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Reactivity Of Mono-halogen Carbene Radical Anions (CHX–˙; X = F, Cl And Br) And The Corresponding Carbanions (CH2X–; X = Cl And Br) In The Gas Phase

Monique Born, S. Ingemann, N. Nibbering
Published 1996 · Chemistry

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The gas-phase reactions of mono-halogen substituted carbene radical anions, CHX–˙(X = F, Cl and Br) and the corresponding carbanions, CH2X–(X = Cl and Br) with halomethanes and organic esters have been examined with the use of Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. The chlorine and bromine containing (radical) anions react by SN2 substitution with the parent chloro- and bromo-urethanes, whereas an SN2 and/or a BAC2 reaction occurs with the methyl ester of trifluoroacetic acid and dimethyl carbonate. The main features of the results are: (i) the SN2 substitution of a given carbene radical anion with CH3Cl or CH3Br is less efficient than this reaction of the corresponding carbanion, (ii) the radical anions react less efficiently with dimethyl carbonate than the carbanions, (iii) the SN2 substitution is less important for the radical anions than for the carbanions in the reactions with the two carbonyl compounds, (iv) for both types of ions, the BAC2 pathway becomes relatively more important as the halogen atom is changed from chlorine to bromine. These findings are discussed in terms of the thermodynamics of the overall processes in combination with considerations of the potential energy surfaces which can describe these gas-phase processes.
This paper references
10.1039/P29900001825
Proton affinities and heats of formation of the imines CH2NH, CH2NMe and PhCHNH
R. Peerboom (1990)
10.1021/JA00258A015
Generation, thermodynamics, and chemistry of the diphenylcarbene anion radical (Ph2C.cntdot.-)
R. Mcdonald (1987)
10.1139/V84-038
The importance of the σ*-π* orbital mixing for the nucleophilic displacement on the unsaturated carbon
S. Yamabe (1984)
10.1021/JA00016A001
Reactions of the benzyne radical anion in the gas phase, the acidity of the phenyl radical, and the heat of formation of o-benzyne
Y. Guo (1991)
10.1021/JA00070A030
Electron affinities of some polycyclic aromatic hydrocarbons, obtained from electron-transfer equilibria
L. Crocker (1993)
10.1126/science.266.5187.998
Simulations of Gas-Phase Chemical Reactions: Applications to SN2 Nucleophilic Substitution
W. Hase (1994)
10.1021/JA00327A008
Gas-phase generation of 1,1,1,3,3,3-hexafluoroisopropylidene anion radical: proton affinity and .DELTA.Hf.degree. of the anion radical (CF3)2C-.bul. and the carbanion (CF3)2CH-
R. Mcdonald (1984)
10.1039/P29850000837
Gas-phase acidity of CH3X[X=P(CH3)2, SCH3, F, Cl, Br or I] compounds
S. Ingemann (1985)
10.1002/MAS.1280080502
Gas‐phase equilibrium affinity scales and chemical ionization mass spectrometry
J. Bartmess (1989)
10.1021/JA00374A005
SN2 reactivity of CH3X derivatives. A valence bond approach
S. Shaik (1982)
10.1021/JA00247A007
Ab initio study of the displacement reactions of chloride ion with formyl and acetyl chloride
J. Blake (1987)
10.1021/JA00095A025
Heats of formation of mono-halogen-substituted carbenes. Stability and reactivity of CH-* (X=F,Cl,Br, and J) radical anions
Monique Born (1994)
10.1021/ja00393a033
Gas-phase ion-molecule reactions of phenylnitrene anion
Mark J. Pellerite (1981)
10.1021/J100407A020
Marcus theory applied to reactions with double-minimum potential surfaces
J. A. Dodd (1986)
10.1002/chin.198246377
Electron transfer reactions in organic chemistry
L. Eberson (1982)
10.1016/0168-1176(90)85003-K
Gas phase ion chemistry of the vinylidene radical anion and the acidity of the vinyl radical
Y. Guo (1990)
10.1039/C39850000094
Can desolvation of an ion be the rate-determining step in a reaction?
