Exploring the potential of the ammine complexes M(NH3)n+ (M = Zr, Re) to activate NH3

Avilés, Alejandro; Colmenares, Fernando

doi:10.1039/d1nj05386h

Cited by 1 publication

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“…In previous reports, we have used a two-step radical reaction scheme to rationalize the shift observed in the spin multiplicity between the reactants and products in reactions leading to the activation of small molecules by transition metal atoms or complexes. − According to this scheme, the first reaction evolves to the radical species obtained by hydrogen-atom abstraction from the molecule that is being activated by the metal-containing system (although this abstraction reaction can involve an atom different from hydrogen or even a small molecular moiety). , Once the radical species are yielded, they can recombine in a second reaction. For the rebounding of the radicals, in those contributions, we focused our attention in the two lowest-lying radical asymptotes whose electronic configurations differ only in the spin (up or down) of the unpaired electron in the nonmetallic fragment.…”

Section: Introductionmentioning

confidence: 99%

Disruptive Model That Explains for the Long-Lived Triplet States Observed for 2-Thiocytosine upon UVA Radiation

Baños,

Avilés,

Colmenares

2024

ACS Omega

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The possible role of radical species in the formation of the long-lived triplet states observed for 2-thiocytosine upon UV irradiation was theoretically investigated. It is predicted that the radical fragments arising from the homolytic rupture of the NH group of the thiobase can be yielded upon ultraviolet-A radiation. Recombination of the radicals through the most favorable singlet channel yields the lowest-lying tautomer of the 2thiocytosine (the amino-thiol form) through a barrierless pathway. The rebounding of the radical fragments along the triplet channels that emerge from the attack of the hydrogen to the nitrogen atoms next to the C−S bond leads to stable structures for the amino-thion-N 1 H and amino-thion-N 3 H tautomers. These results allow for the rationalization of the near-unity triplet yields observed when this pure light-atom organic molecule is exposed to UV irradiation, without invoking intersystem crossings between the electronic states of different spin-multiplicities. A similar study for cytosine showed that the energy required to induce the homolytic breaking of the N−H bond of the nucleobase is not attainable under UVA radiation. This result is consistent with the experimental fact that no triplet states are observed when this molecule is exposed to that light.

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Section: Introductionmentioning

confidence: 99%

Disruptive Model That Explains for the Long-Lived Triplet States Observed for 2-Thiocytosine upon UVA Radiation

Baños,

Avilés,

Colmenares

2024

ACS Omega

Self Cite

View full text Add to dashboard Cite

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Exploring the potential of the ammine complexes M(NH₃)_n⁺ (M = Zr, Re) to activate NH₃

Abstract: The sequential addition of NH3 molecules to Zr+ and Re+ was investigated through CASSCF-CASPT2 calculations with the aim to analyze the effect of the metal-ligand interactions on the potential of...

Cited by 1 publication

References 38 publications

Disruptive Model That Explains for the Long-Lived Triplet States Observed for 2-Thiocytosine upon UVA Radiation

Disruptive Model That Explains for the Long-Lived Triplet States Observed for 2-Thiocytosine upon UVA Radiation

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