A New Titanium Alkoxide–Thiolate Complex as a Versatile Heterofunctional Metalloligand

Abstract

AbstractThe titanium complex [TiCp*(OSBz)(OBzSH)] (1) has been synthesized by reaction of [TiCp*(Me)3] (Cp* = η5‐C5Me5) with 2‐mercaptobenzyl alcohol (H2OSBz). The reaction of complex 1 with H2O gives the dinuclear oxo‐bridged complex [{TiCp*(OSBz)}2(μ‐O)] (2). Complex 1 reacts with [M(μ‐OH)(cod)]2 (M = Rh, Ir) to yield the early–late heterobimetallic complexes [TiCp*(OSBz)2M(cod)] {M = Rh (3); Ir (4)}. Carbon monoxide easily replaces the cod ligand in 3 and 4, which leads to the corresponding dicarbonyl derivatives [TiCp*(OSBz)2M(CO)2] {M = Rh (5); Ir (6)}. Compound 5 reacts with PPh3 to yield the monocarbonyl complex [TiCp*(OSBz)2Rh(CO)(PPh3)] (7). The molecular structures of complexes 2 and 5 have been established by single‐crystal X‐ray diffraction studies. The structure of complex 1 and its coordination mode toward a rhodium moiety have been ascertained by means of calculations based on density functional theory. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)