Abstract
Investigation of the coordination behavior of 4,4′-methylenebis(2,6-di-tert-butylphenol) (or H2-4DBP) with a series of metal alkoxides led to isolation of [(OR)3M]2(µ-4DBP), where M/OR = Ti/OBut (2), Ti/ONep (3), Zr/OBut (4), Hf/OBut (5), and [(py)(OR)3M]2(µ-4DBP) · py (5a), where py = pyridine and ONep = OCH2C(CH3)3. Metal alkyl derivatives of 4DBP were also studied and found to form similar di-substituted species: [(py)2(Et)Zn]2(µ-4DBP) · py (6), [(THF)3(Br)Mg]2(µ-4DBP) (7), [(THF)2(Br)Mg](µ-4DBP)[Mg(Br)(THF)3] · (THF, tol) (7a), and [(py)(R)2Al]2(µ-4DBP), where R = CH3 (8), Et (9), CH2CH(CH3)2 (10); tol = toluene and THF = tetrahydrofuran. All structures demonstrate the bridging nature of 4DBP and the ability to bind a variety of metal centers. Solution state NMR indicates that the structures of 2–10 are retained in solution. Thermal analyses indicate that 4DBP is preferentially lost during heating.
Acknowledgments
The authors thank Mr B. Simmon (Sandia) for PXRD analyses, use of the Bruker X-ray diffractometer [National Science Foundation CRIF : MU award to the University of New Mexico (CHE04-43580)], the National Institute for NanoEngineering (NINE) program, and the Laboratory Directed Research and Development (LDRD) program for supporting this research. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.