Unexpected reversal of stability in strained systems containing one-electron bonds

The energies and heats of ion-molecule reactions have been calculated (MP4/6-31G**//6-31G** or better level) and compared with the experimental values obtained from the heats of formation. Two main types of reactions have been studied: (i) AHn + AHn+• ↔ AHn+1+ + AHn-1• (A = C to F and Si to Cl), (ii) AHn + BHm+• ↔ AHn+1+ + BHm-1• or AHn-1+• + BHm+1+ (A and B = C to F). In contrast to (i), processes of type (ii) permit easy differentiation between the proton transfer and hydrogen atom abstraction mechanisms. A third type of interaction involves reactions with radical anions (A = Li to F); comparison was made with analogous processes with radical cations. A brief comment is made about the influence of the level of computational sophistication on the energies and heats of reaction, as well as on the stabilization energy of a hydrogen bonded intermediate, a structure which is similar to that of the reaction products.

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Evaluation of Triplet Aromaticity by the Isomerization Stabilization Energy

Organic Letters ◽

10.1021/ol400908z ◽

2013 ◽

Vol 15 (10) ◽

pp. 2442-2445 ◽

Cited By ~ 53

Author(s):

Jun Zhu ◽

Ke An ◽

Paul von Ragué Schleyer

Keyword(s):

Stabilization Energy

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Kinetics of the gas-phase thermal bromination of acetone. Heat of formation and stabilization energy of the acetonyl radical

Journal of the American Chemical Society ◽

10.1021/ja00722a001 ◽

1970 ◽

Vol 92 (19) ◽

pp. 5541-5546 ◽

Cited By ~ 39

Author(s):

Keith D. King ◽

David M. Golden ◽

Sidney W. Benson

Keyword(s):

Gas Phase ◽

Heat Of Formation ◽

Stabilization Energy ◽

Kinetics Of ◽

Acetonyl Radical

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Energy band structure and persistent currents in a finite-width mesoscopic two-electron ring

Superlattices and Microstructures ◽

10.1016/s0749-6036(09)80021-9 ◽

1994 ◽

Vol 16 (3) ◽

pp. 311-315 ◽

Cited By ~ 13

Author(s):

L. Wendler ◽

V.M. Fomin ◽

A.V. Chaplik

Keyword(s):

Band Structure ◽

Energy Band ◽

Energy Band Structure ◽

Finite Width ◽

Persistent Currents ◽

Electron Ring

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ChemInform Abstract: THE STABILIZATION ENERGY OF (18)ANNULENE, A THERMOCHEMICAL DETERMINATION

Chemischer Informationsdienst ◽

10.1002/chin.197504085 ◽

1975 ◽

Vol 6 (4) ◽

Author(s):

JEAN F. M. OTH ◽

JEAN-CLAUDE BUENZLI ◽

YVES DE JULIEN DE ZELICOURT

Keyword(s):

Stabilization Energy

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ChemInform Abstract: VERY LOW-PRESSURE PYROLYSIS OF CYCLOBUTYL CYANIDE, THE CYANO STABILIZATION ENERGY

Chemischer Informationsdienst ◽

10.1002/chin.197520141 ◽

1975 ◽

Vol 6 (20) ◽

pp. no-no

Author(s):

KEITH D. KING ◽

RICHARD D. GODDARD

Keyword(s):

Low Pressure ◽

Stabilization Energy

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Electron ring startup model for ELMO Bumpy Torus

The Physics of Fluids ◽

10.1063/1.864832 ◽

1984 ◽

Vol 27 (7) ◽

pp. 1759 ◽

Cited By ~ 2

Author(s):

S. Hamasaki ◽

N. A. Krall ◽

J. L. Sperling

Keyword(s):

Electron Ring

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Substituent effect on N–H bond dissociation enthalpies of carbamates: a theoretical study

Canadian Journal of Chemistry ◽

10.1139/cjc-2014-0326 ◽

2015 ◽

Vol 93 (3) ◽

pp. 279-288 ◽

Cited By ~ 2

Author(s):

Rupinder preet Kaur ◽

Damanjit Kaur ◽

Ritika Sharma

Keyword(s):

Substituent Effect ◽

Density Functional ◽

Theoretical Study ◽

Natural Bond Orbital ◽

Stabilization Energy ◽

Isodesmic Reactions ◽

Bond Dissociation ◽

Density Functional Methods ◽

Functional Methods ◽

Orbital Analysis

The present investigation deals with the study of the N–H bond dissociation enthalpies (BDEs) of the Y-substituted (NH2-C(=X)Y-R) and N-substituted ((R)(H)NC(=X)YH) carbamates (X, Y = O, S, Se; R = H, CH3, F, Cl, NH2), which have been evaluated using ab initio and density functional methods. The variations in N−H BDEs of these Y-substituted and N-substituted carbamates as the effect of substituent have been understood in terms of molecule stabilization energy (ME) and radical stabilization energy (RE), which have been calculated using the isodesmic reactions. The natural bond orbital analysis indicated that the electrodelocalization of the lone pairs of heteroatoms in the molecules and radicals affect the ME and RE values depending upon the type and site of substitution (whether N- or Y-). The variations in N−H BDEs depend upon the combined effect of molecule stabilization and radical stabilization by the various substituents.

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