title: Synthesis, structure and reactivity study of magnesium amidinato complexes derived from carbodiimides and N,N'-bis(2,6-diisopropylphenyl)-1,4-diaza-butadiene ligands.
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 (), [Mg(CH2Ph){(i)PrN[double bond, length as m-dash]C(CH2Ph)N(i)Pr}]2 () and the homoleptic [Mg{(t)BuN[double bond, length as m-dash]C(CH2Ph)N(t)Bu}2] () (Cy = cyclohexyl, (i)Pr = isopropyl, (t)Bu = 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] () (Dipp = 2,6 diisopropylphenyl) in good yield. The solid-state structures of magnesium complexes 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 and N-aryliminopyrrolyl ligand 2-(2,6-(i)Pr2C6H3N[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}] (), with one amidinato and two aryliminopyrrolyl ligands in the coordination sphere, was obtained in good yield. In contrast, the homoleptic magnesium complex 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)] (), with a benzylated DAD ligand and aryliminopyrrolyl ligands in the coordination sphere. Further reaction of complex with benzyl alcohol (PhCH2OH) afforded the third mixed ligated magnesium complex [Mg{DippN[double bond, length as m-dash]C(CH2Ph)CH2NDipp}(OCH2Ph)2] () in very good yield. The magnesium complexes were characterised using standard analytical/spectroscopic techniques and their solid-state structures were established by single-crystal X-ray diffraction analysis.
authors.affiliation: Department of Chemistry, Indian Institute of Technology Hyderabad, Ordnance Factory Estate, Yeddumailaram 502205, Telangana, India. tpanda@iith.ac.in.
authors.forename: Srinivas
authors.initials: S
authors.lastname: Anga
authors.forename: Jayeeta
authors.initials: J
authors.lastname: Bhattacharjee
authors.forename: Adimulam
authors.initials: A
authors.lastname: Harinath
authors.forename: Tarun K
authors.initials: TK
authors.lastname: Panda