Mobility of anions within anion-neutral complexes. Cross ring hydride ion migration upon collisional activation of thepara-formylbenzyloxy anion

Dua, Suresh; Bowie, John H.

doi:10.1002/(sici)1097-0231(199712)11:18<1959::aid-rcm104>3.0.co;2-b

Cited by 1 publication

(2 citation statements)

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“…The deuterium‐labeling experiment proved that the transferred hydride originates uniquely from the hydrogen atoms affixed to the benzylic carbon of the benzyloxy anion. This result agrees with a previous report on cross‐ring hydride addition to the formyl group . Furthermore, the hydride affinities of benzaldehyde and phenyl isocyanate are 183 and 276 kJ·mol −1 , respectively .…”

Section: Resultssupporting

confidence: 92%

“…This result agrees with a previous report on cross-ring hydride addition to the formyl group. [41] Furthermore, the hydride affinities of benzaldehyde and phenyl isocyanate are 183 and 276 kJ·mol À1 , respectively. [42] The fact that phenyl isocyanate is a more active hydride acceptor than benzaldehyde was supported by theoretical calculation (vide infra).…”

Section: Inc-mediated Hydride Transfer Reactionmentioning

confidence: 99%

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Competitive proton and hydride transfer reactions via ion‐neutral complexes: fragmentation of deprotonated benzyl N‐phenylcarbamates in mass spectrometry

et al. 2015

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The gas-phase chemistry of deprotonated benzyl N-phenylcarbamates was investigated by electrospray ionization tandem mass spectrometry. Characteristic losses of a substituted phenylcarbinol and a benzaldehyde from the precursor ion were proposed to be derived from an ion-neutral complex (INC)-mediated competitive proton and hydride transfer reactions. The intermediacy of the INC consisting of a substituted benzyloxy anion and a phenyl isocyanate was supported by both ortho-site-blocking experiments and density functional theory calculations. Within the INC, the benzyloxy anion played the role of either a proton abstractor or a hydride donor toward its neutral counterpart. Relative abundances of the product ions were influenced by the nature of the substituents. Electron-withdrawing groups at the N-phenyl ring favored the hydrogen transfer process (including proton and hydride transfer), whereas electron-donating groups favored direct decomposition to generate the benzyloxy anion (or substituted benzyloxy anion). By contrast, electron-withdrawing and electron-donating substitutions at the O-benzyl ring exhibited opposite effects.

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Section: Resultssupporting

confidence: 92%

Section: Inc-mediated Hydride Transfer Reactionmentioning

confidence: 99%