M. S. Dewar (1985)
10.1021/AR00033A001
Electron transfer, bond breaking, and bond formation
J. Savéant (1993)
10.1021/ja00347a026
Intrinsic barriers in nucleophilic displacements. A general model for intrinsic nucleophilicity toward methyl centers
Mark J. Pellerite (1983)
10.1021/JA00267A003
Determination of the singlet-triplet splitting and electron affinity of o-benzyne by negative ion photoelectron spectroscopy
D. G. Leopold (1986)
10.1007/978-3-642-50207-1_11
A Fourier Transform Ion Cyclotron Resonance Study of Negative Ion-Molecule Reactions of Phenyl Acetate, Phenyl Trifluoroacetate and Acetanilide
J. C. Kleingeld (1982)
10.1063/1.1679615
Theory of ion‐polar molecule collisions. Comparison with experimental charge transfer reactions of rare gas ions to geometric isomers of difluorobenzene and dichloroethylene
T. Su (1973)
10.1016/0009-2614(75)80062-5
Laser photoelectron spectrometry of CH
A. Kasdan (1975)
10.1007/978-1-4684-5874-9_8
On Electron Transfer in Aliphatic Nucleophilic Substitution
H. Lund (1995)
10.1021/JA00541A018
Hypovalent radicals. 4. Gas-phase studies of the ion-molecule reactions of cyclopentadienylidene anion radical in a flowing afterglow
R. Mcdonald (1980)
10.1021/JA00085A030
Intrinsic Structure-Reactivity Relationships in Gas-Phase SN2 Reactions: Identity Exchange of Substituted Benzyl Chlorides with Chloride Ion
B. D. Wladkowski (1994)
10.1146/ANNUREV.PC.15.100164.001103
Chemical and Electrochemical Electron-Transfer Theory
R. Marcus (1964)
10.1021/JA00033A006
Gas-phase electron-transfer reactions between selected molecular anions and halogenated methanes
W. B. Knighton (1992)
10.1002/(SICI)1099-1395(199607)9:7<471::AID-POC807>3.0.CO;2-I
Competing electron transfer proton abstraction and nucleophilic substitutions in gas-phase reactions of (radical) anions with chloro- and bromomethanes.
P. O. Staneke (1996)
10.1139/V56-023
SYNTHESIS OF DEUTERATED DIMETHYL CARBONATE
R. Renaud (1956)
10.1021/J100215A029
Hypovalent radical. Part 12. Gas-phase ion-molecule reactions of phenylnitrene anion radical with certain .alpha.,.beta.-unsaturated molecules. A study of 1,2- vs. 1,4-addition mechanisms
R. Mcdonald (1982)
10.1039/C39910000644
The gas-phase acidity of the phenyl radical and some C6H4X·(X = F, Cl, CN) radicals
H. E. Matimba (1991)
10.1016/S0065-3160(08)60100-8
Gas-phase Nucleophilic Displacement Reactions
J. M. Riveros (1985)
10.1016/0168-1176(89)83047-2
Segmented Fourier transform and its application to Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry: ion abundances and mass measurements
L. D. Koning (1989)
10.1021/JA00250A010
Generation of the distonic ion CH2NH3.bul.+: nucleophilic substitution of the ketene cation radical by ammonia and unimolecular decarbonylation of ionized acetamide
T. Drewello (1987)
10.1016/0304-4173(85)90014-X
Electron transfers in chemistry and biology
R. Marcus (1985)
10.1002/POC.610050403
Multi‐step processes in gas‐phase reactions of halomethyl anions XCH2− (X = Cl,Br) with CH3X and NH3
F. Bickelhaupt (1992)
10.1021/JA00003A012
Hemiacetal anions: a model for tetrahedral reaction intermediates
S. Baer (1991)
10.1002/RCM.1290050907
Mass‐specific selection of ions in Fourier‐transform ion cyclotron resonance mass spectrometry. Unintentional off‐resonance cyclotron excitation of selected ions
A. Heck (1991)
10.1021/JA00412A011
Gas-phase generation of phenylnitrene anion radical - proton affinity and .DELTA.Hf.degree. of phN-.cntdot. and its clustering with ROH molecules
R. Mcdonald (1981)
10.1002/ANIE.198812273
Electron Transfer and Charge Transfer: Twin Themes in Unifying the Mechanisms of Organic and Organometallic Reactions
J. K. Kochi (1988)
10.1021/JA00272A075
Can nucleophiles attack radical cations directly? "Allowed" and "forbidden" polar reactions
A. Pross (1986)
10.1002/RCM.1290070813
Mass spectrometry at the University of Amsterdam
N. Nibbering (1993)
10.1021/JA00508A002
Gas phase nucleophilic displacement reactions of negative ions with carbonyl compounds
O. Asubiojo (1979)
10.1016/0020-7381(73)80104-4
Ion-Polar molecule collisions: the effect of ion size on ion-polar molecule rate constants; the parameterization of the average-dipole-orientation theory
T. Su (1973)
10.1021/JA953665N
