The application of electrospray ionization mass spectrometry to homogeneous catalysis

Vikse, Krista L.; Ahmadi, Zohrab; McIndoe, J. Scott

doi:10.1016/j.ccr.2014.06.012

Cited by 114 publications

(96 citation statements)

References 103 publications

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“…[6] The requirement for the species of interest to be charged is not al imitation for the ESI-MS study of metal complexes, because they are either already charged or ionized by protonation during the spray generation. There are also cases where the cationic and anionic portions of the complex dissociate in the gas phase,t hus allowing inspection of the positively charged metal-ion moiety.I ns ome cases the introduction of acharged moiety on one of the ligands makes it possible to study zero-valent metal complexes.T hus,i n principle,a ll metal-ion complexes are suitable objects for ESI-MS investigation.…”

Section: Homogeneous Metal Catalysismentioning

confidence: 99%

Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

2016

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Just as periscopes allow a submarine to visually search for objects above the surface of the sea, in a reversed periscope fashion electrospray mass spectrometry (ESI-MS) can analyze the compounds at the gas phase/liquid phase interface for chemical entities which may exist in solution. The challenge is the identification and structural characterization of key elusive reaction intermediates in chemical transformations, intermediates which are able to explain how chemical processes occur. This Minireview summarizes recent selected publications on the use of ESI-MS techniques for studying solution intermediates of homogeneous chemical reactions.

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Section: Homogeneous Metal Catalysismentioning

confidence: 99%

Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

2016

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“…[1][2][3][4][5] The introduction of electrospray ionization (ESI) allowed direct probing of reaction mixtures and ESI-MS was established as a method for "fishing out" reaction intermediates. 6,7 A big advantage of using ESI-MS is its sensitivity.…”

Section: Introductionmentioning

confidence: 99%

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

et al. 2015

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A new method to investigate the reaction kinetics of intermediates in solution by electrospray ionization mass spectrometry is presented. The method, referred to as delayed reactant labeling, allows investigation of a reaction mixture containing isotopically labeled and unlabeled reactants with different reaction times. It is shown that we can extract rate constants for the degradation of reaction intermediates and investigate the effects of various reaction conditions on their half-life. This method directly addresses the problem of the relevance of detected gaseous ions toward the investigated reaction solution. It is demonstrated for geminally diaurated intermediates formed in the gold mediated addition of methanol to alkynes. Delayed reactant labeling allows us to directly link the kinetics of the diaurated intermediates with the overall reaction kinetics determined by NMR spectroscopy. It is shown that the kinetics of protodeauration of these intermediates mirrors the kinetics of the addition of methanol demonstrating they are directly involved in the catalytic cycle. Formation as well as decomposition of diaurated intermediates can be drastically slowed down by employing bulky ancillary ligands at the gold catalyst; the catalytic cycle then proceeds via monoaurated intermediates. The reaction is investigated for 1-phenylpropyne (Ph-CC-CH3) using [AuCl(PPh3)]/AgSbF6 and [AuCl(IPr)]/AgSbF6 as model catalysts. Delayed reactant labeling is achieved by using a combination of CH3OH and CD3OH or Ph-CC-CH3 and Ph-CC-CD3.

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“…In particular, it is important for reproducibility purposes across different concentration ranges that we are not perturbing the relative response of different ions, because such effects may provide misleading kinetic data. M a n u s c r i p t 4 Because we mostly use permanently charged ions in our analyses of catalytic reactions by ESI-MS, [9][10][11] we selected two such cations of drastically different mass and shape. [NMe 4 ] + is small (m/z 74; tetramethylammonium = TMA) and near-spherical; [(Ph 3 P) 2 N] + is large (m/z 538; bis(triphenylphosphine)iminium = PPN) and dumbbell-shaped ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Spatial effects on electrospray ionization response

Janusson

Hesketh

Bamford

et al. 2015

International Journal of Mass Spectrometry

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The application of electrospray ionization mass spectrometry to homogeneous catalysis

Cited by 114 publications

References 103 publications

Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

Elusive Reaction Intermediates in Solution Explored by ESI‐MS: Reverse Periscope for Mechanistic Investigations

Reaction Intermediates Kinetics in Solution Investigated by Electrospray Ionization Mass Spectrometry: Diaurated Complexes

Spatial effects on electrospray ionization response

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