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Group IV Coordination Chemistry of a Tetradentate Redox‐Active Ligand in Two Oxidation States
Author(s) -
Blackmore Karen J.,
Lal Neetu,
Ziller Joseph W.,
Heyduk Alan F.
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200800945
Subject(s) - chemistry , ligand (biochemistry) , redox , pyridine , metal , halogen , non innocent ligand , molecule , medicinal chemistry , solvent , coordination complex , oxidative addition , stereochemistry , crystallography , inorganic chemistry , organic chemistry , catalysis , biochemistry , alkyl , receptor
The redox‐active ligand N , N′ ‐bis(3,5‐di‐ tert ‐butyl‐2‐phenoxy)‐1,2‐phenylenediamide [N 2 O 2 red ] 4– reacts with group IV metal salts to form six‐ and seven‐coordinate complexes [N 2 O 2 red ]ML n (M = Ti, L = py, n = 2; M = Zr, Hf, L = thf, n = 3). The redox‐active ligand occupies four equatorial coordination sites in these complexes. In the case of the zirconium and hafnium complexes, two axial solvent molecules coordinate to the metal center with a third solvent molecule coordinating in the equatorial plane. In the case of the smaller titanium metal center, only two pyridine solvent molecules coordinate to the metal atom, leaving an open coordination site. All three complexes react with halogen oxidants to afford oxidative addition products [N 2 O 2 ox ]MCl 2 L n (M = Ti, n = 0; M = Zr, Hf, L = thf, n = 1), in which the redox‐active ligand is oxidized by two electrons to the cyclohexadienediimine state. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)