Theoretical study of the reactions of triplet oxygen atom with 1-propanol and 2-propanol

Shi, Gai; Song, Jinou; Tian, Pengzhen

doi:10.1016/j.cplett.2021.138990

Cited by 3 publications

(1 citation statement)

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“…Dioxygen bond activation has long attracted the attention of chemists and, from many angles, continues to retain its ethereal qualities, making it a vibrant and active area of study even today . The triplet ground state of dioxygen sets the kinetic barrier for the activation of O–O bond which could also be envisaged as a boon in apropos to the sustainability of life on earth . Dioxygen could be excited to a singlet state with an activation energy of about 94 kJ/mol, and most organic compounds that are in singlet ground states react with it quite readily.…”

Section: Introductionmentioning

confidence: 99%

Superoxide to Peroxide Interconversion in Ni-TMC Complexes: The Significance of Structure and Spin States

Ramakrishnan,

Anjukandi

2024

Inorg. Chem.

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A deeper comprehension of the characteristics of metal-superoxide and metalperoxide chemical species is imperative, considering their pivotal functions in oxygen transport, enzymatic activation, and catalytic oxygenations. O 2 activation is mediated by the interconversion of superoxide and peroxide species. Even though there are multiple studies on metal-superoxide and -peroxide intermediates, robust examples of their interconversion processes are scarce synthetically. For example, Ni-superoxide/peroxide complexes have been characterized with N-Tetramethylated Cyclam (TMC) ligands with different ring sizes, i.e., Nickel(II)-superoxide complex is characterized with 14-TMC while Nickel(III)-peroxide complex with 12-TMC. Later, both complexes were obtained with 13-TMC ligand by employing different bases; interestingly, no evidence of interconversion between them was identified. What are the factors influencing these processes and why is this preference? We attempt a computational analysis of this issue and provide arguments based on our conclusions. 2-dimensional potential energy scan is performed on the 12-TMC, 13-TMC, and 14-TMC systems to identify the reaction path connecting superoxide and peroxide species. Analyses indicate that structure and spin states play a significant role in determining the probability of interconversion. The superoxide-peroxide interconversion process appears to be bound by their propensity for distinct structural features and spin states.

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Section: Introductionmentioning

confidence: 99%