Unique Formation of a Pentanuclear Lanthanum(III) Thiolate Oxide Cluster via Control of Hydrolysis

The reaction of [(TMS)2N]3La(μ-Cl)Li(THF)3 (1) and HSPh produced a bimetallic complex [{(TMS)2N}2La(THF)]2(μ-SPh)(μ-Cl)] (2). Compound [{(TMS)2N}2La5O(SPh)10LiCl2(THF)6] (3) was prepared by control of the hydrolysis of 2 and LiCl or 1 and HSPh with the proper amount of water. 1 was treated first with 1/6 equiv of H2O and then with equimolar HSPh; a polymeric complex [{(TMS)2N}2(μ-SPh)La(μ-SPh)Li(THF)2]∞ (4) was isolated. 3 contains a central [(μ-SPh)4(μ3-SPh)2{La(THF)}4(μ3-O)]4+ tetrahedral fragment in which two La atoms are linked by a pair of μ-SPh- and μ3-Cl- ligands to a [{(TMS)2N}2La]+ fragment, while the other two are bridged by two μ-SPh- ligands to a [Li(THF)2]+ fragment, forming a bee-shaped structure.