The syntheses and structures of coordinatively unsaturated aryloxy-hydride complexes of molybdenum, Mo(PMe3)4(OAr)H: reversible CH bond activation and comparison with their tungsten analogues
| Autor: | Tony Hascall, Gerard Parkin, Kevin E. Janak, Vincent J. Murphy |
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| Rok vydání: | 2002 |
| Předmět: |
Hydride
Organic Chemistry Trimethylphosphine chemistry.chemical_element Tungsten Photochemistry Biochemistry Oxidative addition Medicinal chemistry Inorganic Chemistry chemistry.chemical_compound chemistry Deuterium Molybdenum Intramolecular force Yield (chemistry) Materials Chemistry Physical and Theoretical Chemistry |
| Zdroj: | Journal of Organometallic Chemistry. 652:37-49 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/s0022-328x(02)01306-2 |
| Popis: | Mo(PMe 3 ) 6 reacts with ArOH (Ar=2,4,6-C 6 H 2 Me 3 , 2,6-C 6 H 3 Pr i 2 ) to give coordinatively unsaturated aryloxy-hydride derivatives Mo(PMe 3 ) 4 (OAr)H. The formation of Mo(PMe 3 ) 4 (OAr)H is in marked contrast to the cyclometalated products of CH bond activation that are obtained for the corresponding tungsten system. Deuterium labeling and magnetization transfer studies, however, demonstrate that the coordinatively unsaturated molybdenum complexes Mo(PMe 3 ) 4 (OAr)H are in fact kinetically capable of intramolecular oxidative addition of a CH bond of the ortho substituents to yield cyclometalated derivatives that are thermodynamically unstable with respect to the aryloxy-hydride derivatives. |
| Databáze: | OpenAIRE |
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