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Counter-Intuitive Gas-Phase Reactivities of [V₂ ]⁺ and [V₂ O]⁺ towards CO₂ Reduction: Insight from Electronic Structure Calculations.

ABSTRACT: [V₂ O]⁺ remains "invisible" in the thermal gas-phase reaction of bare [V₂ ]⁺ with CO₂ giving rise to [V₂ O₂ ]⁺ ; this is because the [V₂ O]⁺ intermediate is being consumed more than 230 times faster than it is generated. However, the fleeting existence of [V₂ O]⁺ and its involvement in the [V₂ ]⁺ → [V₂ O₂ ]⁺ chemistry are demonstrated by a cross-over labeling experiment with a 1:1 mixture of C¹⁶ O₂ /C¹⁸ O₂ , generating the product ions [V₂ ¹⁶ O₂ ]⁺ , [V₂ ¹⁶ O¹⁸ O]⁺ , and [V₂ ¹⁸ O₂ ]⁺ in a 1:2:1 ratio. Density functional theory (DFT) calculations help to understand the remarkable and unexpected reactivity differences of [V₂ ]⁺ versus [V₂ O]⁺ towards CO₂ .

SUBMITTER: Li J

PROVIDER: S-EPMC7383893 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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Publications

Counter-Intuitive Gas-Phase Reactivities of [V2 ]+ and [V2 O]+ towards CO2 Reduction: Insight from Electronic Structure Calculations.

Li Jilai J Geng Caiyun C Weiske Thomas T Schwarz Helmut H

Angewandte Chemie (International ed. in English) 20200325 30

[V2 O]+ remains "invisible" in the thermal gas-phase reaction of bare [V2 ]+ with CO2 giving rise to [V2 O2 ]+ ; this is because the [V2 O]+ intermediate is being consumed more than 230 times faster than it is generated. However, the fleeting existence of [V2 O]+ and its involvement in the [V2 ]+ → [V2 O2 ]+ che ...[more]

PMID: 32100908

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Project description:Mononuclear non-heme iron complexes that serve as structural and functional mimics of the thiol dioxygenases (TDOs), cysteine dioxygenase (CDO) and cysteamine dioxygenase (ADO), have been prepared and characterized with crystallographic, spectroscopic, kinetic, and computational methods. The high-spin Fe(II) complexes feature the facially coordinating tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine (Ph2TIP) ligand that replicates the three histidine (3His) triad of the TDO active sites. Further coordination with bidentate l-cysteine ethyl ester (CysOEt) or cysteamine (CysAm) anions yielded five-coordinate (5C) complexes that resemble the substrate-bound forms of CDO and ADO, respectively. Detailed electronic-structure descriptions of the [Fe(Ph2TIP)(LS,N)]BPh4 complexes, where LS,N = CysOEt (1) or CysAm (2), were generated through a combination of spectroscopic techniques [electronic absorption, magnetic circular dichroism (MCD)] and density functional theory (DFT). Complexes 1 and 2 decompose in the presence of O2 to yield the corresponding sulfinic acid (RSO2H) products, thereby emulating the reactivity of the TDO enzymes and related complexes. Rate constants and activation parameters for the dioxygenation reactions were measured and interpreted with the aid of DFT calculations for O2-bound intermediates. Treatment of the TDO models with nitric oxide (NO)-a well-established surrogate of O2-led to a mixture of high-spin and low-spin {FeNO}7 species at low temperature (-70 °C), as indicated by electron paramagnetic resonance (EPR) spectroscopy. At room temperature, these Fe/NO adducts convert to a common species with EPR and infrared (IR) features typical of cationic dinitrosyl iron complexes (DNICs). To complement these results, parallel spectroscopic, computational, and O2/NO reactivity studies were carried out using previously reported TDO models that feature an anionic hydrotris(3-phenyl-5-methyl-pyrazolyl)borate (Ph,MeTp-) ligand. Though the O2 reactivities of the Ph2TIP- and Ph,MeTp-based complexes are quite similar, the supporting ligand perturbs the energies of Fe 3d-based molecular orbitals and modulates Fe-S bond covalency, suggesting possible rationales for the presence of neutral 3His coordination in CDO and ADO.

Dataset Information

Counter-Intuitive Gas-Phase Reactivities of [V₂ ]⁺ and [V₂ O]⁺ towards CO₂ Reduction: Insight from Electronic Structure Calculations.

Publications

Counter-Intuitive Gas-Phase Reactivities of [V<sub>2</sub> ]<sup>+</sup> and [V<sub>2</sub> O]<sup>+</sup> towards CO<sub>2</sub> Reduction: Insight from Electronic Structure Calculations.

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