scholarly journals Accurate O−H Bond Dissociation Energy Differences of Hydroxylamines Determined by EPR Spectroscopy: Computational Insight into Stereoelectronic Effects on BDEs and EPR Spectral Parameters

2011 ◽  
Vol 76 (2) ◽  
pp. 631-636 ◽  
Author(s):  
Paul S. Billone ◽  
Paul A. Johnson ◽  
Shuqiong Lin ◽  
J. C. Scaiano ◽  
Gino A. DiLabio ◽  
...  
Keyword(s):  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Epr Spectroscopy ◽  
Spectral Parameters ◽  
Bond Dissociation ◽  
Stereoelectronic Effects ◽  
Insight Into

Insight into the chemoselective aromatic vs. side-chain hydroxylation of alkylaromatics with H2O2 catalyzed by a non-heme imine-based iron complex

2021 ◽  
Author(s):  
Barbara Ticconi ◽  
Giorgio Capocasa ◽  
Andrea Cerrato ◽  
Stefano Di Stefano ◽  
Andrea Lapi ◽  
...  
Keyword(s):  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Iron Complex ◽  
Side Chain ◽  
Chain Ring ◽  
Product Ratio ◽  
Bond Dissociation ◽  
Insight Into

Side-chain/ring oxygenated product ratio increases upon decreasing the benzylic bond dissociation energy in the oxidation of alkylaromatics with H2O2 catalyzed by an imine-based iron complex.

scholarly journals Theoretical Insight into 20-Electron Transition-Metal Complexes (C5H5)2TM(E1E2)2 (TM = Cr, Mo, W; E1E2 = CO, N2, BF): Stabilities, Electronic Structures, and Bonding Nature

2021 ◽  
Author(s):  
Song Xu ◽  
Mengyang Li ◽  
Gerui Pei ◽  
Xintian Zhao ◽  
Jianzhi Xu ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Decomposition Analysis ◽  
Electron Transition ◽  
Energy Decomposition Analysis ◽  
Bond Dissociation ◽  
Insight Into

A systematic first-principles study is performed to investigate the 20-electron transition metal complexes (CH)TM(EE) (TM = Cr, Mo, W; EE = CO, N, BF). The bond dissociation energy (De) based on (CH)TM(EE) → (CH)TM(EE) + EE indicates much lower thermodynamic stability of (CH)TM(N) because of poor binding ability of N ligands. For the thermodynamic stable (CH)TM(EE) complexes (TM = Cr, Mo, W; EE = CO, BF), their 20-electron nature is derived from their occupied nonbonding molecular orbital mainly donated by ligands. Furthermore, charge transfer from TMs to the CH ligands is revealed by the atoms in molecules (AIM) theory, leading to the positive charges of the TM atoms. On the other hand, the nature of the TM-E bond has been thoroughly analyzed by the energy decomposition analysis (EDA) method. The absolute value of interaction energies (|ΔE|) between (CH)TM(EE) and EE has the same trend as the corresponding bond dissociation energy and Wiberg bond orders of TM-E bonds, following the order W > Mo > Cr with same ligands and BF > CO with same TM. Additionally, the largest contribution to the ΔE values is the repulsive term ΔE. Similar contributions from covalent and electrostatic terms to the TM-E bonds were found, which can be described as the classic dative bond with nearly same σ and π contributions. The stronger σ donations and π backdonations in (CH)TM(BF) than in (CH)TM(CO) indicate much more stability of (CH)TM(BF).

The C—Br bond dissociation energy in halogenated bromomethanes

1951 ◽  
Vol 209 (1096) ◽  
pp. 110-131 ◽  
Keyword(s):  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Methyl Bromide ◽  
Frequency Factor ◽  
Unimolecular Dissociation ◽  
Bond Dissociation Energies ◽  
Kcal Mole ◽  
Fast Reaction ◽  
Bond Dissociation ◽  
Dissociation Energies

The pyrolyses of methyl bromide and of the halogenated bromomethanes, CH 2 CI. Br, CH 2 Br 2 , CHCl 2 .Br, CHBr 3 , CF 3 Br, CCI 3 . Br and CBr 4 , have been investigated by the ‘toluene-carrier' technique. It has been shown that all these decompositions were initiated by the unimolecular process R Br → R + Br. (1) Since all these decompositions were carried out in the presence of an excess of toluene, the bromine atoms produced in process (1) were readily removed by the fast reaction C 6 H 5 .CH 3 + Br → C 6 H 5 . CH 2 • + HBr. Hence, the rate of the unimolecular process (1) has been measured by the rate of formation of HBr. The C—Br bond dissociation energies were assumed to be equal to the activation energies of the relevant unimolecular dissociation processes. These were calculated by using the expression k ═ 2 x 10 13 exp (- D/RT ). The reason for choosing this particular value of 2 x 10 13 sec. -1 for the frequency factor of these reactions is discussed. The values obtained for the C—Br bond dissociation energies in the investigated bromomethanes are: D (C—Br) D (C—Br) compound (kcal./mole) compound (kcal./mole) CH 3 Br (67.5) CHBr 3 55.5 CH 2 CIBr 61.0 CF 3 Br 64.5 CH 2 Br 2 62.5 CCI 3 Br 49.0 CHCl 2 Br 53.5 CBr 4 49.0 The possible factors responsible for the variation of the C—Br bond dissociation energy in these compounds have been pointed out.

The mean bond dissociation energy of the carbonmagnesium bond in bis(2,2-dimethylpropyl)magnesium

2010 ◽  
Vol 102 (2) ◽  
pp. 109-113 ◽  
Author(s):  
O. S. Akkerman ◽  
G. Schat ◽  
E. A. I. M. Evers ◽  
F. Bickelhaupt
Keyword(s):  
Bond Dissociation Energy ◽  
Dissociation Energy ◽  
Bond Dissociation ◽  
The Mean
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