Decarboxylation versus Acetonitrile Loss in Silver Acetate and Silver Propiolate Complexes, [RCO2Ag2(CH3CN)n]+ (where R = CH3 and CH3C≡C; n = 1 and 2)

Jiawei Li; George N. Khairallah; Richard A. J. O’Hair

doi:10.1071/CH15210

RESEARCH FRONT

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Decarboxylation versus Acetonitrile Loss in Silver Acetate and Silver Propiolate Complexes, [RCO₂Ag₂(CH₃CN)_n]⁺ (where R = CH₃ and CH₃C≡C; n = 1 and 2)

Jiawei Li ^A ^B ^C , George N. Khairallah ^A ^B ^C ^D and Richard A. J. O’Hair ^A ^B ^C ^E

+ Author Affiliations

- Author Affiliations

^A School of Chemistry, The University of Melbourne, Melbourne, Vic. 3010, Australia.

^B Bio21 Institute of Molecular Science and Biotechnology, The University of Melbourne, Melbourne, Vic. 3010, Australia.

^C ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, The University of Melbourne, Melbourne, Vic. 3010, Australia.

^D Current address: Accurate Mass Scientific Pty Ltd, PO Box 92, Keilor, Vic. 3036, Australia.

^E Corresponding author. Email: rohair@unimelb.edu.au

Australian Journal of Chemistry 68(9) 1385-1391 https://doi.org/10.1071/CH15210
Submitted: 24 April 2015 Accepted: 28 May 2015 Published: 1 July 2015

Abstract

Gas-phase experiments using collision-induced dissociation in an ion trap mass spectrometer have been used in combination with density functional theory (DFT) calculations (at the B3LYP/SDD6–31+G(d) level of theory) to examine the competition between decarboxylation and loss of a coordinated acetonitrile in the unimolecular fragmentation reactions of the silver acetate and silver propiolate complexes, [RCO₂Ag₂(CH₃CN)_n]⁺ (where R = CH₃ and CH₃C≡C; n = 1 and 2), introduced into the gas-phase via electrospray ionisation. When R = CH₃, loss of acetonitrile is the sole reaction channel observed for both complexes (n = 1 and 2), consistent with DFT calculations, which highlight that the barriers for decarboxylation 2.18 eV (n = 2) and 1.96 eV (n = 1) are greater than the binding energies of the coordinated acetonitriles (1.60 eV for n = 2; 1.64 eV for n = 1). In contrast, when R = CH₃C≡C, decarboxylation is the main fragmentation pathway observed for both complexes (n = 1 and 2), with loss of acetonitrile only being a minor product channel. This is consistent with DFT calculations, which reveal that the barriers for decarboxylation are 1.17 eV (n = 2) and 1.16 eV (n = 1), which are both below the binding energies of the coordinated acetonitriles (1.55 eV for n = 2; 1.56 eV for n = 1). The barrier for decarboxylation of [CH₃C≡CCO₂Ag₂]⁺ is 1.22 eV, which is less than the 2.06 eV reported for decarboxylation of [CH₃CO₂Ag₂]⁺ (Al Sharif et al. Organometallics, 2013, 32, 5416). The observed ease of decarboxylation of silver propiolate complexes in the gas-phase is consistent with the recently reported use of silver salts in metal catalysed decarboxylative C–C and C–X bond forming reactions of propiolic acids.

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Decarboxylation versus Acetonitrile Loss in Silver Acetate and Silver Propiolate Complexes, [RCO2Ag2(CH3CN)n]+ (where R = CH3 and CH3C≡C; n = 1 and 2)

Abstract

References

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Decarboxylation versus Acetonitrile Loss in Silver Acetate and Silver Propiolate Complexes, [RCO₂Ag₂(CH₃CN)_n]⁺ (where R = CH₃ and CH₃C≡C; n = 1 and 2)