Synthesis, Structure, and Reactivity of [C5Me5CoLL‘] Complexes with L = Pyridine and L‘ = Olefin or L−L‘ = Bipyridine
| Autor: | Christian P. Lenges, Maurice Brookhart, and Will J. Marshall, Peter S. White |
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| Rok vydání: | 2000 |
| Předmět: | |
| Zdroj: | Organometallics. 19:1247-1254 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om990860s |
| Popis: | The bis(olefin) complex [C5Me5Co(C2H3SiMe3)2] (6) reacts with pyridine at 22 °C to give the pyridine olefin complex [C5Me5Co(C2H3SiMe3)(C5H5N)] (7). The addition of excess pyridine does not result in the formation of a bis(pyridine) adduct. Thermolysis of solutions of 7 in benzene-d6 results in catalytic H/D exchange which incorporates deuterium from the solvent into coordinated olefin. Pyridine dissociation generates a 16-electron intermediate which is formulated as the reactive species. At long times deuteration of the coordinated pyridine is also observed via shuttling of deuterium from the solvent to the olefin ligand and then to the pyridine. The reaction of 6 with pyridine-d5 results in the analogue 7-d5. Thermolysis of 7-d5 shows preference for H/D exchange at the ortho positions of coordinated pyridine, which has been explained by the formation of η2-coordinated intermediates. Reaction of 4-phenylpyridine with 6 yields the analogous pyridine adduct [C5Me5Co(C2H3SiMe3)(4-C6H5-C5H4N)] (12), which wa... |
| Databáze: | OpenAIRE |
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