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

摘要

Dichloro and chloromethyl Ga(III) complexes of general formulae [XClGa-eta(2)-{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-{eta(2)-{Ph2P(Se) NP(Se) Ph-2-Se, Se'})(2)](+) (9(+)). The molecular structures of complexes 2, 4, 5, 7 and 9(+) show non-planar gallacycle rings.