Reactions of anionic transition metal carbonyl hydrides with electrophilic metal carbonyls: Nucleophilic addition (hydride transfer) vs. electron transfer mechanisms
| Autor: | C. P. Janzen, Yong K. Park, Carlton E. Ash, Larry W. Arndt, Marcetta Y. Darensbourg, Kay A. Youngdahl |
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| Rok vydání: | 1990 |
| Předmět: |
Nucleophilic addition
Hydride Chemistry Organic Chemistry Metal carbonyl Photochemistry Biochemistry Medicinal chemistry Inorganic Chemistry Metal Electron transfer Nucleophile Transition metal Metal carbonyl hydride visual_art Materials Chemistry visual_art.visual_art_medium Physical and Theoretical Chemistry |
| Zdroj: | Journal of Organometallic Chemistry. 383:191-199 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/0022-328x(90)85131-h |
| Popis: | The relative reactivity of anionic transition metal carbonyl hydrides towards hydride transfer to monomeric metal carbonyls is consistent with an ionic route, generating, in the best-matched cases of electrophilic carbonyls (highest f CO or average v (CO)) and most nucleophilic hydrides (such as HW(CO) 4 P(OMe) 3 − ), metal formyls as sole product. With the metal carbonyl dimers Co 2 (CO) 8 , [(η 5 -C 5 H 5 )M(CO) 3 ] 2 (M = Mo, W), and Mn 2 (CO) 10 reductive cleavage to the respective anions occurs at rates which correlate with the nucleophilicity of the metal hydride, without observation of intermediate formyls. No reaction occurs with Re 2 (CO) 10 or [(η 5 -C 5 H 5 )Fe(CO) 2 ] 2 . |
| Databáze: | OpenAIRE |
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