Stoichiometric and Catalytic Activation of Si−H Bonds by a Triruthenium Carbonyl Cluster, (μ<sub>3</sub>,η<sup>2</sup>:η<sup>3</sup>:η<sup>5</sup>-acenaphthylene)Ru<sub>3</sub>(CO)<sub>7</sub>: Isolation of the Oxidative Adducts, Catalytic Hydrosilylation of Aldehydes, Ketones, and Acetals, and Catalytic Polymerization of Cyclic Ethers
作者:Hideo Nagashima、Akihiro Suzuki、Takafumi Iura、Kazuhiro Ryu、Kouki Matsubara
DOI:10.1021/om0003887
日期:2000.9.1
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
钌簇的治疗(μ 3,η 2:η 3:η 5 -acenaphthylene)的Ru 3(CO)7(1)配有在CO的解放化学计量量的三烷基硅烷的配体的结果,随后氧化加成在Si-H的键。三核的甲硅烷复合物(μ 3,η 2:η 3:η 5 -acenaphthylene)的Ru 3(H)(SIR 3)(CO)6(2)以良好的收率被分离。它们通过NMR光谱和X射线晶体学表征。化合物1催化烯烃,乙炔,酮和醛的氢化硅烷化。特别地,醛和酮的反应在室温下进行,以高收率形成相应的甲硅烷基醚。催化活性优于RhCl(PPh 3)3。用Me 2(H)SiCH 2 CH 2 Si(H)Me 2的RhCl(PPh 3)3催化的酮的硅氢加成反应仅导致一个Si-H末端的选择性反应,而当类似的反应被1催化时,允许两个Si-H基团的利用。与在RhCl(PPh 3)3催化的反应中获得的区域选择性和立体选择性相比,在α,β-不饱