Synthesis of Homo- or Hetero-trinuclear Palladium(II)/Platinum(II) Compounds with Bridging Phosphido Ligands. Crystal and Electronic Structures (DFT) of [N(PPh3)2]2[Pt3(ΞΌ-PPh2)4(C6F5)4] and of Its Oxidation Product [Pt3(C6F5)4(ΞΌ-PPh2)4]
Synthesis of Homo- or Hetero-trinuclear Palladium(II)/Platinum(II) Compounds with Bridging Phosphido Ligands. Crystal and Electronic Structures (DFT) of [N(PPh3)2]2[Pt3(ΞΌ-PPh2)4(C6F5)4] and of Its Oxidation Product [Pt3(C6F5)4(ΞΌ-PPh2)4]
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Alonso, E.
(EN)
Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας
(EL)
Alonso, E.
(EN)
The synthesis of the trinuclear phosphido complexes [NBu4]2[(C6F5)2M(ΞΌ-PPh2)2M"�(ΞΌ-PPh2)2M"�"‰"�(C6F5)2] (M, M"�, M"�"‰"� = Pd(II), Pt(II), 1β�’5) is described. A study of the electrochemical behavior of these complexes is reported. The chemical oxidation of the homonuclear platinum derivative involving two electrons yields the complex [(C6F5)2Pt(ΞΌ-PPh2)2Pt(ΞΌ-PPh2)2Pt(C6F5)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 properties of these phosphido-bridged trinuclear M3(II) compounds modeled as [(CF3)2M(ΞΌ-PH2)2M"�(ΞΌ-PH2)2M"�"‰"�(CF3)2]2- (M, M"�, M"�"‰"� = Pd(II), Pt(II), 1Mβ�’5M) and the oxidation product [Pt3(ΞΌ-PH2)4(CF3)4] (6M).
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