Observation and characterization of the CH 3S(O)CH - and CH 3S(O)CH -· H 2O carbene anions by photoelectron imaging and photofragment spectroscopy

Luis Velarde, Terefe Habteyes, Richard S Glass, Andrei M Sanov

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3 Citations (Scopus)

Abstract

We report the observation of the CH 3S(O)CH - and CH 3S(O)CH -·H 2O carbene anions formed upon overall H 2 + abstraction from dimethyl sulfoxide by O -. Photoelectron spectroscopy reveals singlet and triplet carbenes for the remaining neutral, with the singlet state assigned as the ground state. Although some formation of the distonic CH 2S(O)CH 2 - radical anion is also expected, no conclusive evidence of the presence of this isomer is found. The photoelectron spectrum of HCSO - is also reported for the first time. Photofragmentation of CH 3S(O)CH - with 532 nm light reveals two main types of anionic products: a dominant HCSO - fragment, resulting from methyl elimination, and a less intense SO - product. For the monohydrated anion, an additional SO - · H 2O fragment is observed. Intriguingly, both the SO -·H 2O and SO - products are produced with much higher yields in the fragmentation of CH 3S(O)CH - · H 2O, compared to the SO - yield from the dissociation of the bare CH 3S(O)CH- anion. Two possible pathways are proposed as likely mechanisms for the SO --based photoproducts, both involving a photoinduced intramolecular rearrangement and the formation of a C-C bond.

Original languageEnglish (US)
Pages (from-to)3528-3534
Number of pages7
JournalJournal of Physical Chemistry A
Volume113
Issue number15
DOIs
StatePublished - Apr 16 2009

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carbenes
Photoelectrons
Anions
photoelectrons
Spectroscopy
methylidyne
anions
Imaging techniques
spectroscopy
Photoelectron spectroscopy
Dimethyl Sulfoxide
Isomers
Ground state
carbene
products
fragments
elimination
fragmentation
isomers
photoelectron spectroscopy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

@article{2081ab6de1d4450c9043b5d0a3238725,
title = "Observation and characterization of the CH 3S(O)CH - and CH 3S(O)CH -· H 2O carbene anions by photoelectron imaging and photofragment spectroscopy",
abstract = "We report the observation of the CH 3S(O)CH - and CH 3S(O)CH -·H 2O carbene anions formed upon overall H 2 + abstraction from dimethyl sulfoxide by O -. Photoelectron spectroscopy reveals singlet and triplet carbenes for the remaining neutral, with the singlet state assigned as the ground state. Although some formation of the distonic CH 2S(O)CH 2 - radical anion is also expected, no conclusive evidence of the presence of this isomer is found. The photoelectron spectrum of HCSO - is also reported for the first time. Photofragmentation of CH 3S(O)CH - with 532 nm light reveals two main types of anionic products: a dominant HCSO - fragment, resulting from methyl elimination, and a less intense SO - product. For the monohydrated anion, an additional SO - · H 2O fragment is observed. Intriguingly, both the SO -·H 2O and SO - products are produced with much higher yields in the fragmentation of CH 3S(O)CH - · H 2O, compared to the SO - yield from the dissociation of the bare CH 3S(O)CH- anion. Two possible pathways are proposed as likely mechanisms for the SO --based photoproducts, both involving a photoinduced intramolecular rearrangement and the formation of a C-C bond.",
author = "Luis Velarde and Terefe Habteyes and Glass, {Richard S} and Sanov, {Andrei M}",
year = "2009",
month = "4",
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TY - JOUR

T1 - Observation and characterization of the CH 3S(O)CH - and CH 3S(O)CH -· H 2O carbene anions by photoelectron imaging and photofragment spectroscopy

AU - Velarde, Luis

AU - Habteyes, Terefe

AU - Glass, Richard S

AU - Sanov, Andrei M

PY - 2009/4/16

Y1 - 2009/4/16

N2 - We report the observation of the CH 3S(O)CH - and CH 3S(O)CH -·H 2O carbene anions formed upon overall H 2 + abstraction from dimethyl sulfoxide by O -. Photoelectron spectroscopy reveals singlet and triplet carbenes for the remaining neutral, with the singlet state assigned as the ground state. Although some formation of the distonic CH 2S(O)CH 2 - radical anion is also expected, no conclusive evidence of the presence of this isomer is found. The photoelectron spectrum of HCSO - is also reported for the first time. Photofragmentation of CH 3S(O)CH - with 532 nm light reveals two main types of anionic products: a dominant HCSO - fragment, resulting from methyl elimination, and a less intense SO - product. For the monohydrated anion, an additional SO - · H 2O fragment is observed. Intriguingly, both the SO -·H 2O and SO - products are produced with much higher yields in the fragmentation of CH 3S(O)CH - · H 2O, compared to the SO - yield from the dissociation of the bare CH 3S(O)CH- anion. Two possible pathways are proposed as likely mechanisms for the SO --based photoproducts, both involving a photoinduced intramolecular rearrangement and the formation of a C-C bond.

AB - We report the observation of the CH 3S(O)CH - and CH 3S(O)CH -·H 2O carbene anions formed upon overall H 2 + abstraction from dimethyl sulfoxide by O -. Photoelectron spectroscopy reveals singlet and triplet carbenes for the remaining neutral, with the singlet state assigned as the ground state. Although some formation of the distonic CH 2S(O)CH 2 - radical anion is also expected, no conclusive evidence of the presence of this isomer is found. The photoelectron spectrum of HCSO - is also reported for the first time. Photofragmentation of CH 3S(O)CH - with 532 nm light reveals two main types of anionic products: a dominant HCSO - fragment, resulting from methyl elimination, and a less intense SO - product. For the monohydrated anion, an additional SO - · H 2O fragment is observed. Intriguingly, both the SO -·H 2O and SO - products are produced with much higher yields in the fragmentation of CH 3S(O)CH - · H 2O, compared to the SO - yield from the dissociation of the bare CH 3S(O)CH- anion. Two possible pathways are proposed as likely mechanisms for the SO --based photoproducts, both involving a photoinduced intramolecular rearrangement and the formation of a C-C bond.

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