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Synthesis and characterisation of a series of alkylmagnesium amide and related oxygen-contaminated 'alkoxy' compounds

Conway, B. and Hevia, E. and Kennedy, A.R. and Mulvey, R.E. and Weatherstone, S. (2005) Synthesis and characterisation of a series of alkylmagnesium amide and related oxygen-contaminated 'alkoxy' compounds. Dalton Transactions, 2005 (8). pp. 1532-1544. ISSN 1472-7773

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Abstract

Synthesised either by an unusual tert - butyl metathesis between tert - butyllithium and a n, s-butylmagnesium amide or by reaction of an alkyl Grignard reagent and a sodium amide, five tert-butylmagnesium amides, Bu(t)MgDBA ( 5) (DBA = dibenzylamide), Bu-t MgDA ( 6) (DA = diisopropylamide), Bu-t MgHMDS ( 7) ( HMDS = 1,1,1,3,3,3-hexamethyldisilazide), (BuMgTMP)-Mg-t ( 8) (TMP = 2,2,6,6-tetramethylpiperidide) and Bu-t MgNCy2 ( 9) (cy = cyclohexyl) have been isolated as crystalline solids. All five amides have been characterised by X-ray crystallography and solution NMR spectroscopic studies. The former studies reveal a common dimeric molecular structure with amido bridges in a planar (MgN)(2) ring and terminal Bu-t ligands on the Mg atoms. Also described is the dodecameric primary amide [Bu-n MgN(H) Dipp](12) ( 10a) and its monomeric solvate Bu-n MgN( H) Dipp center dot TMEDA ( 10b) ( Dipp = 2,6-diisopropylphenyl; TMEDA = N, N, N, N - tetramethylethylenediamine). The crystal structures of the oxo-insertion products Bu-t MgOBut center dot THF (11), Bu-t Mg(mu-OBut) (mu-TMP) MgTMP (12) and Mg(OBun) HMDS center dot solv [solv = THF (13a) or Et2O(13b)], made fortuitously during the course of this work, are also presented.

Item type: Article
ID code: 647
Keywords: ray crystal-structures, 1st structural-characterization, inverse crown-ether, main group elements, metal alkyl, solid-state, magnesium complexes, lithium-magnesium, aryl compounds, organomagnesium reagents, Chemistry
Subjects: Science > Chemistry
Department: Faculty of Science > Pure and Applied Chemistry
Unknown Department
Related URLs:
Depositing user: Mr Derek Boyle
Date Deposited: 28 Mar 2006
Last modified: 12 Mar 2012 10:35
URI: http://strathprints.strath.ac.uk/id/eprint/647

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