The silver acetate cation CH3CO2Ag2+ reacted with allyl iodide via C–O bond coupling to produce Ag2I+ and allyl acetate, but only underwent adduct formation with methyl iodide, highlighting the importance of substrate on reactivity. DFT calculations predicted the reaction with allyl iodide to be exothermic by 0.48 eV and suggested that intermediates in the reaction benefit from multiple interactions between the allyl and iodide moieties of allyl iodide and the two silver atoms in CH3CO2Ag2+.
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3.
For a review of the earlier literature see: DeWolfeR.H.YoungW.G., “Substitution and rearrangement reactions of allylic compounds”, Chem. Rev.56, 753 (1956). doi: 10.1021/cr50010a002
4.
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7.
For an example of gas-phase formation of esters see: LeeYongIIIJoSung-ChanTaoW. AndyCooksR.G., “Metalassisted esterification: Glutaric acid–iron(II) complexes in the gas phase”, Rapid Commun. Mass Spectrom.15, 484 (2001). doi: 10.1002/rcm.254
8.
For other examples of metal mediated C-heteroatom bond formation see: (a) KoszinowskiK.SchröderD.SchwarzH., “Probing Cooperative Effects in Bimetallic Clusters: Indications of C–N Coupling of CH4 and NH3 Mediated by the Cluster Ion PtAu+ in the Gas Phase”, J. Am. Chem. Soc.125, 3676 (2003); doi: 10.1021/ja029791q (b) KoszinowskiK.SchröderD.SchwarzH., “Coupling of methane and ammonia by dinuclear bimetallic platinum-coinage-metal cations PtM+”Angew. Chem. Int. Ed. Engl.43, 121 (2004). doi: 10.1002/anie.200352817
9.
Silver carboxylate cations, RCO2Ag2+, have been observed in a number of mass spectra of silver carboxylates: (a) BuschK.L.CooksR.G.WaltonR.A.WoodK.V., “Mass spectrometric investigation of silver ion promoted carbon-carbon bond scission”, Inorg. Chem.23, 4093 (1984); doi: 10.1021/ic00192a051 (b) SchaeferH.BrendelC.RabeneckH.SchibillaE., “Gaseous acetates”, Z. Anorg. Allg. Chem.518, 168 (1984); (c) AdamsS.K.EdwardsD.A.RichardsR., “Silver(I) carboxylates. I. Mass spectra and low-frequency infrared spectra”, Inorg. Chim. Acta12, 163 (1975); (d) RobertsG.D.WhiteE.V., “The mass spectra of some silver salts”, Org. Mass Spectrom.16, 546 (1981). doi: 10.1002/oms.1210161209
10.
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13.
(a) DolgM.WedigU.PreussH., “Energy-adjusted ab initio pseudopotentials for the first row transition elements”, J. Chem. Phys.86, 866 (1987); doi: 10.1063/1.452288 (b) BergnerA.DolgM.KuechleW.StollH.PreussH., “Ab initio energy-adjusted pseudopotentials for elements of groups 13–17”, Mol. Phys.80, 1431 (1993). doi: 10.1080/00268979300103121
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15.
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16.
KhairallahG.N.O'HairR.A.J.BruceM.I., “Gas-Phase Synthesis and Reactivity Studies of Binuclear Gold Hydride Cations, (R3PAu) 2H+ (R = Me and Ph)”, Dalton Trans.3699 (2006). doi: 10.1039/b604404b
17.
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18.
KhairallahG.N.O'HairR.A.J., “Activation of the C–I and C–OH Bonds of 2-Iodoethanol by Gas Phase Silver Cluster Cations Yields Subvalent Silver–Iodide and –Hydroxide Cluster Cations”, Dalton Trans.3149 (2007). doi: 10.1039/b700132k
