5 years ago

Chemistry of Thermally Generated Transient Phosphanoxyl Complexes

Chemistry of Thermally Generated Transient Phosphanoxyl Complexes
Stefan Grimme, Yaser NejatyJahromy, Zheng-Wang Qu, Tobias Heurich, Rainer Streubel, Olav Schiemann, Gregor Schnakenburg
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.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00347

DOI: 10.1021/acs.organomet.7b00347

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