title: Matrix isolation and theoretical study of the reaction of substituted phosphines with CrCl2O2.
abstract: The reactions between CrO2Cl2 and a series of substituted phosphines have been investigated using matrix isolation infrared spectroscopy. For all of the phosphines except PF3, twin jet co-deposition of the two reagents into argon matrices at 14 K initially led to the formation of weak bands due to the corresponding phosphine oxide. For all of the phosphines, subsequent irradiation with light of lambda > 300 nm led to the growth of a number of intense new bands that have been assigned to the phosphine oxide complexed to CrCl2O, following an oxygen atom transfer reaction. Gas-phase, merged jet reactions prior to matrix deposition led to a significant yield of the uncomplexed phosphine oxide. Theoretical calculations at the B3LYP/6-311++g(d,2p) level were carried out in support of the experimental work, to support product band assignments and clarify the nature of the molecular complexes.
authors.affiliation: Department of Chemistry, University of Cincinnati, P.O. Box 210172, Cincinnati, OH 45220, USA.
authors.forename: Adam J
authors.initials: AJ
authors.lastname: Delson
authors.forename: Bruce S
authors.initials: BS
authors.lastname: Ault