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(μ-PPh2)4(C6F5)4] and of its oxidation product [Pt3(C6F5)4(μ-PPh2)4]

被引:41
作者
Alonso, E
Casas, JM
Forniés, J
Fortuño, C
Martín, A
Orpen, AG
Tsipis, CA
Tsipis, AC
机构
[1] Univ Zaragoza, CSIC, Dept Quim Inorgan, E-50009 Zaragoza, Spain
[2] Univ Zaragoza, CSIC, Inst Ciencia Mat Aragon, E-50009 Zaragoza, Spain
[3] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
[4] Aristotelian Univ Thessaloniki, Fac Chem, Lab Appl Quantum Chem, GR-54006 Thessaloniki, Greece
关键词
D O I
10.1021/om010407s
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The synthesis of the trinuclear phosphido complexes [NBu4](2)[(C6F5)(2)M(mu -PPh2)(2)M'(mu -PPh2)(2)M " (C6F5)(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 derivative involving two electrons yields the complex [(C6F5)(2)Pt(mu -PPh2)(2)Pt(mu -PPh2)(2)Pt(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 M-3(II) compounds modeled as [(CF3)(2)M(mu -PH2)(2)M'(mu -PH2)(2)M " (CF3)(2)](2-) (M, M', M " = Pd(II), Pt(II), 1M-5M) and the oxidation product [Pt-3(mu -PH2)(4)(CF3)(4)] (6M).
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页码:5571 / 5582
页数:12
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