CATALYTIC HYDROFORMYLATION OF ALKENES WITH CATIONIC DINUCLEAR RHODIUM(I) COMPLEXES, AND THE EFFECT OF THE COUNTER IONS

被引:13
|
作者
BAYON, JC [1 ]
ESTEBAN, P [1 ]
REAL, J [1 ]
CLAVER, C [1 ]
POLO, A [1 ]
RUIZ, A [1 ]
CASTILLON, S [1 ]
机构
[1] UNIV BARCELONA,FAC QUIM TARRAGONA,DEPT QUIM,E-43005 TARRAGONA,SPAIN
关键词
D O I
10.1016/0022-328X(91)86488-C
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The complexes [Rh2(mu-L)2L'2L"2] A2 (L = S(CH2)3N(CH3)2(CH2C6H5), derived from 3-mercaptopropylbenzyldimethylammonium bromide; L' = L" = 1/2 cyclooctadiene (cod) or L' = L" = CO or L' = CO and L" = PPh3; A = Br, PF6) have been prepared in good yield from [Rh2(mu-Cl)2(cod)2] by simple ligand substitution methods. The hexafluorophosphates catalyse hydroformylation of 1-heptene under mild conditions, and with no hydrogenation side products, in the presence of various phosphorous ligands as cocatalysts. In contrast, none of the bromides exhibited catalytic activity and furthermore addition of tetrabuthylammonium bromide to a working catalytic system quenched the reaction. The poisoning effect of bromide is discussed in terms of the formation of a labile pentacoordinated species, as indicated by the IR spectra in the sensitive carbonyl region.
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页码:393 / 399
页数:7
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