Stoichiometric and Catalytic Activation of Si−H Bonds by a Triruthenium Carbonyl Cluster, (μ3,η2:η3:η5-acenaphthylene)Ru3(CO)7: Isolation of the Oxidative Adducts, Catalytic Hydrosilylation of Aldehydes, Ketones, and Acetals, and Catalytic Polymerization of Cyclic Ethers
Stoichiometric and Catalytic Activation of Si−H Bonds by a Triruthenium Carbonyl Cluster, (μ3,η2:η3:η5-acenaphthylene)Ru3(CO)7: Isolation of the Oxidative Adducts, Catalytic Hydrosilylation of Aldehydes, Ketones, and Acetals, and Catalytic Polymerization of Cyclic Ethers
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三钌羰基簇 (μ3,η2:η3:η5-苊烯)Ru3(CO)7 对 Si−H 键的化学计量和催化活化：氧化加合物的分离，醛、酮和乙缩醛的催化氢化硅烷化以及催化环醚的聚合
DOI：
10.1021/om0003887
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发表时间：
2000
期刊：
影响因子：
2.8
通讯作者：
Kouki Matsubara
中科院分区：
文献类型：
--
作者：
H. Nagashima;A. Suzuki;T. Iura;and Kazuhiro Ryu;Kouki Matsubara
用化学计量的三烷基硅烷处理钌簇（μ3，η2：η3：η5-苊烯）Ru 3（CO）7（1）导致CO配体的释放，随后氧化加成Si-H键。以较好的产率分离了三核硅配合物（μ3，η2：η3：η5-苊烯）Ru_3（H）（SiR_3）（CO）_6（2）。通过核磁共振谱和X射线晶体学对其进行了表征。化合物1催化烯烃、乙炔、酮和醛的氢化硅烷化。特别是醛和酮的反应在室温下进行，以良好的产率形成相应的甲硅烷基醚;催化活性上级于RhCl（PPh 3）3。RhCl（PPh 3）3催化的酮与Me 2（H）SiCH 2CH 2Si（H）Me 2的氢化硅烷化反应导致仅一个Si-H末端的选择性反应，而类似的反应，当被1催化时，允许利用两个Si-H基团。与RhCl（PPh）催化的反应相比，反应的区域选择性和立体选择性有显著的不同。
Treatment of the ruthenium cluster (μ3,η2:η3:η5-acenaphthylene)Ru3(CO)7 (1) with stoichiometric amounts of trialkylsilanes results in liberation of a CO ligand followed by oxidative addition of a Si−H bond. The trinuclear silyl complexes (μ3,η2:η3:η5-acenaphthylene)Ru3(H)(SiR3)(CO)6 (2) were isolated in good yield. They were characterized by NMR spectroscopy and X-ray crystallography. Compound 1 catalyzes the hydrosilylation of olefins, acetylenes, ketones, and aldehydes. In particular, the reactions of aldehydes and ketones proceed at room temperature to form the corresponding silyl ethers in good yield; the catalytic activities are superior to those with RhCl(PPh3)3. The RhCl(PPh3)3-catalyzed hydrosilylation of ketones with Me2(H)SiCH2CH2Si(H)Me2 results in selective reaction of only one Si−H terminus, while similar reactions, when catalyzed by 1, allow utilization of both Si−H groups. Significantly different regio- and stereoselectivities, compared with those obtained in reactions catalyzed by RhCl(PPh...