Aminotroponiminate and Aminotroponate Complexes of Group 15 (P, As) Elements: Synthesis, X‐ray Diffraction Analysis and Reactivity

Abstract

AbstractNew phosphenium and arsenium cations stabilized by bidentate monoanionic N‐isopropyl‐2‐(isopropylamino)troponiminate or 2‐(isopropylamino)troponate units have been synthesized. These complexes were characterized by 31P, 1H and 13C NMR spectroscopy and the molecular structures were determined by X‐ray crystallography. These data indicate the formation of N,N′‐ and N,O‐chelate derivatives with three‐coordinate Group 15 atoms included in planar heterobicycles. The reactivities of these cationic species were investigated. The phosphenium cations were found to be more reactive than their arsenium analogues, especially towards an o‐quinone, with the formation of a phosphate ester derivative. Complexation reactions with [(THF)W(CO)5] afforded the first aminotroponiminato hydroxyphosphenium cation stabilized by coordination to a transition metal.