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Probing the Reactivity and Radical Nature of Oxidized Transition Metal-Thiolate Complexes by Mass Spectrometry

Transition metal thiolate complexes such as [PPN] + [RuL 3 ] - (PPN = bis(triphenylphosphoranylidene) ammonium and L = diphenylphosphinobenzenethiolate) are known to undergo addition reactions with unsaturated hydrocarbons via the formation of new C-S bonds in solution upon oxidation. The reaction m... Full description

Journal Title: Journal of The American Society for Mass Spectrometry 2013, Vol.24(4), pp.502-512
Main Author: Lu, Mei
Other Authors: Campbell, J. Larry , Chauhan, Rajat , Grapperhaus, Craig A. , Chen, Hao
Format: Electronic Article Electronic Article
Language: English
Subjects:
ID: ISSN: 1044-0305 ; E-ISSN: 1879-1123 ; DOI: 10.1007/s13361-012-0537-1
Link: http://dx.doi.org/10.1007/s13361-012-0537-1
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recordid: springer_jour10.1007/s13361-012-0537-1
title: Probing the Reactivity and Radical Nature of Oxidized Transition Metal-Thiolate Complexes by Mass Spectrometry
format: Article
creator:
  • Lu, Mei
  • Campbell, J. Larry
  • Chauhan, Rajat
  • Grapperhaus, Craig A.
  • Chen, Hao
subjects:
  • Distonic ion
  • Thiyl radical
  • Mass spectrometry
  • Ion/molecule reaction
ispartof: Journal of The American Society for Mass Spectrometry, 2013, Vol.24(4), pp.502-512
description: Transition metal thiolate complexes such as [PPN] + [RuL 3 ] - (PPN = bis(triphenylphosphoranylidene) ammonium and L = diphenylphosphinobenzenethiolate) are known to undergo addition reactions with unsaturated hydrocarbons via the formation of new C-S bonds in solution upon oxidation. The reaction mechanism is proposed to involve metal-stabilized thiyl radical intermediates, a new type of distonic ions such as [RuL 3 ] + ion in the case of [PPN] + [RuL 3 ] - . This study presents the reactivity and structure investigation of [RuL 3 ] + by mass spectrometry (MS) in conjunction with ion/molecule reactions. The addition reactions of [RuL 3 ] + with alkenes or methyl ketones in the gas phase are indeed observed, in agreement with the proposed mechanism. Such reactivity is also maintained by several fragment ions of [RuL 3 ] + , indicating the preserved thiyl diradical core structure is responsible for the addition reaction. The thiyl radical nature of [RuL 3 ] + was further verified by the ion/molecule reaction of [RuL 3 ] + with dimethyl disulfide, in which the characteristic CH 3 S• transfer occurs, both at atmospheric pressure and also at low pressure (~mTorr). These results provide, for the first time, clear mass spectrometric evidence of the radical nature of [RuL 3 ] + (i.e., the distonic ion structure of [RuL 3 ] + ), arising from the oxidation of non-innocent thiolate ligands of the complex [PPN] + [RuL 3 ] - . Similar thiolate complexes, including ReL 3 and NiL 2 , were also examined. Although reactions of oxidized ReL 3 or NiL 2 with CH 3 SSCH 3 take place at atmospheric pressure, the corresponding reaction did not occur in vacuum. Consistent with these data, the addition of ethylene was not observed either, indicating lower reactivities of [ReL 3 ] + and [NiL 2 ] + in comparison to [RuL 3 ] + .
language: eng
source:
identifier: ISSN: 1044-0305 ; E-ISSN: 1879-1123 ; DOI: 10.1007/s13361-012-0537-1
fulltext: fulltext
issn:
  • 1879-1123
  • 18791123
  • 1044-0305
  • 10440305
url: Link


