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Strong Evidence of a Phosphanoxyl Complex: Formation, Bonding, and Reactivity of Ligated Phosphorus Analogues of Nitroxides
Author(s) -
Heurich Tobias,
Nesterov Vitaly,
Schnakenburg Gregor,
Qu ZhengWang,
Grimme Stefan,
Hazin Khatera,
Gates Derek P.,
Engeser Marianne,
Streubel Rainer
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201608169
Subject(s) - reactivity (psychology) , phosphorus , chemistry , organic chemistry , medicine , alternative medicine , pathology
Facile access to [W(CO) 5 (Ph 2 P‐OTEMP)] is used to initiate a study on the generation, properties, and reactions of transient phosphanoxyl complexes [ML n (R 2 PO)], 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.