Copper mediated decyano decarboxylative coupling of cyanoacetate ligands: Pesci versus Lewis acid mechanism

A combination of gas-phase ion trap multistage mass spectrometry (MSn) experiments and density functional theory (DFT) calculations have been used to examine the mechanisms of the sequential decomposition reactions of copper cyanoacetate anions, [(NCCH2CO2)2Cu]−.

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Formation and reactions of the 1, 8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu2(Ph)]+, [(napy)Ag2(Ph)]+ and [(napy)CuAg(Ph)]+

European Journal of Mass Spectrometry ◽

10.1177/1469066718795959 ◽

2019 ◽

Vol 25 (1) ◽

pp. 30-43 ◽

Cited By ~ 1

Author(s):

Qiuyan Jin ◽

Jiaye Li ◽

Alireza Ariafard ◽

Allan J Canty ◽

Richard AJ O’Hair

Keyword(s):

Density Functional Theory ◽

Gas Phase ◽

Density Functional ◽

Ion Trap ◽

Density Functional Theory Calculations ◽

Collision Induced Dissociation ◽

Ion Trap Mass Spectrometry ◽

Functional Theory ◽

Organometallic Cations ◽

Gas Phase Ion

Gas-phase ion trap mass spectrometry experiments and density functional theory calculations have been used to examine the routes to the formation of the 1,8-naphthyridine (napy) ligated geminally dimetallated phenyl complexes [(napy)Cu2(Ph)]+, [(napy)Ag2(Ph)]+ and [(napy)CuAg(Ph)]+ via extrusion of CO2 or SO2 under collision-induced dissociation conditions from their corresponding precursor complexes [(napy)Cu2(O2CPh)]+, [(napy)Ag2(O2CPh)]+, [(napy)CuAg(O2CPh)]+ and [(napy)Cu2(O2SPh)]+, [(napy)Ag2(O2SPh)]+, [(napy)CuAg(O2SPh)]+. Desulfination was found to be more facile than decarboxylation. Density functional theory calculations reveal that extrusion proceeds via two transition states: TS1 enables isomerization of the O, O-bridged benzoate to its O-bound form; TS2 involves extrusion of CO2 or SO2 with the concomitant formation of the organometallic cation and has the highest barrier. Of all the organometallic cations, only [(napy)Cu2(Ph)]+ reacts with water via hydrolysis to give [(napy)Cu2(OH)]+, consistent with density functional theory calculations which show that hydrolysis proceeds via the initial formation of the adduct [(napy)Cu2(Ph)(H2O)]+ which then proceeds via TS3 in which the coordinated H2O is deprotonated by the coordinated phenyl anion to give the product complex [(napy)Cu2(OH)(C6H6)]+, which then loses benzene.

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Nb2BN2− cluster anions reduce four carbon dioxide molecules: reactivity enhancement by ligands

Dalton Transactions ◽

10.1039/d0dt02680h ◽

2020 ◽

Vol 49 (40) ◽

pp. 14081-14087 ◽

Cited By ~ 1

Author(s):

Hai-Yan Zhou ◽

Ming Wang ◽

Yong-Qi Ding ◽

Jia-Bi Ma

Keyword(s):

Mass Spectrometry ◽

Carbon Dioxide ◽

Density Functional Theory ◽

Gas Phase ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Cluster Anions ◽

Gas Phase Reactions ◽

Functional Theory ◽

Flight Mass Spectrometry

The thermal gas-phase reactions of Nb2BN2− cluster anions with carbon dioxide have been explored by using the art of time-of-flight mass spectrometry and density functional theory calculations.

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Speciation of platinum-benzoylthiourea in the gas phase using electrospray ionization mass spectrometry and density functional theory

Rapid Communications in Mass Spectrometry ◽

10.1002/rcm.6532 ◽

2013 ◽

Vol 27 (9) ◽

pp. 947-954 ◽

Cited By ~ 6

Author(s):

Pranaw Kumar ◽

P. G. Jaison ◽

Mahesh Sundararajan ◽

Vijay M. Telmore ◽

Swapan K. Ghosh ◽

...

Keyword(s):

Mass Spectrometry ◽

Density Functional Theory ◽

Electrospray Ionization ◽

Gas Phase ◽

Electrospray Ionization Mass Spectrometry ◽

Density Functional ◽

Ionization Mass Spectrometry ◽

Ionization Mass ◽

Functional Theory

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Competing Gas-Phase Substitution and Elimination Reactions of Gemini Surfactants with Anionic Counterions by Mass Spectrometry. Density Functional Theory Correlations with Their Bolaform Halide Salt Models†

The Journal of Physical Chemistry B ◽

10.1021/jp802801r ◽

2008 ◽

Vol 112 (46) ◽

pp. 14435-14445 ◽

Cited By ~ 8

Author(s):

Carole Aimé ◽

Benoit Plet ◽

Sabine Manet ◽

Jean-Marie Schmitter ◽

Ivan Huc ◽

...

Keyword(s):

Mass Spectrometry ◽

Density Functional Theory ◽

Gas Phase ◽

Density Functional ◽

Gemini Surfactants ◽

Functional Theory ◽

Halide Salt ◽

Elimination Reactions

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The Elusive Formaldonitrone, CH2N(H)O. Preparation in the Gas Phase and Characterization by Variable-Time Neutralization−Reionization Mass Spectrometry, and Ab Initio and Density Functional Theory Calculations

Journal of the American Chemical Society ◽

10.1021/ja993234v ◽

2000 ◽

Vol 122 (3) ◽

pp. 525-531 ◽

Cited By ~ 10

Author(s):

Miroslav Polášek ◽

František Tureček

Keyword(s):

Mass Spectrometry ◽

Density Functional Theory ◽

Ab Initio ◽

Gas Phase ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Functional Theory ◽

Variable Time

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Decomposition of nitric oxide by rhodium cluster cations at high temperatures

Physical Chemistry Chemical Physics ◽

10.1039/d1cp04633k ◽

2021 ◽

Author(s):

Toshiaki Nagata ◽

Kimihiro Kawada ◽

Xuemei Chen ◽

Masato Yamaguchi ◽

Ken Miyajima ◽

...

Keyword(s):

Nitric Oxide ◽

Density Functional Theory ◽

Gas Phase ◽

High Temperatures ◽

Thermal Desorption ◽

Density Functional ◽

Density Functional Theory Calculations ◽

Functional Theory ◽

Decomposition Reactions ◽

Thermal Desorption Spectrometry

Decomposition reactions of NO molecules on gas-phase Rhn+ (n = 6–9) clusters were investigated by gas-phase thermal desorption spectrometry and density functional theory calculations. We found that NO adsorbs on...

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