Matrix Isolation and Theoretical Study of the Photochemical Reaction of PH₃ with OVCl₃ and CrCl₂O₂

Abstract

The matrix isolation technique has been combined with theoretical calculations to identify and characterize the photoproducts in the reaction of PH 3 with OVCl 3 and CrCl 2 O 2 . In contrast to previous studies, HCl elimination from an initial complex is not observed. Instead, a number of product bands, some quite intense, were observed and have been assigned to phosphine oxide, H 3 PO, through the direct O atom transfer from the transition metal oxo compound. This identification was supported by extensive isotopic labeling, and by comparison to theoretical calculations. H 3 PO formed in this manner is cage-paired and interacts with the transition metal fragment (VCl 3 or Cl 2 CrO), leading to a 113 cm -1 red-shift of the PdO stretching mode relative to isolated monomeric H 3 PO.

Matrix isolation and theoretical investigation of the photochemical reaction of CrCl2O2 with benzenes substituted with electron withdrawing groups

“…However, subsequent irradiation of these matrices led to the formation of product bands in a manner that is similar to the previous systems studied in this lab [23,[32][33][34]. Since diffusion of most molecules does not occur within the argon lattice at 14 K, for a photochemical reaction to occur after twin jet deposition the reactants must be trapped within the same matrix cage.…”

“…Past studies in this laboratory have examined the matrixisolated products of the thermal and photochemical reactions of CrCl 2 O 2 , OVCl 3 , and OVF 3 with organic and inorganic substrates [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32]. Specifically, two recent studies in this lab [33,34] examined the reactions of CrCl 2 O 2 with benzene and with methyl-substituted benzenes.…”

Experimental Evidence of Phosphine Oxide Generation in Solution and Trapping by Ruthenium Complexes

“…[4] Finally, Ault and Kayser observed the formation of H 3 PO in argon matrices after photochemical irradiation of a mixture of VOCl 3 , CrO 2 Cl 2 , and PH 3 . [5] Both molecules have been studied by theoretical methods. [6] Application of an adequate phosphorus basis set has recently shown that, in contrast with previous ab initio studies, [7] I is more stable than II by only about 1 kcal mol À1 in the gas phase.…”

Chemistry in low-temperature matrices

“…Phosphine (PH 3 ) reacts with OVCl 3 and CrO 2 Cl 2 on irradiation in a low temperature matrix to give the phosphine oxide OPH 3 by O-atom transfer. 281 There was no sign of HCl elimination here. With water both OVCl 3 and CrO 2 Cl 2 react to give 1:1 complexes which do undergo HCl elimination on photolysis and l 4 300 nm.…”