Water-soluble hydroxyalkylated phosphines: examples of their differing behaviour toward ruthenium and rhodium
作者:Lee J. Higham、Michael K. Whittlesey、Paul T. Wood
DOI:10.1039/b411701h
日期:——
phenyl groups of the latter reduce the extent of the network compared to 1. The generation of these mixed secondary and tertiary phosphine complexes is unprecedented. Under the same reaction conditions, the tris(hydroxypropyl)phosphine III formed no ruthenium complex. The reaction of P(CH2OH)3, P(C6H5)(CH2OH)2 and P(CH2)3OH}3 with [RhCl(1,5-cod)]2 in an aqueous/dichloromethane biphasic medium yielded
P(CH2OH)3(I)和P(C6H5)(CH2OH)2(II)与RuCl3在甲醇中的反应消除了两当量的甲醛,从而生成了全反式[RuCl2(P( CH 2 OH)3)2(P(CH 2 OH)2 H)2](1)和[RuCl 2(P(C 6 H 5)(CH 2 OH)2)2(P(C 6 H 5)(CH 2 OH)H)2](2)。尽管1和2中的羟甲基之间的氢键相互作用程度很高,但与1相比,后者的苯基降低了网络的程度。这些混合的仲和叔膦配合物的产生是空前的。在相同的反应条件下,三(羟丙基)膦III没有形成钌络合物。在水/二氯甲烷双相介质中,P(CH2OH)3,P(C6H5)(CH2OH)2和P (CH2)3OH} 3与[RhCl(1,5-cod)] 2的反应生成[RhH2(P (CH 2 OH)3)4] +(3),[RhH2(P(C6H5)(CH2OH)2)4] +(4)和[Rh(P(C6H5)(CH2OH)2)4]