Highly Fluorinated Tris(indazolyl)borate Silylamido Complexes of the Heavier Alkaline Earth Metals: Synthesis,Characterization, and Efficient Catalytic Intramolecular Hydroamination |
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| Authors: | Nuria Romero Sorin‐Claudiu Ro?ca Dr Yann Sarazin Prof Jean‐François Carpentier Dr Laure Vendier Sonia Mallet‐Ladeira Dr Chiara Dinoi Prof Michel Etienne |
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| Institution: | 1. CNRS, LCC (Laboratoire de Chimie de Coordination), BP 44099, 205?route de Narbonne, 31077 Toulouse Cedex 4 (France);2. Université de Toulouse, UPS, INPT, LCC, 31077 Toulouse Cedex 4 (France);3. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS‐Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex (France);4. Institut de Chimie de Toulouse (FR 2599), Université Paul Sabatier, 118?route de Narbonne, 31062 Toulouse Cedex 9 (France) |
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| Abstract: | Heteroleptic silylamido complexes of the heavier alkaline earth elements calcium and strontium containing the highly fluorinated 3‐phenyl hydrotris(indazolyl)borate {F12‐Tp4Bo, 3Ph}? ligand have been synthesized by using salt metathesis reactions. The homoleptic precursors Ae{N(SiMe3)2}2] (Ae=Ca, Sr) were treated with Tl(F12‐Tp4Bo, 3Ph)] in pentane to form the corresponding heteroleptic complexes (F12‐Tp4Bo, 3Ph)Ae{N(SiMe3)2}] (Ae=Ca ( 1 ); Sr ( 3 )). Compounds 1 and 3 are inert towards intermolecular redistribution. The molecular structures of 1 and 3 have been determined by using X‐ray diffraction. Compound 3 exhibits a Sr ??? MeSi agostic distortion. The synthesis of the homoleptic THF‐free compound Ca{N(SiMe2H)2}2] ( 4 ) by transamination reaction between Ca{N(SiMe3)2}2] and HN(SiMe2H)2 is also reported. This precursor constitutes a convenient starting material for the subsequent preparation of the THF‐free complex (F12‐Tp4Bo, 3Ph)Ca{N(SiMe2H)2}] ( 5 ). Compound 5 is stabilized in the solid state by a Ca???β‐Si?H agostic interaction. Complexes 1 and 3 have been used as precatalysts for the intramolecular hydroamination of 2,2‐dimethylpent‐4‐en‐1‐amine. Compound 1 is highly active, converting completely 200 equivalents of aminoalkene in 16 min with 0.50 mol % catalyst loading at 25 °C. |
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| Keywords: | agostic interactions alkaline earth metals hydroamination ligands metathesis |
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