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Abstract
Continued exploration of the coordination behavior of derivatives of 2-benzophenone-based ligands with metal alkoxides ([M(OR)4]) was undertaken from the reaction of 2-(2-hydroxy-4-methoxybenzoyl)benzoic acid (H2-OBzA) with a series of Group 4 precursors. The products of these reactions were identified as: [(OR)2Ti(μ-(c,c-OBzA))]2 (OR = OCHMe2 (OPri; 1 •2tol); OCMe3 (OBut; 2 •THF); OCH2CMe3 (ONep; 3)), [[(OPri)3Ti(μ-OPri)Ti(OPri)2]2(μ-(μc,μ-OBzA))2]2 (4), [(ONep)3Zr(μ-ONep)2Zr(ONep)2]2(μ-(c,μ-OBzA)2) (5 •tol), [(py)(OBut)3Zr]2(μ-(c,c-OBzA)) (6), [(OBut)2Hf(μ-OBut)]2(μ-(c,η1-OBzA)) (7) where ‘c’ = chelating or η2; ‘μ’ = bridging or η1,η1(O,O’); and μc = bridging chelating or η1,η1(O,O’); η2 : η1. The metal centers for each of these compounds adopt a pseudo-octahedral geometry employing the OBzA ligand in numerous binding modes. The different functional oxygens (carboxylate, hydroxyl, and carbonyl) were employed in a variety of coordination modes for 1–7. The complexity of these OBzA-modified compounds is driven by a combination of the coordination behavior of the OBzA moieties, the size of the metal cation, and the pendant chain of the OR ligand. Solution NMR indicates a complex structure exists in solution that was considered to be consistent with the solid-state structure.
Graphical Abstract
Acknowledgements
This work was supported by the Laboratory Directed Research and Development (LDRD) program at Sandia National Laboratories. The Bruker X-ray diffractometer used for some crystal solutions was purchased via a National Science Foundation CRIF:MU award to the University of New Mexico (CHE04-43580). Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy’s National Nuclear Security Administration under Contract DE-AC04-94AL85000.