A new Titanium Alkoxide-Thiolate complex as a versatile heterofunctional Metalloligand

Abstract

The 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(u-OH)(cod)]3 (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)(PPh 3)] (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.