12591-02-5Relevant articles and documents
Reaction kinetics of PO2Cl-, PO2Cl 2-, POCl2- and POCl3 - with O2 and O3 from 163 to 400 K
Fernandez, Abel I.,Midey, Anthony J.,Miller, Thomas M.,Viggiano
, p. 9120 - 9125 (2008/10/09)
Rate constants and product ion branching fractions for the gas-phase reactions of O2 and O3 with the anions (a) PO 2Cl-, (b) POCl3-, (c) POCl 2-, and (d) PO2Cl2- were measured in a selected-ion flow tube (SIFT). The kinetics were measured at temperatures of 163-400 K and a He pressure of 0.4 Torr. Only PO 2Cl- reacts with O2 to a measurable extent, having k(163-400 K) = 1.1 × 10-8(T/K)-1.0 cm 3 molecule-1 s-1, while O3 reacts with all of the anions except PO2Cl2-. The fitted rate constant expressions for the O3 reaction with anions a-c are as follows: ka(163-400 K) = 3.5 × 10-6(T/K) -1.6, kb(163-400 K) = 4.0 × 10 -7(T/K)-1.2, and kc(163-400 K) = 3.7 × 10-7(T/K)-1.4 cm3 molecule-1 s -1. Calculations were performed at the G3 level of theory to obtain optimized geometries, energies, and electron affinities (EAs) of the reactant and product species, as well as to determine the reaction thermochemistry to help understand the experimental results. The POxCly - anions that have lower electron binding energies (eBE) and higher spin multiplicities are more reactive. The doublets are more labile than the singlets. How the extra electron density is distributed in the anion does not predict the observed reactivity of the ion. The reactions of PO 2Cl- with O2 and O3 yield predominantly PO3- and PO4-. The reaction of POCl2- with O3 yields mostly Cl- and PO2Cl2-, while the POCl 3- reaction with O3 yields mostly O 3- and PO2Cl2-.
PRINCIPLES OF PHOSPHORUS CHEMISTRY
Bock, Hans
, p. 3 - 53 (2007/10/02)
An up-to-date concept of bonding in phosphorus compounds has to be based on the reality of molecular states.Molecules, which change their structure with energy, at present are best rationalized in terms of topology and symmetry, effective nuclear potentials and charge distribution.To reduce the complexity of the resulting manifold, comparison of equivalent states of chemical calculations, is strongly recommended.Adding the time-scale, molecular dynamics within the numerous degrees of freedom become important, also as a basis to gain some understanding og the rather complex microscopic reaction pathways of medium-sized molecules.Examples are presented to illustrate the use of spectroscopic "fingerprints" for the analysis and optimization of gasphase reactions as well as the benefit of inherent information on molecular states for the preparative phosphorus chemist.The catalytic dehydrochlorination of alkyldichlorophosphanes RH2C-PCl2 -> RHC=PCl -> R-CP and their dechlorination on magnesium metal surface are discussed in some detail as well as the generation of other unsaturated phosphorus molecules like Cl-P=O, Cl-P=S, ClP(=O)2, Cl-P(=S)2 or H3C-P=CH2.Approximate energy hypersurface calculations for the gasphase equilibrium P4 = 2P2 or for the unexpected dehydration (H3C)2HP=O -> H2O + H3C-P=CH2, which includes chemical activation, provide some insight into microscopic reaction pathways of phosphorus compounds.
