Andrews, Philip C., Forsyth, Craig M., Junk, Peter C., Nuzhnaya, Iryna, and Spiccia, Leone (2009) Synthesis and structural characterisation of gallium and indium fluoroalkoxide 'ate' complexes. Journal of Organometallic Chemistry, 694 (3). pp. 373-381.

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Abstract

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.

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