Addition of 2,2′-bipyridine (bpy) to an acetonitrile solution of Fp2GaCl (1: Fp = CpFe(CO)2; Cp = η-C5H5) afforded quantitatively a salt consisting of a diiron cation bridged by a Ga·bpy fragment [Fp2(μ-Ga·bpy)]+ ([2a]+) and μ-GaCl2 diiron anion [Fp2(μ-GaCl2)]- (-). The reaction of 1 with Do2 (Do2 = N,N,N′,N′-tetramethylethylenediamine (tmeda), 1,10-phenanthroline (phen), and (4-(dimethylamino)pyridine)2 (= dmap2)) in the presence of 1 equiv of NaBPh4 in acetonitrile afforded [Fp2(μ-Ga·Do2)]+BPh4 - (Do2 = tmeda (2b), phen (2c), and (dmap)2 (2d)). Cation [2a-d]+ is the first example of a dinuclear complex bridged by a base-coordinated gallium atom Ga·Do2 (Do = Lewis base). X-ray crystal structure analysis of [2a]·CH3CN revealed that the Fe-Ga bond lengths (2.3969(16) and 2.4037(14) A) in [2a]+ are shorter than those of - (2.4234(13) and 2.4359(15) Å), but within the range previously observed for Fp-gallyl complexes (2.36-2.46 Å). The Ga - Cl bonds in - (2.3259(19) and 2.3537(19) A) are longer than those of known chlorogallyl complexes (2.18-2.29 Å).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Organic Chemistry
- Inorganic Chemistry