An Approach to Pin Down the Solid-State Structure of the %26quot;Turbo Grignard%26quot;

作者：Bla**erg Florian; Bolte Michael; Wagner Matthias; Lerner Hans Wolfram^*

来源：Organometallics, 2012, 31(3): 1001-1005.

DOI：10.1021/om201080t

Single crystals of [iPrMgCl(THF)](2)[MgCl2(THF)(2)](2) were obtained by layering a THF solution of the %26quot;turbo Grignard%26quot; iPrMgCl center dot LiCl with Et2O at ambient temperature. The isolated 1:1 Grignard-MgCl2 adduct is isostructural with crystalline compounds which were obtained from pure RMgCl solutions (R = Me, tBu, Ph, Bn). The structure of [iPrMgCl(THF)](2)[MgCl2(THF)(2)](2) reveals an open-cube motif (monoclinic, P2(1)/c). When dioxane was added to a THF solution of iPrMgCl center dot LiCl, single crystals of [LiCl(THF)(2)](2) and [iPr(2)Mg(dioxane)](infinity) (monoclinic, C2/c) were isolated. From 1:1 mixtures of (Me3Si)(2)CHMgCl (DisylMgCl) and LiCl (prepared analogously to iPrMgCl center dot LiCl) two different Grignard compounds, the monomer [DisylMgCl(THF)(2)] (monoclinic, P2(1)) and the dimer [DisylMgCl(THF)](2) (monoclinic, P2(1)/c), were isolated as single crystals. During our studies, two oxidation products of iPrMgCl and DisylMgCl, respectively, resulting from oxygen insertion, were obtained and structurally characterized. Colorless plates of [iPrMg(OiPr)](4) (monoclinic, P2(1)/m) grew from a THF/benzene solution. The dimeric alkoxide {[DisylOMgCl][LiCl(THF)(2)]}(2) (monoclinic, C2/c), which was obtained from DisylMgCl center dot LiCl by oxidation through residual oxygen, displays the only structure in which incorporation of LiCl in the molecular framework of a Mg alkoxide was observed.

• 出版日期2012-2-13