Trimethylsilylmethylcalcium Iodide, an Easily Accessible Grignard-Type Reagent of a Heavy Alkaline Earth Metal
作者： Mathias Köhler , Alexander Koch , Helmar Görls , Matthias Westerhausen
DOI: 10.1021/ACS.ORGANOMET.5B00956
关键词: Schlenk equilibrium 、 Iodide 、 Chemistry 、 Ether 、 Medicinal chemistry 、 Inorganic chemistry 、 Bond length 、 Reagent 、 Tetrahydropyran 、 Adduct 、 Magnesium
摘要: The direct synthesis of iodomethyltrimethylsilane with calcium and magnesium in ether yields the corresponding adducts [(thf)4Ca(I)(CH2SiMe3)] (1a) [(Et2O)2Mg(I)(CH2SiMe3)] (2a). 1,4-dioxane method allows shifting Schlenk equilibrium toward bis(trimethylsilylmethyl)magnesium 2b. After substitution ligated thf ligands by tetrahydropyran (thp) crystalline [(thp)4Ca(I)(CH2SiMe3)] (1b) can be isolated. Ca–C Ca–I bond lengths 252.7(3) 319.11(3) pm represent characteristic values. Steric repulsion between thp rather bulky trimethylsilylmethyl group widens Ca–C–Si angle to 131.19(14)°. NMR data quantum chemical studies support that hyperconjugative effects might operative, leading a shortened Si–C this fragment.
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