Metal-dependent stabilization of Si-S bonds to hydrolysis in iridium and rhodium silyls. Hydrolyzability as a probe for Si-H reductive elimination
Metal-dependent stabilization of Si-S bonds to hydrolysis in iridium and rhodium silyls. Hydrolyzability as a probe for Si-H reductive elimination
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金属依赖性铱和铑甲硅烷基中 Si-S 键的水解稳定性。
DOI：
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发表时间：
1996
期刊：
影响因子：
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通讯作者：
D. Milstein
中科院分区：
文献类型：
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作者：
M. Aizenberg;Roman Goikhman;D. Milstein
铱通过HSi（SEt）3（1）与HIr（CO）（PPh 3）3（2）、CH 3 Ir（PMe 3）4（3）和C6 F5 Ir（PMe 3）3（4）的氧化加成反应，合成了（三乙硫基）硅烷基配合物cis-（PPh 3）2（CO）IrH 2（Si（SEt）3）（5）、fac-（PMe 3）3 Ir（CH 3）（H）（Si（SEt）3）（6）和mer-（PMe 3）3 Ir（C6 F5）（H）（Si（SEt）3）（7），分别4是由Ir（PMe 3）4Cl和C6 F5 MgBr反应合成的。7的铑类似物mer-（PMe 3）3Rh（C6 F5）（H）（Si（SEt）3）（9）类似地从C6 F5 Rh（PMe 3）3（8）和1获得。与极易水解的母体硅烷1不同，化合物5-7在H2O/THF中，甚至在NaOH/H2O/THF溶液中都是稳定的。这种稳定性归因于Ir中心的供电子能力，其有效地降低了硅的亲电性。铑络合物9的反应性显著不同，在5当量H2O存在下干净地产生乙硫基络合物mer-（PMe 3）3Rh（C6 F5）（H）（SEt）（10）。化合物10通过光谱鉴定，并独立于8和HSEt合成。A plau.
The iridium (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 obtained similarly from C6F5Rh(PMe3)3, (8) and 1. Unlike the extremely easily hydrolyzable parent silane 1, compounds 5-7 are stable in H2O/THF and even in NaOH/H2O/THF solutions. This stabilization is attributed to the electron-donating capacity of the Ir centers, which efficiently reduces electrophilicity of the silicon. Reactivity of the rhodium complex 9 is strikingly different, cleanly producing in the presence of 5 equiv of H2O the ethylthio-complex mer-(PMe3)3Rh(C6F5)(H)(SEt) (10). Compound 10 was identified spectroscopically and was synthesized independently from 8 and HSEt. A plau...