Dataset Information

Mechanistic Study for the Photochemical Reactions of d⁶ M(CO)₅(CS) (M = Cr, Mo, and W) Complexes.

ABSTRACT: The mechanisms of photoextrusion reactions are determined theoretically for the model system of six-coordinated M(CO)₅(CS) (M = Cr, Mo, and W), using both CASSCF and MP2-CAS methods and the Def2-SVPD basis set. Three types of elimination reaction pathways (i.e., path I, path II, and path III for axial CO extrusion, equatorial CO extrusion, and CS ligand extrusion, respectively) are considered in this study. Theoretical findings show that the photoextrusion mechanism for Cr and Mo complexes proceeds as follows: M-S₀-Rea + h? ? M-S₁-FC ? M-CI ? M-Pro + CO. This study shows that when the reactant, M(CO)₅(CS) (M-S₀-Rea), is photoirradiated by UV light, it is excited vertically to many low-lying singlet excited states. It then relaxes to the first singlet excited state from the Franck-Condon point (M-S₁-FC). After passing through a conical intersection point (M-CI), this species eliminates a CO group to yield a five-coordinated product, M(CO)₄(CS) (M-S₀-Pro). However, for the W analogue, the photolysis mechanism is represented as W-S₀-Rea + h? ? W-T₁-Min ? W-T₁-TS ? W-T₁/S₀ ? W-S₀-Pro + CO. That is to say, when the reactant, W(CO)₅(CS) (W-S₀-Rea), absorbs UV light, it is excited to its several low-lying excited states by a vertical excitation. This species may then return to an intermediate at the first triplet excited state (W-T₁-Min) by means of intersystem crossings or conical intersections. After passing through a triplet transition state (W-T₁-TS) and a subsequent intersystem crossing (W-T₁/S₀), this molecule finally loses a CO ligand to produce a photoproduct at the ground singlet state (W-S₀-Pro). In other words, conical intersections and intersystem crossings play a decisive role in these photoextrusion reactions for M(CO)₅(CS). Theoretical evidence from a kinetic viewpoint strongly supports the theory that the photolysis of M(CO)₅(CS) only produces CO-loss photoproducts rather than the CS-loss photoproduct. Theoretical analysis using the results of this study allows a good interpretation of the available experimental observations.

SUBMITTER: Zhang ZF

PROVIDER: S-EPMC6641059 | biostudies-literature | 2017 Jun

REPOSITORIES: biostudies-literature

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Mechanistic Study for the Photochemical Reactions of d6 M(CO)5(CS) (M = Cr, Mo, and W) Complexes.

Zhang Zheng-Feng ZF Su Ming-Der MD

ACS omega 20170619 6

The mechanisms of photoextrusion reactions are determined theoretically for the model system of six-coordinated M(CO)5(CS) (M = Cr, Mo, and W), using both CASSCF and MP2-CAS methods and the Def2-SVPD basis set. Three types of elimination reaction pathways (i.e., path I, path II, and path III for axial CO extrusion, equatorial CO extrusion, and CS ligand extrusion, respectively) are considered in this study. Theoretical findings show that the photoextrusion mechanism for Cr and Mo comp ...[more]

PMID: 31457619

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Project description:Photochemical CO2 reduction catalysed by trans(Cl)-Ru(bpy)(CO)2Cl2 (bpy = 2,2'-bipyridine) efficiently produces carbon monoxide (CO) and formate (HCOO-) in N,N-dimethylacetamide (DMA)/water containing [Ru(bpy)3]2+ as a photosensitizer and 1-benzyl-1,4-dihydronicotinamide (BNAH) as an electron donor. We have unexpectedly found catalyst concentration dependence of the product ratio (CO/HCOO-) in the photochemical CO2 reduction: the ratio of CO/HCOO- decreases with increasing catalyst concentration. The result has led us to propose a new mechanism in which HCOO- is selectively produced by the formation of a Ru(i)-Ru(i) dimer as the catalyst intermediate. This reaction mechanism predicts that the Ru-Ru bond dissociates in the reaction of the dimer with CO2, and that the insufficient electron supply to the catalyst results in the dominant formation of HCOO-. The proposed mechanism is supported by the result that the time-course profiles of CO and HCOO- in the photochemical CO2 reduction catalysed by [Ru(bpy)(CO)2Cl]2 (0.05 mM) are very similar to those of the reduction catalysed by trans(Cl)-Ru(bpy)(CO)2Cl2 (0.10 mM), and that HCOO- formation becomes dominant under low-intensity light. The kinetic analyses based on the proposed mechanism could excellently reproduce the unusual catalyst concentration effect on the product ratio. The catalyst concentration effect observed in the photochemical CO2 reduction using [Ru(4dmbpy)3]2+ (4dmbpy = 4,4'-dimethyl-2,2'-bipyridine) instead of [Ru(bpy)3]2+ as the photosensitizer is also explained with the kinetic analyses, reflecting the smaller quenching rate constant of excited [Ru(4dmbpy)3]2+ by BNAH than that of excited [Ru(bpy)3]2+. We have further synthesized trans(Cl)-Ru(6Mes-bpy)(CO)2Cl2 (6Mes-bpy = 6,6'-dimesityl-2,2'-bipyridine), which bears bulky substituents at the 6,6'-positions in the 2,2'-bipyridyl ligand, so that the ruthenium complex cannot form the dimer due to the steric hindrance. We have found that this ruthenium complex selectively produces CO, which strongly supports the catalytic mechanism proposed in this work.

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Dataset Information

Mechanistic Study for the Photochemical Reactions of d⁶ M(CO)₅(CS) (M = Cr, Mo, and W) Complexes.

Publications

Mechanistic Study for the Photochemical Reactions of d<sup>6</sup> M(CO)<sub>5</sub>(CS) (M = Cr, Mo, and W) Complexes.

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