Gas-Phase Non-Identity SN2 Reactions of Halide Anions with Methyl Halides: A High-Level Computational Study
ab Mikhail N. Glukhovtsev (1995)
10.1021/J100182A021
Negative ion photoelectron spectroscopy of halocarbene anions (HCF-, HCCl-, HCBr-, and HCI-); photoelectron angular distributions and neutral triplet excitation energies
M. Gilles (1992)
10.1021/AR00155A005
Single-electron transfer, a major reaction pathway in organic chemistry. An answer to recent criticisms
E. C. Ashby (1988)
10.1021/CR00079A003
Electron affinities and electron-transfer reactions
P. Kebarle (1987)
10.1021/JA00016A044
Use of ionization potentials, electron affinities and singlet-triplet excitation energies for the estimation of reaction barriers
V. Parker (1991)
10.1016/S0065-3160(08)60157-4
Gas-phase Reactions of Organic Anions
N. Nibbering (1988)
10.1021/AR50131A003
Aromatic substitution by the SRN1 mechanism
J. Bunnett (1978)
10.1021/JA00316A023
SN2 reactions in the gas phase. Temperature dependence of the rate constants and energies of the transition states. Comparison with solution
G. Caldwell (1984)
10.1002/RECL.19961150304
Electron transfer as a possible initial step in nucleophilic addition elimination raections between (radical) anions and carbonyl compounds in the gas phase
P. O. Staneke (1996)
10.1016/S0040-4020(01)81303-X
Generation, thermochemistry, and chemistry of carbene anion radicals and related species
R. Mcdonald (1989)
10.1021/JA00025A058
The nonstatistical dissociation dynamics of chloride(bromomethane) Cl-(CH3Br): evidence for vibrational excitation in the products of gas-phase SN2 reactions
S. Graul (1991)
10.1021/JA00194A023
Nucleophilic attack on cation radicals and cations. A theoretical analysis
S. Shaik (1989)
10.1016/0168-1176(92)85024-T
Gas-phase bimolecular chemistry of the ż−CHNC and ż−CHCN radical anions
H. E. Matimba (1992)
10.1021/JO00002A023
Gas-phase chemistry of the negative ions derived from azo- and hydrazobenzene
S. Ingemann (1991)



This paper is referenced by
10.1002/(SICI)1098-2787(1997)16:4<181::AID-MAS2>3.0.CO;2-D
Formation and chemistry of radical anions in the gas phase
Monique Born (1997)
10.1002/RCM.1787
Reactions of (di)manganese carbonyl ions with 1,4,7-trimethyl-1,4,7-triazacyclononane (Me3TACN) in the gas phase.
Eric S E van Beelen (2005)
10.1016/J.THEOCHEM.2010.07.024
Reactivity of hydrogen abstraction in CH2Cl2 by CHX− (X = F, Cl, Br, I) from a theoretical viewpoint
Jun-Xi Liang (2010)
10.1016/J.IJMS.2008.07.007
Gas-phase reactions of halogenated radical carbene anions with sulfur and oxygen containing species
Stephanie M. Villano (2009)
10.1016/S1044-0305(01)00235-5
Reactions of O−. with methyl benzoate: A negative ion chemical ionization and Fourier transform ion cyclotron resonance study
E. Stemmler (2001)
10.1007/s13738-013-0404-4
Reaction of CS2 with CHBr•− and CBr2•− in the gas phase: a Theoretical Mechanistic Study
Liang Jun-xi (2014)
10.1002/POC.3276
Understanding halogen‐substituent assistance in H‐atom abstraction‐based reactions of CHCl•− with CH4 − nXn (X = H, F, Cl; n = 0–3)
Liang Jun-xi (2014)
10.1016/J.COMPTC.2012.07.023
Theoretical investigation of the conventional CX1X2− (X1, X2 = H, F, Cl, Br, and I) compounds☆
Liang Jun-xi (2012)
10.1142/S0219633615500091
Computational comparison of reactions of CS2 with CHX•- (X = F, Cl, and Br): Do F, Cl, and Br substitutions effect differently?
J. Liang (2015)
10.1002/MAS.20099
Four decades of joy in mass spectrometry.
N. Nibbering (2006)
10.1007/S11426-012-4596-8
Exploring the H-abstraction reactions of CHCl ?- /CCl 2 ?- with CX 3 H (X = F, Cl, Br and I) using the density functional theory method
Liang Jun-xi (2012)
Mass spectrometric characterization of remotely charged amino acids and peptides
D. Koirala (2016)
10.1007/s11224-012-0095-y
Substituent effects on the compounds CX1X2•− (X1, X2 = H, F, Cl, Br, I) from theoretical investigation
J. Liang (2012)
10.1007/s11426-012-4596-8
Exploring the H-abstraction reactions of CHCl·−/CCl2·− with CX3H (X = F, Cl, Br and I) using the density functional theory method
Junxi Liang (2012)
10.1016/J.IJMS.2014.07.017
Reactivity of 3- and 4-pyridinylnitrene-n-oxide radical anions
D. Koirala (2015)
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