2019
DOI: 10.1039/c8ra07669c
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The mechanistic investigations of photochemical decarbonylations and oxidative addition reactions for M(CO)5 (M = Fe, Ru, Os) complexes

Abstract: The mechanisms for the photochemical CO-dissociation and the oxidative addition reactions are studied theoretically using three model systems: M(CO) 5 (M ¼ Fe, Ru, and Os) and the CASSCF/Def2-SVP (fourteen-electron/ten-orbital active space) and MP2-CAS/Def2-SVP//CASSCF/Def2-SVP methods. The structures of the intersystem crossings and the conical intersections, which play a decisive role in these CO photo-extrusion reactions, are determined. The intermediates and the transition structures in either the singlet … Show more

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Cited by 3 publications
(4 citation statements)
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References 78 publications
(184 reference statements)
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“…These calculations were carried out with Karlsruhe def2-SVP basis set for lighter atoms and def2-ECP basis set for the osmium atom. [30][31] To avail the calculations, first a single point calculation on the respective optimized geometries is carried out with dispersion corrected PBE0 (PBE0-D3) and def2-TZVPP basis set and noted the energies of HOMO-5 to LUMO + 5 molecular orbitals. A near degeneracy has been observed in the energies of the occupied MOs.…”
Section: Computational Detailsmentioning
confidence: 99%
“…These calculations were carried out with Karlsruhe def2-SVP basis set for lighter atoms and def2-ECP basis set for the osmium atom. [30][31] To avail the calculations, first a single point calculation on the respective optimized geometries is carried out with dispersion corrected PBE0 (PBE0-D3) and def2-TZVPP basis set and noted the energies of HOMO-5 to LUMO + 5 molecular orbitals. A near degeneracy has been observed in the energies of the occupied MOs.…”
Section: Computational Detailsmentioning
confidence: 99%
“…This is initially driven by the harness of electric field to achieve the reaction selectivity or obtain a desired mechanism . To this extent, the oriented EEF was developed and used in theoretical studies more and more on the bond activations, such as the halogen bond and σ‐bonds, and chemical reactions, such as the substitution reactions, Menshutkin reaction, Diels‐Alder reaction, hydroboration reaction, and Azide‐alkyne reactions . Especially, one of the predictions on the Diels‐Alder reaction was supported in a STM‐based experimental study, which resolves the dilemma of how to orient the reactants and simultaneously deliver unidirectional oriented EEF pulses that bring about catalysis of the reaction.…”
Section: Introductionmentioning
confidence: 99%
“…Therefore, it would be very fascinating and yet challenging to develop new approaches for the catalysis of hydrosilylation of alkynes with broad generality to generate α‐vinylsilanes. Because our group has some successful experiences in the studies of EEF catalyzing chemical reactions, we tried to combine the external electric field to catalyze the hydrosilylation of terminal alkyne, with the aim of obtaining the α‐vinylsilanes easier. The acetylene and phenylacetylene molecules were selected to react with phenylsilane, respectively (Scheme ).…”
Section: Introductionmentioning
confidence: 99%
“…Main group metal element germanium (Ge) and its oxides have important applications in fields like aerospace, solar cells, and biomedicine, in addition to their potential as catalysts in the optical industry. Moreover, ruthenium (Ru), as a homotope of iron, has similar chemical reactivity. Investigating the reaction of CO with the Ru–GeO heterodimers would not only help understand the chemical bonding between main group metal and transition metal but also can be used as a model system to study CO/GeO oxidation on metal surface from the molecular level, thereby facilitating the exploration and development of novel catalysts.…”
mentioning
confidence: 99%