Strong Evidence of a Phosphanoxyl Complex: Formation,Bonding, and Reactivity of Ligated Phosphorus Analogues of Nitroxides |
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| Authors: | Tobias Heurich Dr. Vitaly Nesterov Dr. Gregor Schnakenburg Dr. Zheng‐Wang Qu Prof. Dr. Stefan Grimme Khatera Hazin Prof. Dr. Derek P. Gates Priv.‐Doz. Dr. Marianne Engeser Prof. Dr. Rainer Streubel |
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| Affiliation: | 1. Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universit?t Bonn, Bonn, Germany;2. Institut für Siliciumchemie, Technische Universit?t München, Garching, Germany;3. Mulliken Center for Theoretical Chemistry, Rheinische Friedrich-Wilhelms-Universit?t Bonn, Bonn, Germany;4. Chemistry Department, University of British Columbia, Vancouver, BC, Canada;5. Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universit?t Bonn, Bonn, Germany |
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| Abstract: | Facile access to [W(CO)5(Ph2P‐OTEMP)] is used to initiate a study on the generation, properties, and reactions of transient phosphanoxyl complexes [MLn(R2PO)], the first example of which could be trapped via heterocoupling with the trityl radical. It is also demonstrated that the phosphorus nitroxyl complex acts as radical initiator in the polymerization of styrene. The quest for P?O versus O?N bond homolysis, as well as the initial steps of the polymerization were studied by DFT methods. |
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| Keywords: | density functional theory phosphanoxyl phosphanyl spin density TEMPO |
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