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titleProbing the Reactivity and Radical Nature of Oxidized Transition Metal-Thiolate Complexes by Mass Spectrometry
creatorLu, Mei ; Campbell, J. Larry ; Chauhan, Rajat ; Grapperhaus, Craig A. ; Chen, Hao
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subjectDistonic ion ; Thiyl radical ; Mass spectrometry ; Ion/molecule reaction
descriptionTransition metal thiolate complexes such as [PPN] + [RuL 3 ] - (PPN = bis(triphenylphosphoranylidene) ammonium and L = diphenylphosphinobenzenethiolate) are known to undergo addition reactions with unsaturated hydrocarbons via the formation of new C-S bonds in solution upon oxidation. The reaction mechanism is proposed to involve metal-stabilized thiyl radical intermediates, a new type of distonic ions such as [RuL 3 ] + ion in the case of [PPN] + [RuL 3 ] - . This study presents the reactivity and structure investigation of [RuL 3 ] + by mass spectrometry (MS) in conjunction with ion/molecule reactions. The addition reactions of [RuL 3 ] + with alkenes or methyl ketones in the gas phase are indeed observed, in agreement with the proposed mechanism. Such reactivity is also maintained by several fragment ions of [RuL 3 ] + , indicating the preserved thiyl diradical core structure is responsible for the addition reaction. The thiyl radical nature of [RuL 3 ] + was further verified by the ion/molecule reaction of [RuL 3 ] + with dimethyl disulfide, in which the characteristic CH 3 S• transfer occurs, both at atmospheric pressure and also at low pressure (~mTorr). These results provide, for the first time, clear mass spectrometric evidence of the radical nature of [RuL 3 ] + (i.e., the distonic ion structure of [RuL 3 ] + ), arising from the oxidation of non-innocent thiolate ligands of the complex [PPN] + [RuL 3 ] - . Similar thiolate complexes, including ReL 3 and NiL 2 , were also examined. Although reactions of oxidized ReL 3 or NiL 2 with CH 3 SSCH 3 take place at atmospheric pressure, the corresponding reaction did not occur in vacuum. Consistent with these data, the addition of ethylene was not observed either, indicating lower reactivities of [ReL 3 ] + and [NiL 2 ] + in comparison to [RuL 3 ] + .
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titleProbing the Reactivity and Radical Nature of Oxidized Transition Metal-Thiolate Complexes by Mass Spectrometry
descriptionTransition metal thiolate complexes such as [PPN] + [RuL 3 ] - (PPN = bis(triphenylphosphoranylidene) ammonium and L = diphenylphosphinobenzenethiolate) are known to undergo addition reactions with unsaturated hydrocarbons via the formation of new C-S bonds in solution upon oxidation. The reaction mechanism is proposed to involve metal-stabilized thiyl radical intermediates, a new type of distonic ions such as [RuL 3 ] + ion in the case of [PPN] + [RuL 3 ] - . This study presents the reactivity and structure investigation of [RuL 3 ] + by mass spectrometry (MS) in conjunction with ion/molecule reactions. The addition reactions of [RuL 3 ] + with alkenes or methyl ketones in the gas phase are indeed observed, in agreement with the proposed mechanism. Such reactivity is also maintained by several fragment ions of [RuL 3 ] + , indicating the preserved thiyl diradical core structure is responsible for the addition reaction. The thiyl radical nature of [RuL 3 ] + was further verified by the ion/molecule reaction of [RuL 3 ] + with dimethyl disulfide, in which the characteristic CH 3 S• transfer occurs, both at atmospheric pressure and also at low pressure (~mTorr). These results provide, for the first time, clear mass spectrometric evidence of the radical nature of [RuL 3 ] + (i.e., the distonic ion structure of [RuL 3 ] + ), arising from the oxidation of non-innocent thiolate ligands of the complex [PPN] + [RuL 3 ] - . Similar thiolate complexes, including ReL 3 and NiL 2 , were also examined. Although reactions of oxidized ReL 3 or NiL 2 with CH 3 SSCH 3 take place at atmospheric pressure, the corresponding reaction did not occur in vacuum. Consistent with these data, the addition of ethylene was not observed either, indicating lower reactivities of [ReL 3 ] + and [NiL 2 ] + in comparison to [RuL 3 ] + .
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abstractTransition metal thiolate complexes such as [PPN] + [RuL 3 ] - (PPN = bis(triphenylphosphoranylidene) ammonium and L = diphenylphosphinobenzenethiolate) are known to undergo addition reactions with unsaturated hydrocarbons via the formation of new C-S bonds in solution upon oxidation. The reaction mechanism is proposed to involve metal-stabilized thiyl radical intermediates, a new type of distonic ions such as [RuL 3 ] + ion in the case of [PPN] + [RuL 3 ] - . This study presents the reactivity and structure investigation of [RuL 3 ] + by mass spectrometry (MS) in conjunction with ion/molecule reactions. The addition reactions of [RuL 3 ] + with alkenes or methyl ketones in the gas phase are indeed observed, in agreement with the proposed mechanism. Such reactivity is also maintained by several fragment ions of [RuL 3 ] + , indicating the preserved thiyl diradical core structure is responsible for the addition reaction. The thiyl radical nature of [RuL 3 ] + was further verified by the ion/molecule reaction of [RuL 3 ] + with dimethyl disulfide, in which the characteristic CH 3 S• transfer occurs, both at atmospheric pressure and also at low pressure (~mTorr). These results provide, for the first time, clear mass spectrometric evidence of the radical nature of [RuL 3 ] + (i.e., the distonic ion structure of [RuL 3 ] + ), arising from the oxidation of non-innocent thiolate ligands of the complex [PPN] + [RuL 3 ] - . Similar thiolate complexes, including ReL 3 and NiL 2 , were also examined. Although reactions of oxidized ReL 3 or NiL 2 with CH 3 SSCH 3 take place at atmospheric pressure, the corresponding reaction did not occur in vacuum. Consistent with these data, the addition of ethylene was not observed either, indicating lower reactivities of [ReL 3 ] + and [NiL 2 ] + in comparison to [RuL 3 ] + .
copNew York
pubSpringer-Verlag
doi10.1007/s13361-012-0537-1
pages502-512
date2013-04