Synthesis, structure and reactivity study of magnesium amidinato complexes derived from carbodiimides and N,N′-bis(2,6-diisopropylphenyl)-1,4-diaza-butadiene ligands

Anga, S and Bhattacharjee, J and Adimulam, H and Panda, Tarun K (2015) Synthesis, structure and reactivity study of magnesium amidinato complexes derived from carbodiimides and N,N′-bis(2,6-diisopropylphenyl)-1,4-diaza-butadiene ligands. Dalton Transactions, 44. pp. 955-965. ISSN 1477-9226

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Abstract

We report an amidinato ligand-supported series of magnesium complexes obtained from the insertion of a magnesium–carbon bond into a carbon–nitrogen double bond of different carbodiimides and α-diimine ligands. The magnesium complexes [Mg(CH2Ph){CyN[double bond, length as m-dash]C(CH2Ph)NCy}]2 (1), [Mg(CH2Ph){iPrN[double bond, length as m-dash]C(CH2Ph)NiPr}]2 (2) and the homoleptic [Mg{tBuN[double bond, length as m-dash]C(CH2Ph)NtBu}2] (3) (Cy = cyclohexyl, iPr = isopropyl, tBu = tert-butyl) were prepared by the reaction of dibenzyl magnesium [Mg(CH2Ph)2(Et2O)2] with the respective carbodiimides either in 1 : 1 or 1 : 2 molar ratio in toluene. The analogous reaction of [Mg(CH2Ph)2(Et2O)2] with the N,N′-bis(2,6-diisopropylphenyl)-1,4-diaza-1,3-butadiene (Dipp2DAD) ligand afforded the corresponding homoleptic magnesium complex [Mg{DippN[double bond, length as m-dash]C(CH2Ph)CH2NDipp}2] (4) (Dipp = 2,6 diisopropylphenyl) in good yield. The solid-state structures of magnesium complexes 1–4 were confirmed by single-crystal X-ray diffraction analysis. It was observed that in each case, a magnesium–carbon bond was inserted into the carbon–nitrogen double bond of either carbodiimides or Dipp2DAD resulting in a monoanionic amido–imino ligand. In a further reaction between 1 and N-aryliminopyrrolyl ligand 2-(2,6-iPr2C6H3N[double bond, length as m-dash]CH)C4H3NH (ImpDipp-H) in 1 : 2 molar ratio, a new magnesium complex [Mg(ImpDipp)2{CyN[double bond, length as m-dash]C(CH2Ph)NHCy}] (5), with one amidinato and two aryliminopyrrolyl ligands in the coordination sphere, was obtained in good yield. In contrast, the homoleptic magnesium complex 4 reacted with one equivalent of N-aryliminopyrrolyl ligand (ImpDipp-H) to produce another mixed ligated magnesium complex [Mg{DippN[double bond, length as m-dash]C(CH2Ph)CH2NDipp}(ImpDipp)] (6), with a benzylated DAD ligand and aryliminopyrrolyl ligands in the coordination sphere. Further reaction of complex 4 with benzyl alcohol (PhCH2OH) afforded the third mixed ligated magnesium complex [Mg{DippN[double bond, length as m-dash]C(CH2Ph)CH2NDipp}(OCH2Ph)2] (7) in very good yield. The magnesium complexes 5–7 were characterised using standard analytical/spectroscopic techniques and their solid-state structures were established by single-crystal X-ray diffraction analysis.

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