ABSTRACT
The bicoordinated dihydroxyphosphenium ion P(OH)2+ (1+) was generated specifically by charge-exchange dissociative ionization of triethylphosphite and its connectivity was confirmed by collision induced dissociation and neutralization-reionization mass spectra. The major dissociation of 1+ forming PO+ ions at m/z 47 involved another isomer, O=P-OH2+ (2+), for which the optimized geometry showed a long P-OH2 bond. Dissociative 70-eV electron ionization of diethyl phosphite produced mostly 1+ together with a less stable isomer, HP(O)OH+ (3+). Ion 2+ is possibly co-formed with 1+ upon dissociative 70-eV electron ionization of methylphosphonic acid. Neutralization-reionization of 1+ confirmed that P(OH)2* (1) was a stable species. Dissociations of neutral 1, as identified by variable-time measurements, involved rate-determining isomerization to 2 followed by fast loss of water. A competitive loss of H occurs from long-lived excited states of 1 produced by vertical electron transfer. The A and B states undergo rate-determining internal conversion to vibrationally highly excited ground state that loses an H atom via two competing mechanisms. The first of these is the direct cleavage of one of the O-H bonds in 1. The other is an isomerization to 3 followed by cleavage of the P-H bond to form O=P-OH as a stable product. The relative, dissociation, and transition state energies for the ions and neutrals were studied by ab initio and density functional theory calculations up to the QCISD(T)/6-311+G(3df,2p) and CCSD(T)/aug-cc-pVTZ levels of theory. RRKM calculations were performed to investigate unimolecular dissociation kinetics of 1. Excited state geometries and energies were investigated by a combination of configuration interaction singles and time-dependent density functional theory calculations.
