Concomitant hydride and proton transfer: an essay on competing and consecutive key reactions occurring in gaseousion/neutral complexes.
The interplay of proton transfer and hydride transfer reactions in alkylbenzenium ions and related protonated di- and oligophenylalkanes is presented and discussed. While intra- and interannular proton exchange has been recognised to be an ubiquitous feature in protonated arenes, hydride abstraction is much less obvious but can become a dominating fragmentation channel in metastable ions of tert-butyl-substituted alkylbenzenium ions and related carbocations. In such cases, proton-induced release of the tert-butyl cation gives rise to ion/neutral complexes as reactive intermediates, for example, [(CH(3))(3)C(+)...arylCH(2)(α)(CH(2))(n)CH(2)(ω)aryl '] with n ≥ 0, and highly regioselective intra-complex hydride transfer occurs from all of the benzylic methylene hydride ion donor groups (α-CH(2) and ω-CH(2)) to the tert-butyl cation acting as a Lewis acid. Substituent effects on the individual contributions to the overall hydride transfer from different donor sites, including ortho-methyl groups, in particular, and the concomitant intra- complex proton transfer from the tert-butyl cation to the neutral diarylalkane constituent corroborate the view of "bisolvated" complexes as the central intermediates, in which the carbenium ion is coordinated to both of the aromatic π-electron systems. The role of cyclisation processes converting the benzylic, [M - H](+) type, ions into the isomeric benzenium, [M + H](+)-type, ions prior to fragmentation is demonstrated for several cases. This overall scenario, consisting of consecutive and/or competing intra-complex hydride abstraction and proton transfer, intraannular proton shifts (H+ ring walk) and interannular proton transfer, hydrogen exchange ("scrambling") processes, and cyclisation and other electrophilic substitution reactions, is of general importance in this field of gas-phase ion chemistry, and more recent examples concerning protonated ethers, benzylpyridinium and benzylammmonium ions are discussed in which these recurring features play central and concerted mechanistic roles as well.
Department of Chemistry, Bielefeld University, Universitätsstrasse 25, 33615 Bielefeld, Germany. dietmar.kuck@uni-bielefeld.de
Dietmar
D
Kuck