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Highly fluorinated tris(indazolyl)borate silylamido complexes of the heavier alkaline earth metals: synthesis, characterization, and efficient catalytic intramolecular hydroamination.

Abstract : Heteroleptic silylamido complexes of the heavier alkaline earth elements calcium and strontium containing the highly fluorinated 3-phenyl hydrotris(indazolyl)borate {F12-Tp(4Bo, 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-Tp(4Bo, 3Ph))] in pentane to form the corresponding heteroleptic complexes [(F12-Tp(4Bo, 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-Tp(4Bo, 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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https://hal-univ-rennes1.archives-ouvertes.fr/hal-01141110
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Submitted on : Friday, April 10, 2015 - 2:27:19 PM
Last modification on : Thursday, March 5, 2020 - 2:07:13 PM

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Nuria Romero, Sorin-Claudiu Roşca, Yann Sarazin, Jean-François Carpentier, Laure Vendier, et al.. Highly fluorinated tris(indazolyl)borate silylamido complexes of the heavier alkaline earth metals: synthesis, characterization, and efficient catalytic intramolecular hydroamination.. Chemistry - A European Journal, Wiley-VCH Verlag, 2015, 21 (10), pp.4115-4125. ⟨10.1002/chem.201405454⟩. ⟨hal-01141110⟩

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