Tomer Kanishk, Schnakenburg Gregor, Das Ujjal, Filippou Alexander C
Institut für Anorganische Chemie, Universität Bonn Gerhard-Domagk-Str. 1 Bonn 53121 Germany
Chem Sci. 2025 Mar 24;16(18):7773-7793. doi: 10.1039/d5sc01063b. eCollection 2025 May 7.
The different reactivity pattern of M[triple bond, length as m-dash]Si and M[triple bond, length as m-dash]C bonds (M = transition metal) is illustrated by a series of reactions of the silylidyne complexes [Cp*(CO)M[triple bond, length as m-dash]Si-Tbb] (1-M) (M = Cr - W; Cp* = -pentamethylcyclopentadienyl; Tbb = 4--butyl-2,6-bis(bis(trimethylsilyl)methyl)phenyl)). Complexes 1-M were obtained selectively from Li[Cp*M(CO)] and the 1,2-dibromodisilene ()-Tbb(Br)Si[double bond, length as m-dash]Si(Br)Tbb. The reaction of 1-Mo and 1-W with two equivalents of mesityl isocyanate leads selectively to complex 2-Mo and 2-W, respectively, featuring a novel ,-imidocarbonatosilyl ligand. Ring opening of ethyloxirane occurs rapidly with 1-Mo and leads to the hydrido-enolatosilylidene complex 3-Mo illustrating the Si-centered electrophilicity of the silylidyne complex. Trimethylsilyldiazomethane induces a cleavage of the Mo[triple bond, length as m-dash]Si bond of 1-Mo after a rapid double [2 + 1] cycloaddition of the terminal N-atom, resulting in the first silaamidinato complex 4-Mo. In comparison, the reaction of 1-Mo with mesityl azide gives, after N elimination, the Mo-silaiminoacyl complex 5-Mo. All compounds were fully characterized and the isomerism and dynamics of 3-Mo in solution were analysed by a combination of spectroscopic and quantum-chemical studies.
甲硅烷基炔配合物[Cp*(CO)M≡Si-Tbb] (1-M)（M = Cr - W；Cp* = η⁵-五甲基环戊二烯基；Tbb = 4-叔丁基-2,6-双（双（三甲基硅基）甲基）苯基）的一系列反应说明了M≡Si和M≡C键（M = 过渡金属）不同的反应模式。配合物1-M是由Li[Cp*M(CO)]与1,2-二溴二硅烯(±)-Tbb(Br)Si═Si(Br)Tbb选择性得到的。1-Mo和1-W与两当量的均三甲苯异氰酸酯反应分别选择性地生成配合物2-Mo和2-W，其具有新型的η²,κ²-亚氨基碳酸硅基配体。环氧乙烷与1-Mo迅速发生开环反应，生成氢化烯醇硅酸炔配合物3-Mo，这说明了硅烷基炔配合物以硅为中心的亲电性。三甲基硅基重氮甲烷在末端N原子快速进行双[2 + 1]环加成后，诱导1-Mo的Mo≡Si键断裂，生成首个硅脒基配合物4-Mo。相比之下，1-Mo与均三甲苯叠氮化物反应，在消除N后，生成Mo-硅亚氨基酰基配合物5-Mo。所有化合物均得到了充分表征，并通过光谱和量子化学研究相结合的方法分析了3-Mo在溶液中的异构现象和动力学。
