Synthesis, structure and reactivity of cationic base‐stabilized gallyleneiron complexes

Addition of 2,2′‐bipyridine (bpy) to an acetonitrile solution of dichlorogallyliron complex FpGaCl 2 (1: Fp = (η‐C 5 H 5 )Fe(CO) 2 ) afforded almost quantitatively a salt consisting of a cationic base‐stabilized gallylene complex [FpGaCl·bpy] + ([3a] + ) and an anionic complex [FpGaCl 3 ] − ([4] − ). Reaction of Fp′GaCl 2 (Fp′ = Fp (1), Fp* (2); Fp* = (η‐C 5 Me 5 )Fe(CO) 2 ) with NaBPh 4 in the presence of a bidentate donor (Do 2 ) gave [Fp′GaCl·Do 2 ]BPh 4 where Do 2 was bpy or 1,10‐phenanthroline (phen). These cationic complexes may be useful precursors for the synthesis of gallyleneiron complexes with various substituents on the gallium atom. Indeed, reaction of [Fp*GaCl·phen]BPh 4 ([5b]BPh 4 ) with NaS p Tol or Me 3 SiS p Tol afforded the gallyleneiron complex [Fp*GaS p Tol·phen]BPh 4 ([6]BPh 4 ), the first example of a gallium–transition metal complex having a thiolate group on the gallium atom. The molecular structures of [5b]BPh 4 and [6]BPh 4 were determined by single crystal X‐ray diffraction. Copyright © 2003 John Wiley & Sons, Ltd.