Synthesis of Homo-or Hetero-trinuclear palladium(II)/Platinum(II) Compounds with Bridging Phosphido Ligands. Crystal and Electronic Structures (DFT) of [NPPh_3)_2]_2[Pt_3(#mu#-PPH_2)_4(C_6F_5)_4] and of It Oxidation product [Pt_3(C_6F_5)_4(#mu#-PPh_2

摘要

The synthesis of the trinuclear phosphido complexes[NBu_4]_2[(C_6F_5)_2M(#mu#-PPh_2)_2M'(#mu#-PPh_2)_2M''(C_6F_5)_2](M,M',M''=Pd(II), Pt(II),1-5) is described. A study of the electrochemical behavior of these complexes is reported. The chemical oxidation of the homonuclear platinum behavior of involving two electrons yields the complox[(C_6F_5)_2Pt(#mu#-PPh_2)_2Pt(#mu#-PPh_2)_2Pt(C-6F_5)_2] (6), which contains pt in average formal oxidation state 2.67. The structure of the complexes has been established by spectroscopic means, and X-ray diffraction studies have been carried out on 1 and 6. Quantum chemical calculations at the B3LYP level of theory , using the LANL2DZ basis set, provide a satisfactory description of the structural , bonding energetic, and electronic prpperties of these phosphido-bridege trinuclear M_3(II )compounds modeled as [(CF_3)_2M(#mu#-PH_2)_2M'(#mu#''(CF_3)_2)]~(2-) (M,M,'M''=Pd(II), Pt(II), 1M-5M) and the oxidation product [Pt_3(#mu#-PH_2)_4(CF_3)_4](6M)