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Chemistry of Thermally Generated Transient Phosphanoxyl Complexes

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journal contribution
posted on 2017-07-06, 18:03 authored by Tobias Heurich, Zheng-Wang Qu, Gregor Schnakenburg, Yaser NejatyJahromy, Olav Schiemann, Stefan Grimme, Rainer Streubel
Investigations on the reactivity of the transiently formed phosphanoxyl complex [(CO)5W­(Ph2PO)], thermally generated from [(CO)5W­(Ph2PO-TEMP)] in toluene, is presented. Apart from self-reactions, trapping of this radical complex was achieved using group 14 hydrides Ph3EH (E = Si, Ge, Sn), leading to new phosphane complexes possessing a P–O–EPh3 bonding motif and the corresponding TEMP-H as byproduct. Reaction pathways, derived from DFT calculations, clearly revealed the intermediacy of various open-shell complexes; EPR measurements showed the presence of radicals, but unfortunately interpretation was not achieved.