ISSN:
0009-2940
Schlagwort(e):
Dinuclear complexes
;
Sulfur dioxide bridges
;
Chemistry
;
Inorganic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Sulfur(IV) Compounds as Ligands, XIII. - Sulfur Dioxide as a Bridging Ligand in Unsymmetrical Dinuclear ComplexesA series of known or newly synthesized dinuclear complexes with the following combinations of elements: Mo/Ir, Mo/Pd, W/Pd, Mn/Pd, Fe/Rh, Rh/Pt, Ir/Pd, and Ir/Pt has been treated with sulfur dioxide. Only electron-rich systems are capable of taking up SO2 into a bridging position. [Mo(CO)3(η2-dppe) (η1-dppm)] (2) reacts with [PdCl2(C8H12)] to form [MoPdCl2(CO)3(dppe)(μ-dppm)] (3), which is unstable and does not take up SO2. However, the complexes [FeRhCl(CO)4(μ-SO2)(μ-dppee)] (5), [MoIr(μ-Cl)(CO)3(μ-SO2)(μ-dppm)2] (8), and [MnPdBr(CO)2(μ-SO2)(μ-dppm)2] (14) have been obtained. Reactions of fac;-[M(CO)3(η2-dppm)(η1-dppm)] (M=Mo: 6a, W: 6b) or the corresponding mer-isomers 10a, b with [PdCl2;-(C8H12)] give the dinuclear complexes [MPdCl(μ-Cl)(CO)2(μ-CO)(μ-dppm)2] (11a, b). From [Ir(CO)(dppm)2]Cl and [Pd(dba)2] in the presence of CO [IrPdCl(CO)2(μ-dppm)2] (16) is obtained, whereas in dichloromethane under an inert gas the oxidation product [IrPdC]3(CO)(μ-dppm)2] (17) is formed. 11a, b, 16, and 17 apparently are too electron-poor to form stable adducts with SO2. However, from 17 and (Me3Si)2S the sulfur-bridged complex [IrPdCl(μ-S)(CO)(μ-dppm)2] (18) is obtained. The alkynyl complexes [MPtCl(C=CPh)2(μ-dppm)2] (M — Rh: 19, Ir: 21) readily add SO2, reversibly in the case of 19. From [IrPtCl-(C ≡ CPh)2(μ-SO2)](μ-dppm)2] (22) the salt [IrPt(C ≡ CPh)2(SO2) (μ-dppm)2]PF6 (23) is formed by Cl abstraction. 23 is one of the rare examples of terminal coordination of SO2 in a dinuclear complex.
Zusätzliches Material:
1 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/cber.19911240305
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