10.1021/acs.jpca.7b12094.s001
Yuanyuan Zheng
Yuanyuan
Zheng
Wenrui Zheng
Wenrui
Zheng
Jiaoyang Wang
Jiaoyang
Wang
Huifang Chang
Huifang
Chang
Danfeng Zhu
Danfeng
Zhu
Computational Study on N–N Homolytic Bond Dissociation Enthalpies
of Hydrazine Derivatives
American Chemical Society
2018
ab initio methods
CBS-APNO
CBS-QB
3B
homolytic bond dissociation enthalpies
BDE
M 05-2X method
ROCBS-QB
NBO
DFT
CBS-Q
hydrazine derivatives
58 organonitrogen compounds
RMSE
4MP
13 organonitrogen compounds
2018-02-22 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Computational_Study_on_N_N_Homolytic_Bond_Dissociation_Enthalpies_of_Hydrazine_Derivatives/5938702
The
hydrazine derivatives have been regarded as the important building
blocks in organic chemistry for the synthesis of organic N-containing
compounds. It is important to understand the structure–activity
relationship of the thermodynamics of N–N bonds, in particular,
their strength as measured by using the homolytic bond dissociation
enthalpies (BDEs). We calculated the N–N BDEs of 13 organonitrogen
compounds by eight composite high-level <i>ab initio</i> methods including G3, G3B3, G4, G4MP2, CBS-QB3, ROCBS-QB3, CBS-Q,
and CBS-APNO. Then 25 density functional theory (DFT) methods were
selected for calculating the N–N BDEs of 58 organonitrogen
compounds. The M05-2X method can provide the most accurate results
with the smallest root-mean-square error (RMSE) of 8.9 kJ/mol. Subsequently,
the N–N BDE predictions of different hydrazine derivatives
including cycloalkylhydrazines, <i>N</i>-heterocyclic hydrazines,
arylhydrazines, and hydrazides as well as the substituent effects
were investigated in detail by using the M05-2X method. In addition,
the analysis including the natural bond orbital (NBO) as well as the
energies of frontier orbitals were performed in order to further understand
the essence of the N–N BDE change patterns.