The potential energy surface (PES) of the oxidative pathways and unimolecular decomposition of
CH3CH2C(O)OCH2CH2O radical formed from ethyl propionate has been investigated in details using
ab initio density functional method. In present study, it is revealed that five major decomposition
pathways with their kinetic and thermodynamics parameters. The geometries of reactants, transition
states and product radicals were optimized using the model DFT method M06-2X along with the
6-31+G(d,p) basis set. The mechanistic, kinetic and thermochemical analysis was carried out at the
M06-2X/aug-cc-pVTZ//M06-2X/6-311++G(d,p) level. Based on present results, it can be concluded
that the oxidative pathway is the most significant for decomposition of CH3CH2C(O)OCH2CH2O
radical. The rate coefficients for each reaction channels were determined in a wide range of temperature
250-450 K.
A porphyrin compound manganese(III) meso-5,10,15,20-tetrakis(4-pyridyl)porphyrin, Mn(Py)4P
containing manganese(III) and 4-pyridyl ligands was synthesized. The UV-visible spectrophotometry
and cyclic voltammetry were used to investigate the axial ligand and the redox behaviours of Mn(Py)4P.
This study investigates the reduction properties of Mn(Py)4P using primary amine, imidazole and
2-methylimidazole as axial ligands. Reduction of Mn(Py)4P leads to a shift in absorption bands,
indicating the conversion from manganese(III) to manganese(II) porphyrin. The addition of primary
amine results in a square pyramidal structure for Mn(II) porphyrin, while imidazole or
2-methylimidazole leads to the formation of tetragonal complexes. These changes in geometry result in
a decrease in π-bonding. The observed spectral patterns support the involvement of axial ligands in the
5th and 6th positions of manganese(III) porphyrin. The cyclic voltammogram confirmed the alteration
in geometry, indicating changes in the redox properties of compound. As a whole, the results of this
study provide light on the ways where the behaviour of in which Mn(Py)4P can be altered by the
presence of other molecules.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.