Journal ArticleDOI
Gas-phase carbene radical anions: new mechanistic insights.
TLDR
The gas-phase reactivity of the CHCl*- anion has been investigated with a series of halomethanes using a FA-SIFT instrument and shows that this anion primarily reacts via substitution and by proton transfer.Abstract:
The gas-phase reactivity of the CHCl*- anion has been investigated with a series of halomethanes (CCl4, CHCl3, CH2Cl2, and CH3Cl) using a FA-SIFT instrument. Results show that this anion primarily reacts via substitution and by proton transfer. In addition, the reactions of CHCl*- with CHCl3 and CH2Cl2 form minor amounts of Cl2*- and Cl-. The isotopic distribution of these two products is consistent with an insertion-elimination mechanism, where the anion inserts into a C-Cl bond to form an unstable intermediate, which eliminates either Cl2*- or Cl- and Cl*. Neutral and cationic carbenes are known to insert into single bonds; however, this is the first observation of such reactivity for carbene anions.read more
Citations
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Journal ArticleDOI
Carbanions in the Gas Phase
Zhixin Tian,Steven R. Kass +1 more
TL;DR: The use of molecular fluorine to produce radical anions is developed because these species can be used to obtain valuable thermodynamic data on reactive intermediates such as biradicals, carbenes, and other fleetingly stable compounds and requires an instrument outfitted with an ESI source.
Journal ArticleDOI
Charge-tagged N-heterocyclic carbenes
Yuri E. Corilo,Fabiane M. Nachtigall,Patrícia V. Abdelnur,Gunter Ebeling,Jairton Dupont,Marcos N. Eberlin +5 more
TL;DR: In this article, the first stable, long-lived charge-tagged N-heterocyclic carbenes of the general type 4x+ (x = 1-3) and analogues are reported.
Journal ArticleDOI
Gas-phase reactions of halogenated radical carbene anions with sulfur and oxygen containing species
TL;DR: In this paper, the reactivities of mono-and dihalocarbene anions (CHCl −, CHBr −, CF 2 −, CCl 2 −, and CBrCl − ) were studied using a tandem flowing afterglow-selected ion flow tube instrument.
Journal ArticleDOI
Density functional study of S(N) 2 substitution reactions for CH(3) Cl + CX(1) X(2•-) (X(1) X(2) = HH, HF, HCl, HBr, HI, FF, ClCl, BrBr, and II).
TL;DR: The back‐SN2 reaction was discussed in detail and the less size of substitution required for the gas‐phase reaction with α‐nucleophile is related to the α‐effect and it is predicted that the reaction with the stronger PA nucleophile, holding the lighter substituted atom, corresponds to the greater exothermicity given out from reactants to products.
Journal ArticleDOI
Autocatalytic cathodic dehalogenation triggered by dissociative electron transfer through a C–H⋯O hydrogen bond
TL;DR: The reaction proceeds as a series of consecutive alternating direct or Mo(II/I)-mediated electron and proton transfers, and competitive inhibition in the studied system may be viewed as analogous to those operating in enzymatic catalysis.
References
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Journal ArticleDOI
Parametrization of the ion–polar molecule collision rate constant by trajectory calculations
Timothy Su,Walter J. Chesnavich +1 more
TL;DR: In this paper, a recently reported calculation by chesnavich, Su and Bowers on classical trajectory study of thermal energy ion-polar molecule capture collisions is further extended.
Journal ArticleDOI
The tandem flowing afterglow-shift-drift
TL;DR: In this paper, the design of a new tandem flowing afterglow-SIFT-drift instrument which provides high sensitivity, resolution, and chemical versatility is described, and the performance of the instrument is evaluated in terms of the intensity and variety of ions which can be generated, mass-selected, and injected; the efficiency of the dual annulus SIFT injector as a venturi inlet; and reliability of the kinetic data.
Journal ArticleDOI
Negative ion photoelectron spectroscopy of halocarbene anions (HCF-, HCCl-, HCBr-, and HCI-); photoelectron angular distributions and neutral triplet excitation energies
TL;DR: In this article, photo-electron spectra and angular distributions for the HCX( 1 A')+e - ←HCX - (X 2 A'') and HCX ( 3 A''+e − ← HCX -(X 2 Ao'') transitions of the halocarbenes (X=F, Cl, Br, and I) are reported.