Dichloro and alkylchloro gallium derivatives of dichalcogenoimidodiphosphinate ligands: isolation of a spirogallium cation

Abstract

Dichloro and chloromethyl Ga(III) complexes of general formulae [XClGa-η²-{R₂P(E)NP(E′)R′₂-E,E′}] (X = Cl, R, R′ = Ph, E, E′ = O (1), S (2), Se (3); R = Ph, R′ = OEt, E = O, E′ = S (4); R = Me, R′ = Ph, E, E′ = S (5) and X = Me, E, E′ = O (6), S (7), Se (8)) were synthesised by either metathesis reactions between GaCl₃ and the potassium salt of the ligand (X = Cl) or by methane eliminations from in situ prepared GaMe₂Cl and the protonated ligands LH (X = Me). Redistribution reaction of 3 in either CDCl₃ or THF afforded the solvent-free tetracoordinate gallium spirocycle cation [Ga-{η²-{Ph₂P(Se)NP(Se)Ph₂-Se,Se′})₂]⁺ (9⁺). The molecular structures of complexes 2, 4, 5, 7 and 9⁺ show non-planar gallacycle rings.