Early–Late Heterobimetallic Alkoxides as Model Systems for Late‐Transition‐Metal Catalysts Supported on Titania

Titanium complexes with chelating alkoxide ligands [TiCp*(O 2 Bz)(OBzOH)] ( 1 ) and [TiCp*(Me){(OCH 2 ) 2 Py}] ( 2 ) were synthesised by reaction of [TiCp*Me 3 ] (Cp*= η 5 ‐C 5 Me 5 ) with 2‐hydroxybenzyl alcohol ((HO) 2 Bz) and 2,6‐pyridinedimethanol ((HOCH 2 ) 2 Py), respectively. Complex 1 reacts with [{M( μ ‐OH)(cod)} 2 ] (M=Rh, Ir) to yield the early–late heterobimetallic complexes [TiCp*(O 2 Bz) 2 M(cod)] [M=Rh ( 3 ), Ir ( 4 )]. Carbon monoxide readily replaces the COD ligand in 3 to give the rhodium dicarbonyl derivative [TiCp*(O 2 Bz) 2 Rh(CO) 2 ] ( 5 ). Compound 2 reacts with [{M( μ ‐OH)(cod)} 2 ] (M=Rh, Ir) with protonolysis of a TiMe bond to give [TiCp*{(OCH 2 ) 2 Py}( μ ‐O)M(cod)] [M=Rh ( 6 ), Ir ( 7 )]. The molecular structures of complexes 3, 5 and 7 were established by single‐crystal X‐ray diffraction studies.