Department of Chemistry, Colorado State University, Fort Collins, CO 80523-1872 (USA).
Angew Chem Int Ed Engl. 2015 Jun 1;54(23):6842-6. doi: 10.1002/anie.201502400. Epub 2015 Apr 23.
The super acidity of the unsolvated Al(C6F5)3 enabled isolation of the elusive silane-alane complex [Si-H⋅⋅⋅Al], which was structurally characterized by spectroscopic and X-ray diffraction methods. The Janus-like nature of this adduct, coupled with strong silane activation, effects multifaceted frustrated-Lewis-pair-type catalysis. When compared with the silane-borane system, the silane-alane system offers unique features or clear advantages in the four types of catalytic transformations examined in this study, including: ligand redistribution of tertiary silanes into secondary and quaternary silanes, polymerization of conjugated polar alkenes, hydrosilylation of unactivated alkenes, and hydrodefluorination of fluoroalkanes.
未配位的 Al(C6F5)3 的超强酸性使得难以捉摸的硅烷-铝烷配合物 [Si-H⋅⋅⋅Al]得以分离，该配合物通过光谱和 X 射线衍射方法进行了结构表征。该加合物具有类扬尼斯性质，同时具有很强的硅烷活化作用，可实现多方面受挫折的路易斯对型催化。与硅烷-硼烷体系相比，在本研究中考察的四种催化转化类型中，硅烷-铝烷体系具有独特的特征或明显的优势，包括：叔硅烷配体重排为仲硅烷和季硅烷、共轭极性烯烃的聚合、不饱和烯烃的硅氢化以及氟烷烃的氢去氟化。
