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Hydrosilylation of Carbonyl Compounds Catalyzed through a Lithiated Hydrazone Derivative

机译：通过锂化腙衍生物催化的羰基化合物的氢化硅烷化物质

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摘要

A well-defined lithiated hydrazone derivative has been synthesized and fully characterized through various analytical platforms, including multinuclear (H-1, C-13, N-15, Li-7) and two-dimensional NMR, high-resolution MS spectrometry, IR, and X-ray diffraction crystallography. It behaves as a binuclear species in the solid state and as a monomeric contact ion pair in solution. It has also been tested as a catalyst in hydrosilylation reactions, being the first lithium hydrazone reported to catalyze the full conversion of carbonyls of different nature into alcohols in short reaction times, at room temperature, and with catalyst loadings equal to or below 0.5 mol %. Kinetic studies have proven fractional order dependences with respect to ketone and silane and first order dependence in the case of the catalyst. The proposed reaction mechanism is characterized by the nucleophilic addition of the lithium hydrazonide to the silicon atom of the silane to give a five-coordinate silicon species.
机译：通过各种分析平台合成并充分地合成了明确的锂酸锂衍生物，包括多核（H-1，C-13，N-15，Li-7）和二维NMR，高分辨率MS光谱法IR 和X射线衍射晶体学。 它表现为固态中的双核物种，作为溶液中的单体接触离子对。 还在氢化硅烷化反应中作为催化剂进行测试，是据报道的第一锂腙在室温下在短反应时间内催化不同性质的羰基羰基，并且在室温下等于或低于0.5mol％的催化剂载量 。 动力学研究已经证明了酮和硅烷的分数依赖性，并且在催化剂的情况下依赖于第一阶依赖性。 所提出的反应机理的特征在于将氮氧化锂的亲核加成到硅烷的硅原子中，得到五坐标硅种类。

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