. Treatment of several complexes of the type [PtR2(dppma-PP′)] with MeI gives [PtR2Me(I)(dppma-PP′)] with trans addition of MeI. Treatment of [PtR2(dppma-PP′)] with HCl gives [Pt Cl (R) (dppma-PP′)] for R─C6H2Me3-2,4,6, C6H4-CH3-2, C6H4-Me-4, Me, 1-naphthyl. The 1H, 31P NMR parameters for these complexes are discussed. Attempted preparation of complexes of the type [PtR2 (dppma-P)2M] (R─C6H4-Me-2, Me CN-C6H4-Me-4); M─Pd, Pt, Au,) are reported.