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“Dibutylmagnesium”, a convenient reagent for the synthesis of useful organic magnesium reagents MgA2 including cyclopentadienyls,aryloxides, and amides. Preparation of Zr(C5H5)Cl3. X-ray structure of [Mg{μ-N(SiMe)3C6H4N}(SiMe3)-o(OEt2)]2
Authors:Alan W Duff  Peter B Hitchcock  Michael F Lappert  Richard G Taylor  John A Segal
Institution:School of Chemistry and Molecular Sciences, University of Sussex, Brighton BN1 9QJ Great Britain;New Science Group, Imperial Chemical Industries, PLC, PO Box 11, The Heath, Runcorn, Cheshire WA7 4QE U.K.
Abstract:n-Heptane-soluble “di-butylmagnesium” (I) (a commercially available material, prepared by addition of LiBus to MgBunCl, and subsequent addition of ca. 5% MgOct2n) has been found to be a useful starting material for obtaining numerous organic magnesium compounds. This is illustrated by its reaction with a number of protic compounds HA to give in good yields Mg(C5H5)2, Mg(C5H4Me)2, or the new compounds MgA2: IV (A = C5H4SiMe3), V A = C5H3(SiMe3)2], VII (A = OC6H2Bu2t-2,6-Me-4), and X A2 = N(SiMe3)C6H4N(SiMe3)-o(OEt2)]. The value of such compounds MgA2 as mild ligand transfer reagents is illustrated by the synthesis of Zr(C5H3X2)Cl3 (X = H or SiMe3). Compound X was isolated from OEt2 solution as the crystalline dimer
with two o-N(SiMe3)C6H4N(SiMe3) ligands bridging two magnesium atoms and a terminal OEt2 ligand completing a distorted tetrahedral environment around each Mg. Some key parameters are: MgNt 1.997(7), MgNb 2.083(8), MgO 2.041(7) Å; OMgNt 112.1(3), OMgNb 119.7(3), and NtMgNb 118.5(3)°.
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