NH and NCl homolytic bond dissociation energies and radical stabilization energies: An assessment of theoretical procedures through comparison with benchmark-quality W2w data

2011 ◽  
Vol 112 (8) ◽  
pp. 1862-1878 ◽  
Author(s):  
Robert J. O'reilly ◽  
Amir Karton ◽  
Leo Radom
Keyword(s):  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Stabilization Energies

Shortcomings of Basing Radical Stabilization Energies on Bond Dissociation Energies of Alkyl Groups to Hydrogen

2010 ◽  
Vol 75 (16) ◽  
pp. 5697-5700 ◽  
Author(s):  
Andreas A. Zavitsas ◽  
Donald W. Rogers ◽  
Nikita Matsunaga
Keyword(s):  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Alkyl Groups ◽  
Stabilization Energies

Acidities and homolytic bond dissociation energies of the αC—H bonds in ketones in DMSO

1990 ◽  
Vol 68 (10) ◽  
pp. 1714-1718 ◽  
Author(s):  
Frederick G. Bordwell ◽  
John A. Harrelson Jr
Keyword(s):  
Gas Phase ◽  
Radical Cations ◽  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Oxidation Potentials ◽  
Stabilization Energies ◽  
Conjugate Bases

Equilibrium acidities in DMSO are reported for nine cycloalkanones, acetone, acetophenone, and 19 of their α-substituted derivatives. Oxidation potentials in DMSO for the conjugate bases of most of these ketones are also reported. Combination of these EOX(A−) and pKHA values gives estimates of the homolytic bond dissociation energies (BDEs) of the acidic C—H bonds in the ketones. The ΔBDEs, relative to the BDE of CH3-H, or a parent ketone, provide a measure of the radical stabilization energies (RSEs) of the corresponding radicals. The effects of successive α-Me and α-Ph substitutions on RSEs, relative to those of CH3COCH2-H or PhCOCH2-H, are similar to those reported in the gas phase for methane. The RSE for the MeĊHCOPh radical, relative to CH3• is 17 kcal/mol, which is smaller than the sum of the RSEs of the MeCH2• and PhCOCH2• radicals relative to CH3• (7 + 12 = 19), contrary to the prediction of the captodative postulate. When G in PhCOCH2G is PhCO, CH3CO, or CN the ΔBDEs (relative to PhCOCH2-H) are 0, 1, and 3 respectively; for MeCOCH2SO2Ph, PhCOCH2SO2Ph, and PhCOCH2NMe3+ the ΔBDEs are −5, −2, and −4, respectively. The BDEs in C5, C6, C7, C8, C10, and C12 cycloalkanones are within ±2.5 kcal/mol of that of 3-pentanone. Acetophenones bearing meta or para substituents all have BDEs of 93-94 kcal/mol. Ketone radical cations, [RCOR′]+•, appear to be superacids with estimated [Formula: see text] values below −25. Keywords: acidities, bond dissociation energies, ketones.

Bond Dissociation Energies and Radical Stabilization Energies Associated with Substituted Methyl Radicals

2001 ◽  
Vol 105 (27) ◽  
pp. 6750-6756 ◽  
Author(s):  
David J. Henry ◽  
Christopher J. Parkinson ◽  
Paul M. Mayer ◽  
Leo Radom
Keyword(s):  
Bond Dissociation Energies ◽  
Methyl Radicals ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Stabilization Energies

scholarly journals Bond Dissociation Energies and Radical Stabilization Energies: An Assessment of Contemporary Theoretical Procedures

2008 ◽  
Vol 112 (24) ◽  
pp. 5554-5554 ◽  
Author(s):  
Ambili S. Menon ◽  
Geoffrey P. F. Wood ◽  
Damian Moran ◽  
Leo Radom*
Keyword(s):  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Stabilization Energies

C−H Bond Dissociation Energies of Alkyl Amines:  Radical Structures and Stabilization Energies§

1997 ◽  
Vol 119 (38) ◽  
pp. 8925-8932 ◽  
Author(s):  
D. D. M. Wayner ◽  
K. B. Clark ◽  
A. Rauk ◽  
D. Yu ◽  
D. A. Armstrong
Keyword(s):  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Alkyl Amines ◽  
Stabilization Energies

O - H Bond Dissociation Energies

2011 ◽  
Vol 64 (4) ◽  
pp. 394 ◽  
Author(s):  
Bun Chan ◽  
Michael Morris ◽  
Leo Radom
Keyword(s):  
Density Functional ◽  
Cost Effective ◽  
Closed Shell ◽  
Bond Dissociation Energies ◽  
Functional Theory ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Stabilization Energies ◽  
High Level ◽  
Precursor Molecules

High-level composite, ab initio and density functional theory (DFT) procedures have been employed to study O–H bond dissociation energies (BDEs), as well as radical stabilization energies (RSEs) in the oxygen-centred radicals that are formed in the dissociation of the O–H bonds. Benchmark values are provided by Wn results up to W3.2 and W4.x. We are able to recommend revised BDE values for FO–H (415.6 ± 3 kJ mol–1), MeC(O)O–H (459.8 ± 6 kJ mol–1) and CF3CH2O–H (461.9 ± 6 kJ mol–1) on the basis of high-level calculations. We find that Gn-type procedures are generally reliable and cost-effective, and that some contemporary functionals and double-hybrid DFT procedures also provide adequate O–H BDEs/RSEs. We note that the variations in the O–H BDEs are associated with variations in the stabilities of not only the radicals but also the closed-shell precursor molecules. Most substituents destabilize both species, with σ-electron-withdrawing groups having larger destabilizing effects, while π-electron acceptors are stabilizing. Although there is little correlation between the stabilizing/destabilizing effects of the substituents and the RSEs, we present some general patterns in the RSEs that emerge from the present study.

scholarly journals Estimation of Bond Dissociation Energies and Radical Stabilization Energies by ESR Spectroscopy

1998 ◽  
Vol 63 (6) ◽  
pp. 1935-1943 ◽  
Author(s):  
Jochen J. Brocks ◽  
Hans-Dieter Beckhaus ◽  
Athelstan L. J. Beckwith ◽  
Christoph Rüchardt
Keyword(s):  
Esr Spectroscopy ◽  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Stabilization Energies

scholarly journals Bond Dissociation Energies and Radical Stabilization Energies:  An Assessment of Contemporary Theoretical Procedures

2007 ◽  
Vol 111 (51) ◽  
pp. 13638-13644 ◽  
Author(s):  
Ambili S. Menon ◽  
Geoffrey P. F. Wood ◽  
Damian Moran ◽  
Leo Radom
Keyword(s):  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Stabilization Energies
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