A comparison of the ion-molecule reactions of Group 11 metal ions with alcohols

Abstract

A systematic study of gas-phase reactions of gold cations with alcohols is reported. These reactions are compared with the reactions of silver and copper cations with alcohols. In contrast with previous laser desorption/ionization studies, metal salts and/or metal oxides served as metal ion sources. Hydride abstraction is the dominant reaction of Au+ with alcohols.Study of methide and hydroxide abstraction reactions allows estimation of lower limits for Au-CH3, Cu-CH3, Au-OH, and Cu-OH bond dissociation energies (Z)(Au-CH3) > 27.1 kcal/mol, Z)(Cu-CH3) > 59 kcal/mol, D(Au-OH) > 62.5 kcal/mol, and Z)(Cu-OH) > 97.0 kcal/mol). Other primary reactions of Cu+ and Au+ include dehydration, with competitive elimination of H20 and the alkene via (¡-hydrogen transfer, and dehydrogenation, with elimination of H2, via -hydrogen transfer. Direct cationization is also observed. Silver cations mainly undergo cationization. The gas-phase acidity of AuH has been experimentally determined to be A//acid(AuH) = 331 ± 3 kcal/mol by using the bracketing technique.Gas phase metal ion chemistry studies have proliferated during recent years, particularly with the advent of laser desorption/ ionization (LD/I) methodologies introduced by Freiser and coworkers.1 To date, the majority have concentrated on the reactivity of Fe, Co, and Ni and variations in reactivity between

Guided ion beam and theoretical study of the reactions of Au+ with H2, D2, and HD

“…11 Related gas phase studies include reactions of neutral and cationic gold clusters with O 2 , [12][13][14][15] and oxidation of CO on oxidized gold cluster cations and anions. 20,21 Under such conditions, Au + has also been shown to react with dimethyl peroxide to yield Au + (CH 2 O), AuCO + , as well as the dihydride AuH 2 + . 20,21 Under such conditions, Au + has also been shown to react with dimethyl peroxide to yield Au + (CH 2 O), AuCO + , as well as the dihydride AuH 2 + .…”

Theoretical Survey of the Potential Energy Surface of Ti+ + Methanol Reaction

“…4 By using FTMS, Weil and Wilkins demonstrated that Au + predominantly affords AuH + CH 2 OH + via reaction with methanol, whereas Cu + exclusively gives the Cu(CH 3 OH) + addition. 5 The Fourier transform ICR (FT-ICR) study showed that reaction of M + (M ) V, Nb, and Ta) with CH 3 OH accounts for the dominant products of MO + and MOH + , accompanied by fewer NbOCH 2 + and VOCH 3 + . 9 Although experimental works are very extensive, it still remains open to address the mechanistic details of the reaction of transition-metal ions with primary alcohols.…”

Novel product ions of 2‐aminoanilide and benzimidazole Ag(I) complexes using electrospray ionization with multi‐stage tandem mass spectrometry

“…The vast majority of unimolecular dissociation reactions involving gas‐phase coordination complexes (or bond insertion reactions) of metal ions with organic ligands result in product ions that retain the metal ion, likely as the site of charge localization. Notable exceptions are observed for Au + and Ag + ions, both of which have been observed to eliminate the metal ion as a neutral metal hydride, a process that has been postulated in the condensed‐phase thermal decomposition of alkylphosphine Ag(I) reagents .…”