Generation and characterization of ionic and neutral P(OH)2+/* in the gas phase by tandem mass spectrometry and computational chemistry

Journal of the American Society for Mass Spectrometry
R SrikanthFrantisek Turecek

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 isome...Continue Reading

References

Aug 1, 1996·Journal of Mass Spectrometry : JMS·V Q Nguyen, F Turecek
Jul 1, 1992·Journal of the American Society for Mass Spectrometry·F TurecekS A Shaffer

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Citations

Jul 19, 2002·Journal of Mass Spectrometry : JMS
Jul 17, 2012·European Journal of Mass Spectrometry·M Vairamani, S Prabhakar

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