title: Strong Evidence of a Phosphanoxyl Complex: Formation, Bonding, and Reactivity of Ligated Phosphorus Analogues of Nitroxides.
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.
authors.affiliation: Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121, Bonn, Germany.
authors.forename: Tobias
authors.initials: T
authors.lastname: Heurich
authors.affiliation: Institut für Siliciumchemie, Technische Universität München, Lichtenbergstrasse 4, 85748, Garching, Germany.
authors.forename: Vitaly
authors.initials: V
authors.lastname: Nesterov
authors.affiliation: Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121, Bonn, Germany.
authors.forename: Gregor
authors.initials: G
authors.lastname: Schnakenburg
authors.affiliation: Mulliken Center for Theoretical Chemistry, Rheinische Friedrich-Wilhelms-Universität Bonn, Beringstrasse 4, 53115, Bonn, Germany. qu@thch.uni-bonn.de.
authors.forename: Zheng-Wang
authors.initials: ZW
authors.lastname: Qu
authors.affiliation: Mulliken Center for Theoretical Chemistry, Rheinische Friedrich-Wilhelms-Universität Bonn, Beringstrasse 4, 53115, Bonn, Germany.
authors.forename: Stefan
authors.initials: S
authors.lastname: Grimme
authors.affiliation: Chemistry Department, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1, Canada.
authors.forename: Khatera
authors.initials: K
authors.lastname: Hazin
authors.affiliation: Chemistry Department, University of British Columbia, 2036 Main Mall, Vancouver, BC, V6T 1Z1, Canada.
authors.forename: Derek P
authors.initials: DP
authors.lastname: Gates
authors.affiliation: Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121, Bonn, Germany.
authors.forename: Marianne
authors.initials: M
authors.lastname: Engeser
authors.affiliation: Institut für Anorganische Chemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Strasse 1, 53121, Bonn, Germany. r.streubel@uni-bonn.de.
authors.forename: Rainer
authors.identifier: 0000-0001-5661-8502
authors.initials: R
authors.lastname: Streubel
keywords: TEMPO; density functional theory; phosphanoxyl; phosphanyl; spin density