A Series of Lithium Complexes of Bulky Rind-based Arylthiolate Ligands: Synthesis, Characterization, and Crystal Structures

Abstract

The bulky Rind-based thiols, (Rind)SH (1) [Rind = 1,1,7,7-tetra-R1-3,3,5,5-tetra-R2-s-hydrindacen-4-yl: EMind (a: R1 = Et, R2 = Me), Eind (b: R1 = R2 = Et), and MPhind (c: R1 = Me, R2 = Ph)], reacted with nBuLi in THF to afford a series of lithium arylthiolates, [(Rind)SLi]n(THF)m (2), whose structures were confirmed by an X-ray diffraction analysis. In the solid state, while the less bulky EMind-based lithium thiolate exhibited a linear dimer, [(EMind)SLi]2(THF)4 (2a), or trimer, [(EMind)SLi]3(THF)5 (2a′), the monomeric structures of (Eind)SLi(THF)3 (2b) and (MPhind)SLi(THF)2 (2c) were found for the bulky Eind- and the bulkier MPhind-based systems. The salt metathesis reaction between 2a and FeCl2(THF)1.5 in THF produced the anionic three-coordinate planar Fe(II) thiolate complex, [Li(THF)3][{(EMind)S}3Fe] (3a).