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Early–Late Heterobimetallic Alkoxides as Model Systems for Late‐Transition‐Metal Catalysts Supported on Titania
Author(s) -
Fandos Rosa,
Hernández Carolina,
Otero Antonio,
Rodríguez Ana,
Ruiz María José,
Terreros Pilar
Publication year - 2003
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200390075
Subject(s) - transition metal , catalysis , materials science , chemistry , organic chemistry
Abstract 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.