Reactivity of the palladium dimer [Pd2(μ-SO2)(μ-dba)(PBz3)2].: Syntheses and structural characterisation of [Pd3(μ-SO2)3(PBz3)3], [Pd2(μ-SO2)(μ-dppm)(PBz3)2], [Pd(SO2)(PBz3)2], [Pd3(μ-CO)2(μ-SO2)(PBz3)3] and [Pd3(μ-SO2)2(CNBut)2(PBz3)3] (Bz = benzyl)

被引:16
作者
Arifhodzic-Radojevic, S
Burrows, AD
Choi, N
McPartlin, M
Mingos, DMP [1 ]
Tarlton, SV
Vilar, R
机构
[1] Univ London Imperial Coll Sci Technol & Med, Dept Chem, London SW7 2AY, England
[2] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England
[3] Univ N London, Sch Appl Chem, London N7 8DB, England
来源
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1999年 / 22期
关键词
crystal structure; ketone; palladium; sulfur dioxide;
D O I
10.1039/a906444c
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The reaction between [Pd-2(dba)(3)]. solvent (dba=dibenzylideneacetone, solvent=CHCl3 or C6H6) and PBz(3) (Bz=benzyl) in the presence of SO2 led to either [Pd-2(mu-SO2)(mu-dba)(PBz(3))(2)] 1 or [Pd-3(mu-SO2)(3)(PBz(3))(3)] 2 depending on the absence or presence of an excess of SO2 in solution or in the recrystallisation. The crystal structure of 2 shows it to be a regular triangulo -cluster with Pd-Pd bond distances 2.7225(9) Angstrom. Complex 1 reacted with dppm with displacement of dba to give [Pd-2(mu-SO2)(mu-dppm)(PBz(3))(2)] 3. The crystal structure of 3 shows it to have a much shorter Pd-Pd bond length than 1 [2.670(2) Angstrom for 3 cf. 2.885(2) Angstrom for 1], which can be rationalised on the basis of the palladium atoms having been formally oxidised to Pd-I and the SO2 reduced to SO22-. Complex 1 reacted with PBz(3) to give two mononuclear complexes, the previously characterised [Pd(dba)(PBz(3))(2)] and the new complex [Pd(SO2)(PBz(3))(2)] 4 which was characterised by a single crystal X-ray analysis. Complex 4 forms a distorted T-shaped structure with the P-Pd-P angle 163.67(14)degrees. It contains a eta(1)-pyramidal SO2 ligand, and is the first mononuclear palladium SO2 complex to be crystallographically characterised. Complex 1 reacts with CO to give a mixture of the triangulo -clusters [Pd-3(mu-CO)(2)(mu-SO2)(PBz(3))(3)] 5 and [Pd-3(mu-CO)(mu-SO2)(2)(PBz(3))(3)] 6. Reaction with an excess of CO converted 6 into 5, and the crystal structure of 5 reveals relatively short Pd-Pd bond lengths consistent with a 42-electron cluster. Complex 1 reacted with CNBut to give [Pd-3(mu-SO2)(2)(CNBut)(2)(PBz(3))(3)] which has also been crystallographically characterised.
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收藏
页码:3981 / 3988
页数:8
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