Periodic Trends in the Binding of a Phosphine-Tethered Ketone Ligand to Fe, Co, Ni, and Cu
| Autor: | Verhoeven, Dide G. A., Van Wiggen, Maxime A. C., Kwakernaak, Joost, Lutz, Martin, Klein Gebbink, Robertus J. M., Moret, Marc-etienne, Organic Chemistry and Catalysis, Crystal and Structural Chemistry, Sub Organic Chemistry and Catalysis, Sub Crystal and Structural Chemistry |
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| Přispěvatelé: | Organic Chemistry and Catalysis, Crystal and Structural Chemistry, Sub Organic Chemistry and Catalysis, Sub Crystal and Structural Chemistry |
| Rok vydání: | 2017 |
| Předmět: |
Ketone
ketones Homogeneous catalysis 010402 general chemistry Photochemistry 01 natural sciences Catalysis transition metals chemistry.chemical_compound Ketyl Transition metal pi ligands Taverne Benzophenone Moiety chemistry.chemical_classification coordination modes 010405 organic chemistry Ligand Organic Chemistry General Chemistry 0104 chemical sciences Crystallography chemistry density functional calculations Phosphine |
| Zdroj: | Chemistry-A European Journal, 24(20), 5163. Wiley |
| ISSN: | 1521-3765 0947-6539 |
| Popis: | π-Coordinating ligands are commonly found in intermediate structures in homogeneous catalysis, and are gaining interest as supporting ligands for the development of cooperative catalysts. Herein, we systematically investigate the binding of the ketone group - a strongly accepting π-ligand - to mid-to-late metals of the first transition series. To this end, the coordination of 2,2'-bis(diphenylphosphino)benzophenone (Phdpbp), featuring a ketone moiety flanked by two strongly binding P-donor groups, to Fe, Co, Ni and Cu is explored. The ketone moiety does not bind to the metal in M(II) complexes, whereas M(I) complexes (Fe, Co, Ni) adopt an η2(C,O)-coordination. A structural and computational investigation of periodic trends in this series was performed. These data suggest that the coordination of the ketone to M(I) can mostly be described by the resonance extremes of the Dewar-Chatt-Duncanson model, i.e. the π-complex and the metallaoxacycle extreme, with a possible minor contribution of a ketyl radical resonance structure in the case of the iron complex. |
| Databáze: | OpenAIRE |
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