Issue 18, 2022

Photoelectron spectroscopy of low valent organophosphorus compounds, P–CH3, H–P[double bond, length as m-dash]CH2 and P[double bond, length as m-dash]CH2

Abstract

We report the mass-selected slow photoelectron spectra of three reactive organophosphorus species, P[double bond, length as m-dash]CH2, and the two isomers, methylenephosphine or phosphaethylene, HP[double bond, length as m-dash]CH2 and methylphosphinidine, P–CH3. All spectra were recorded by double imaging photoelectron–photoion coincidence spectroscopy (i2PEPICO) using synchrotron radiation and all species were generated in a flow reactor by the reaction of trimethyl phosphine with fluorine atoms. Adiabatic ionisation energies of 8.80 ± 0.02 eV (P[double bond, length as m-dash]CH2), 10.07 ± 0.03 eV (H–P[double bond, length as m-dash]CH2) and 8.91 ± 0.04 eV (P–CH3) were determined and the vibronic structure was simulated by calculating Franck–Condon factors from optimised structures based on quantum chemical methods. Observation of biradicalic P–CH3 isomer with its triplet ground state is surprising because it is less stable than H–P[double bond, length as m-dash]CH2.

Graphical abstract: Photoelectron spectroscopy of low valent organophosphorus compounds, P–CH3, H–P [[double bond, length as m-dash]] CH2 and P [[double bond, length as m-dash]] CH2

Supplementary files

Article information

Article type
Paper
Submitted
05 Mar 2022
Accepted
18 Apr 2022
First published
18 Apr 2022

Phys. Chem. Chem. Phys., 2022,24, 10993-10999

Photoelectron spectroscopy of low valent organophosphorus compounds, P–CH3, H–P[double bond, length as m-dash]CH2 and P[double bond, length as m-dash]CH2

D. P. Mukhopadhyay, M. Gerlach, S. Hartweg, I. Fischer and J. Loison, Phys. Chem. Chem. Phys., 2022, 24, 10993 DOI: 10.1039/D2CP01082H

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