Synthesis, Characterization, and Reduction Chemistry of Mixed-Cyclopentadienyl/Arylsulfide Titanium Dichlorides

Abstract

A series of titanium derivatives [CpTi(SAr)Cl2] containing both cyclopentadienyl and various substituted arylsulfide ligands (SAr = SC6H4Me-4 (1), SC6H2Me3-2,4,6 (2), SC6H2Pri3-2,4,6 (3), SC6H2Ph3-2,4,6 (4)) has been synthesized from the reaction of [CpTiCl3] with 1 equiv of the lithium salt of the corresponding arylsulfides in benzene. X-ray diffraction studies show that each metal center possesses a pseudo-tetrahedral geometry. The compounds undergo one-electron reduction to produce sulfur-bridged dimers of the type [CpTiCl(μ-SAr)]2 (SAr = SC6H2Me3-2,4,6 (5), SC6H2Pri3-2,4,6 (6)). The solid-state structures of these dimers show that the cyclopentadienyl rings are arranged in a transoid fashion about the [Ti(μ-SAr)2Ti] core. The Ti−Ti distances, 3.242(1) and 3.225(1) Å, respectively, are similar to those found in previously reported Cp/aryloxide dimers with terminal aryloxides and bridging chlorides.