Highly Fluorinated Tris(indazolyl)borate Hydrocarbyl Complexes of Calcium and Magnesium: Synthesis and Structural Studies

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• 作者：Nuria Romero ; Quentin Dufrois ; Laure Vendier ; Chiara DinoiMichel Etienne
• 刊名：Organometallics
• 出版年：2017
• 出版时间：February 13, 2017
• 年：2017
• 卷：36
• 期：3
• 页码：564-571
• 全文大小：455K
• ISSN：1520-6041

文摘

Heteroleptic phenylacetylide complexes [{F₁₂-Tp^4Bo,3Ph}Ae(C≡CPh)]_x of calcium (Ae = Ca, x = 2; 2) and magnesium (Ae = Mg, x = 1; 4) containing the highly fluorinated 3-phenyl hydrotris(indazolyl)borate {F₁₂-Tp^4Bo,3Ph}⁻ ligand have been synthesized by acid–base reactions between the corresponding silylamido derivatives [{F₁₂-Tp^4Bo,3Ph}Ae{N(SiRMe₂)₂}] (R = Me, Ae = Ca (1); R = H, Ae = Mg (3)) and PhC≡CH. Compounds 2 and 4 have been characterized by NMR spectroscopy and X-ray diffraction analysis. 2 crystallizes as a dinuclear complex, showing two nonsymmetrical “side-on” (π-type) interactions between the acetylide units and the Ca centers, whereas 4 crystallizes as a mononuclear complex, displaying a four-coordinate magnesium. The molecular structure of the complex [{F₁₂-Tp^4Bo,3Ph}Mg{N(SiMe₂H)₂}] (3), obtained by the salt metathesis reaction between [Mg{N(SiMe₂H)₂}₂] and [Tl{F₁₂-Tp^4Bo,3Ph}], is also reported. 3 is also four-coordinate and exhibits a Mg···β-Si–H agostic distortion. The synthesis and in situ characterization of the heteroleptic alkyl complex [{F₁₂-Tp^4Bo,3Ph}Ca{CH(SiMe₃)₂}(THF)] (5) is also reported, although attempts to isolate this compound failed due to its extreme sensitivity to temperature.