Trimethylsilylmethylcalcium Iodide, an Easily Accessible Grignard-Type Reagent of a Heavy Alkaline Earth Metal
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https://figshare.com/articles/dataset/Trimethylsilylmethylcalcium_Iodide_an_Easily_Accessible_Grignard_Type_Reagent_of_a_Heavy_Alkaline_Earth_Metal/2084407
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资源简介：
The
direct synthesis of iodomethyltrimethylsilane with calcium
and magnesium in ether yields the corresponding ether adducts [(thf)4Ca(I)(CH2SiMe3)] (1a) and
[(Et2O)2Mg(I)(CH2SiMe3)] (2a). The 1,4-dioxane method allows shifting the
Schlenk equilibrium toward bis(trimethylsilylmethyl)magnesium 2b. After substitution of ligated thf ligands by tetrahydropyran
(thp) crystalline [(thp)4Ca(I)(CH2SiMe3)] (1b) can be isolated. The Ca–C and Ca–I
bond lengths of 252.7(3) and 319.11(3) pm represent characteristic
values. Steric repulsion between ligated thp ligands and the rather
bulky trimethylsilylmethyl group widens the Ca–C–Si
angle to 131.19(14)°. NMR data and quantum chemical studies support
that hyperconjugative effects might be operative, leading to a shortened
Si–C bond of this Ca–C–Si fragment.
创建时间：
2016-02-12
