涉及 1,1-插入 XylNC 到 σ-硅烷配体的 Si-H 键的硅烷-异氰化物偶联。
Silane-isocyanide coupling involving 1,1-insertion of XylNC into the Si-H bond of a σ-silane ligand.
机构信息
Department of Chemistry, University of California, Berkeley, California 94720, United States.
出版信息
J Am Chem Soc. 2013 Jul 17;135(28):10298-301. doi: 10.1021/ja404910h. Epub 2013 Jul 8.
Complexes [PhBP(Ph)3]RuH(η(3)-H2SiRR') (R,R' = Me,Ph, 1a; RR' = Ph2, 1b) react with XylNC (Xyl = 2,6-dimethylphenyl) to form Fischer carbene complexes [PhBP(Ph)3]Ru(H)═[C(H)(N(Xyl)(η(2)-H-SiRR'))] (2a,b) that feature a γ-agostic Si-H bond. The ruthenium isocyanide complexes [PhBP(Ph)3]Ru(H)(CNXyl)(η(2)-HSiHRR') (6a,b) are not intermediates as they do not convert to 2a,b. Experimental and theoretical investigations indicate that XylNC is activated by initial coordination to the silicon center in 1a,b, followed by 1,1-insertion into an Si-H bond of the coordinated silane and then rearrangement to 2a,b.
复合物[PhBP(Ph)3]RuH(η(3)-H2SiRR')（R，R'=Me，Ph，1a；RR'=Ph2，1b）与XylNC（Xyl=2,6-二甲基苯基）反应生成 Fischer 卡宾复合物[PhBP(Ph)3]Ru(H)=[C(H)(N(Xyl)(η(2)-H-SiRR'))]（2a，b），其特征是γ-螯合 Si-H 键。钌异氰化物复合物[PhBP(Ph)3]Ru(H)(CNXyl)(η(2)-HSiHRR')（6a，b）不是中间体，因为它们不会转化为 2a，b。实验和理论研究表明，XylNC 通过初始与 1a，b 中的硅中心配位而被激活，随后进行 1,1-插入到配位硅烷的 Si-H 键中，然后重排为 2a，b。
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