Metal-Dependent Stabilization of Si−S Bonds to Hydrolysis in Iridium and Rhodium Silyls. Hydrolyzability as a Probe for Si−H Reductive Elimination
作者:Michael Aizenberg、Roman Goikhman、David Milstein
DOI:10.1021/om950791r
日期:1996.2.6
(triethylthio)silyl complexes cis-(PPh3)2(CO)IrH2(Si(SEt)3) (5), fac-(PMe3)3Ir(CH3)(H)(Si(SEt)3) (6), and mer-(PMe3)3Ir(C6F5)(H)(Si(SEt)3) (7) were synthesized by oxidative addition of HSi(SEt)3 (1) to HIr(CO)(PPh3)3 (2), CH3Ir(PMe3)4 (3), and C6F5Ir(PMe3)3 (4), respectively. 4 was synthesized by the reaction between Ir(PMe3)4Cl and C6F5MgBr. The rhodium analog of 7, mer-(PMe3)3Rh(C6F5)(H)(Si(SEt)3) (9), was
铱(三乙硫基)甲硅烷基络合物顺-(PPh 3)2(CO)IrH 2(Si(SEt)3)(5),fac-(PMe 3)3 Ir(CH 3)(H)(Si(SEt)3)(6),和聚体- (PME 3)3的Ir(C 6 ˚F 5)(H)硅烷(Si(SET)3)(7)由氧化加成在HSi(SET)中合成3(1)至HIR (CO)(PPh 3)3(2),CH 3 Ir(PMe 3)4(3)和C 6 F 5 Ir(PMe 3)3(4)。4变更为Ir(PME之间的反应合成的3)4氯和C 6 ˚F 5 MgBr。铑类似物的7,聚体- (PME 3)3的Rh(C 6 ˚F 5)(H)硅烷(Si(SET)3)(9)中,同样地从C中获得6 ˚F 5Rh(PMe 3)3,(8)和1。不同于极易水解母体硅烷1,化合物5 - 7是H中稳定2 O / THF,甚至在NaOH / H 2 O / THF溶液。这种稳定性归因于