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.
二
氯和
氯甲基Ga(III)配合物,通式为[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) 和 X = Me, E, E′
= O (6), S (7), Se (8)),通过GaCl3与
配体的
钾盐的复分解反应(X = Cl)或从原位制备的GaMe2Cl与质子化
配体LH的
甲烷消除反应(X = Me)合成。3的再分配反应在CDCl3或THF中进行,形成了不含溶剂的四配位
镓螺环阳离子[Ga-η2-Ph2P(Se)NP(Se)Ph2-Se,Se′})2]+
(9+)。配合物2, 4, 5, 7和9+的分子结构显示非平面
镓环。