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

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), Bu(t)MgTMP (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.TMEDA (10b)(Dipp=2,6-diisopropylphenyl; TMEDA=N,N,N',N'-tetramethylethylenediamine). The crystal structures of the oxo-insertion products Bu(t)MgOBu(t).THF (11), Bu(t)Mg(mu-OBu(t))(mu-TMP)MgTMP (12) and Mg(OBu(n))HMDS.solv solv=THF (13a) or Et2O (13b)], made fortuitously during the course of this work, are also presented.