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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共 53 条
[31]   Oxidant-induced hydride abstraction from [Pt(μ-PBut2)(H)(PBut2H)]2 yielding [Pt2(μ-PBut2)2(H)(PBut2H)2]C3(CN)5.: Spectroscopic, crystallographic, and theoretical comparison of the structures of two "Tautomers" [J].
Leoni, P ;
Pasquali, M ;
Fortunelli, A ;
Germano, G ;
Albinati, A .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (37) :9564-9573
[32]   Synthesis and structure of Pd-4(mu-(PBu2)-Bu-t)(2)(mu-CS2)(PPh3)(2)I-2, a neutral palladium(I) derivative with a hexacoordinate carbon and a CS2 molecule bridging four palladium centers [J].
Leoni, P ;
Pasquali, M ;
Fadini, L ;
Albinati, A ;
Hofmann, P ;
Metz, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (37) :8625-8629
[33]   CO-induced reductive elimination of P(t-Bu)(2)H from the platinum(II) dinuclear derivative Pt2Cu[mu-P(t-BU)(2)](2)(H)(2)[P(t-BU)(2)H](2), affording mononuclear platinum(0) or triangulo triplatinum(I,I,II) derivatives [J].
Leoni, P ;
Manetti, S ;
Pasquali, M ;
Albinati, A .
INORGANIC CHEMISTRY, 1996, 35 (21) :6045-6052
[34]   Proton lability in highly hindered dinuclear palladium(I) mu-phosphido-secondary phosphine complexes. Crystal structures of [Pd-2(mu-PBu(2)(t))(PCy(2)H)(3)(CO)]BF4 and [Pd-2(mu-PBu(2)(t)) (PCy(2)H)(2)(mu,eta(2),eta(2)-isoprene)]BF4 [J].
Leoni, P ;
Pasquali, M ;
Sommovigo, M ;
Albinati, A ;
Pregosin, PS ;
Ruegger, H .
ORGANOMETALLICS, 1996, 15 (08) :2047-2052
[35]   Manganese-group 11 element and -zinc mixed-metal clusters derived from the binuclear dianion [Mn-2{mu-P(OEt)(2)}{mu-eta(2)-OP(OEt)(2)}(CO)(6)](2-). X-ray structures of [Mn2Zn{mu-P(OEt)(2)}{mu-eta(2)-OP(OEt)(2)}(CO)(6)(C10H8N2-N,N')] and [Mn2Au3{mu-P(OEt)(2)}(CO)(6)(PPh(3))(3)] [J].
Liu, XY ;
Riera, V ;
Ruiz, MA ;
Tiripicchio, A ;
TiripicchioCamellini, M .
ORGANOMETALLICS, 1996, 15 (03) :974-983
[36]   Structural systematics .6. Apparent flexibility of metal complexes in crystals [J].
Martin, A ;
Orpen, AG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (06) :1464-1470
[37]   ALKYL, ARYL, ACYL, FORMYL, AND HYDRIDE DERIVATIVES OF PHOSPHIDO-BRIDGED WRE COMPLEXES - CRYSTAL AND MOLECULAR-STRUCTURE OF (CO)5W(MU-PPH2)RE(CO)4 [J].
MERCER, WC ;
WHITTLE, RR ;
BURKHARDT, EW ;
GEOFFROY, GL .
ORGANOMETALLICS, 1985, 4 (01) :68-74
[38]   BINUCLEAR TUNGSTEN RHENIUM ALKYL ACYL AND ALKYL CARBENE COMPLEXES - CRYSTAL AND MOLECULAR-STRUCTURE OF (CO)4W(MU-PPH2)2RE(CO)3CH3 [J].
MERCER, WC ;
GEOFFROY, GL ;
RHEINGOLD, AL .
ORGANOMETALLICS, 1985, 4 (08) :1418-1425
[39]   Density functional theory studies of zeolite structure, acidity, and reactivity [J].
Nicholas, JB .
TOPICS IN CATALYSIS, 1997, 4 (1-2) :157-171
[40]   A theoretical explanation of solvent effects in zeolite catalysis [J].
Nicholas, JB .
TOPICS IN CATALYSIS, 1999, 9 (3-4) :181-189