Selective phosphanyl complex trapping using TEMPO. Synthesis and reactivity of P-functional P-nitroxyl phosphane complexes

摘要

Open-shell phosphanyl complexes (OC)_5W{(Me_3Si)_2HCP(X)} (X = F, H), obtained by one-electron oxidation of lithium phosphanido complexes, were trapped by TEMPO to yield novel thermally labile P-nitroxyl phosphane complexes. First experimental evidence for an open-shell P-F phosphanoxyl complex (OC)_5W{(Me_3Si)_2HCP(O)F), formed upon thermolysis of corresponding P-nitroxyl derivative, is reported; reaction pathways are also theoretically investigated.