Synthesis and structural characterisation of gallium and indium fluoroalkoxide ‘ate’ complexes

The treatment of InCl3 with MOCH(CF3)2 (M = Li, Na, K) in a 1:6 stoichiometry, followed by recrystallisation results in the formation of the bimetallic "ate" complexes [Na3In(OCH(CF3)2)6(THF)3] (2) and [Li3In(OCH(CF3)2)6(THF)3] (5) from hexane, and [K3In(OCH(CF3)2)6]n (4) from a THF and toluene mixture. If a 1:3 stoichiometry is used chloride containing compounds [Na2InCl(OCH(CF3)2)4(THF)4] (1) and [KInCl2 (OCH(CF3)2)2(THF)3]n · THF (3) are obtained on recrystallisation from hexane. Treatment of GaCl3 with 6 equivalents of LiOC(CH3)2CF3 gives [LiGa(OC(CH3)2CF3)4(THF)2] (6) on recrystallisation from hexane. The protolysis reaction between In(N(SiMe3)2)3, formed in situ from (Me3Si)2NH, nBuLi and Incl3, and HOCH(CH3)CF3 results in isolation of [LiIn(OCH(CH3)CF3)3Bu]2 (7) from hexane. The structures of 2, 4, and 5 all contain the tetranuclear core InO6M3. Compounds 1 and 3 have residual chloride; 1 is a trinuclear species with two THF ligands per Na, while 3 is a linear polymer. Compound 6 has a GaO2Li four-membered parallelogram at its core. Complex 7 has a tetranuclear In2O6Li2 core and an unexpected nBu group on the In atoms. The coordination spheres of the alkali metals in 1–6 include solvated THF while 1–5 display additional close M⋯F interactions.