Rh(I) and Rh(III) silyl PMe3 complexes. Syntheses, reactions and 103Rh NMR spectroscopy
作者:Michael Aizenberg、Juergen Ott、Cornelis J. Elsevier、David Milstein
DOI:10.1016/s0022-328x(97)00433-6
日期:1998.1
Synthetic approaches to Rh(I) silyls are described. The complexes LnRhSiR3 (L=PMe3; 6, n=4, R3=(OEt)3; 7, n=4, R3=Me(OMe)2; 21, n=3, R3=Ph3) resulted from the reactions of MeRhL4 (1) with the corresponding silanes HSiR3. Complex 21 was prepared alternatively from PhRhL3 (2) and HSiPh3, while analogous reactions of HSi(OEt)3, HSiMe(OMe)2 and HSi(OMe)3 led to the bis(silyl)hydrides fac-L3Rh(SiR3)2(H)
描述了合成Rh(I)甲硅烷基的方法。络合物L n RhSiR 3(L = PMe 3 ; 6,n = 4,R 3 =(OEt)3 ; 7,n = 4,R 3 = Me(OMe)2 ; 21,n = 3,R 3 = Ph 3)是MeRhL 4(1)与相应的硅烷HSiR 3的反应产生的。替代物21由PhRhL 3(2)和HSiPh 3制备,而HSi(OEt)3,HSiMe(OMe)2和HSi(OMe)3的类似反应导致双(甲硅烷基)氢化物fac -L 3 Rh(SiR 3)2(H)(8,R 3 =( OEt)3;9,R 3= Me(OMe)2;13,R 3=(OMe)3)。像在类似的铱基体系中一样,这些反应的结果很大程度上取决于硅原子上取代基的性质。不能通过该途径合成的Rh(I)甲硅烷基,即具有烷基的那些利用相应的甲硅烷基锂在[L 4 Rh]处的亲核攻击,获得了硅上的取代基L n RhSiR 3(19,n