Two geometrically constrained phosphorus compounds have been shown to undergo rapid oxidative addition to O-H and N-H bonds. The planar s3-phosphorus compound 1  has been demonstrated to undergo facile addition to the N-H bonds of ammonia and primary alkyl and aryl amines. Kinetic and computational studies have implicated an entropy-controlled mechanism involving initial attack of the amine at the electrophilic phosphorus center followed by a rate determining amine-assisted proton transfer. Compound 2 , which adopts a cis-divacant trigonal bipyramidal structure, also undergoes rapid oxidative addition to both O-H and N-H bonds via a distinct mechanism. These reactions represent rare examples of well characterized intermolecular oxidative addition at a P(III) center to yield structurally robust P(V) adducts. The reactivities of the pentacoordinate compounds, specifically with respect to alcohol and amine transfer, will be evaluated and discussed.

Oxidative addition of N-H and O-H bonds to geometrically constrained phosphorus compounds

248th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.