Flash and Continuous Photolysis Studies of the Thionitrosyl Complex Cr(CH3CN)5(NS)2+ and the Nitric Oxide Analogs. Reactions of Nitrogen Monosulfide in Solution

Johannes Wied Dethlefsen; Erik Hedegård; R. Dale Rimmer; Peter Ford; Anders Rørbæk Døssing

Flash and Continuous Photolysis Studies of the Thionitrosyl Complex Cr(CH₃CN)₅(NS)²⁺ and the Nitric Oxide Analogs. Reactions of Nitrogen Monosulfide in Solution

Johannes Wied Dethlefsen, Erik Hedegård, R. Dale Rimmer, Peter Ford, Anders Rørbæk Døssing

Department of Chemistry

12 Citations (Scopus)

Abstract

Photolysis of the thionitrosyl complex Cr(CH₃CN)₅(NS)²⁺ (1) in acetonitrile solution leads to the dissociation of nitrogen monosulfide (NS). In deaerated solution, this reaction is reversible, and flash photolysis studies demonstrate that NS reacts with Cr(CH₃CN)₆²⁺ according to the rate law d[1]/dt = k_on [Cr(CH₃CN)₆²⁺][NS] (k_on = 2.3 x 10⁸M^-1 s^-1 at 298 K). Photolysis of 1 in deaerated acetonitrile with the added Fe(S₂CNEt₂)₂ leads to transfer of NS and formation of a species concluded to be Fe(S₂CNEt₂)₂(NS) based on its EPR spectrum. Analogous photolysis of 1 in the presence of added NO leads to clean formation of the nitrosyl complex Cr(CH₃CN)₅(NO)²⁺ (2) presumably by NO capture of the photoproduct Cr(CH₃CN)₆²⁺ (3). When 1 was photolyzed in aerated acetonitrile solution, the reactive species 3 is trapped, thus leading to net photochemical transformations with excitation wavelength dependent quantum yields of 0.3-1.0 mol/Einstein. Mass spectroscopic studies of the product solutions demonstrate formation of S₈, presumably from the decomposition of NS. The quantitative photochemical behaviors of 1 and the nitrosyl analog 2 are compared.
Udgivelsesdato: Jan.

Original language	English
Journal	Inorganic Chemistry
Volume	48
Issue number	1
Pages (from-to)	231-238
Number of pages	8
ISSN	0020-1669
Publication status	Published - 2009

Cite this

Flash and Continuous Photolysis Studies of the Thionitrosyl Complex Cr(CH₃CN)₅(NS)²⁺ and the Nitric Oxide Analogs. Reactions of Nitrogen Monosulfide in Solution. / Dethlefsen, Johannes Wied; Hedegård, Erik; Rimmer, R. Dale et al.

In: Inorganic Chemistry, Vol. 48, No. 1, 2009, p. 231-238.

Research output: Contribution to journal › Journal article › Research › peer-review

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title = "Flash and Continuous Photolysis Studies of the Thionitrosyl Complex Cr(CH3CN)5(NS)2+ and the Nitric Oxide Analogs. Reactions of Nitrogen Monosulfide in Solution",

abstract = "Photolysis of the thionitrosyl complex Cr(CH3CN)5(NS)2+ (1) in acetonitrile solution leads to the dissociation of nitrogen monosulfide (NS). In deaerated solution, this reaction is reversible, and flash photolysis studies demonstrate that NS reacts with Cr(CH3CN)62+ according to the rate law d[1]/dt = kon [Cr(CH3CN)62+][NS] (kon = 2.3 x 108 M-1 s-1 at 298 K). Photolysis of 1 in deaerated acetonitrile with the added Fe(S2CNEt2)2 leads to transfer of NS and formation of a species concluded to be Fe(S2CNEt2)2(NS) based on its EPR spectrum. Analogous photolysis of 1 in the presence of added NO leads to clean formation of the nitrosyl complex Cr(CH3CN)5(NO)2+ (2) presumably by NO capture of the photoproduct Cr(CH3CN)62+ (3). When 1 was photolyzed in aerated acetonitrile solution, the reactive species 3 is trapped, thus leading to net photochemical transformations with excitation wavelength dependent quantum yields of 0.3-1.0 mol/Einstein. Mass spectroscopic studies of the product solutions demonstrate formation of S8, presumably from the decomposition of NS. The quantitative photochemical behaviors of 1 and the nitrosyl analog 2 are compared. Udgivelsesdato: Jan.",

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AU - Dethlefsen, Johannes Wied

AU - Hedegård, Erik

AU - Rimmer, R. Dale

AU - Ford, Peter

AU - Døssing, Anders Rørbæk

N1 - Paper id:: DOI: 10.1021/ic8016936

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N2 - Photolysis of the thionitrosyl complex Cr(CH3CN)5(NS)2+ (1) in acetonitrile solution leads to the dissociation of nitrogen monosulfide (NS). In deaerated solution, this reaction is reversible, and flash photolysis studies demonstrate that NS reacts with Cr(CH3CN)62+ according to the rate law d[1]/dt = kon [Cr(CH3CN)62+][NS] (kon = 2.3 x 108 M-1 s-1 at 298 K). Photolysis of 1 in deaerated acetonitrile with the added Fe(S2CNEt2)2 leads to transfer of NS and formation of a species concluded to be Fe(S2CNEt2)2(NS) based on its EPR spectrum. Analogous photolysis of 1 in the presence of added NO leads to clean formation of the nitrosyl complex Cr(CH3CN)5(NO)2+ (2) presumably by NO capture of the photoproduct Cr(CH3CN)62+ (3). When 1 was photolyzed in aerated acetonitrile solution, the reactive species 3 is trapped, thus leading to net photochemical transformations with excitation wavelength dependent quantum yields of 0.3-1.0 mol/Einstein. Mass spectroscopic studies of the product solutions demonstrate formation of S8, presumably from the decomposition of NS. The quantitative photochemical behaviors of 1 and the nitrosyl analog 2 are compared. Udgivelsesdato: Jan.

AB - Photolysis of the thionitrosyl complex Cr(CH3CN)5(NS)2+ (1) in acetonitrile solution leads to the dissociation of nitrogen monosulfide (NS). In deaerated solution, this reaction is reversible, and flash photolysis studies demonstrate that NS reacts with Cr(CH3CN)62+ according to the rate law d[1]/dt = kon [Cr(CH3CN)62+][NS] (kon = 2.3 x 108 M-1 s-1 at 298 K). Photolysis of 1 in deaerated acetonitrile with the added Fe(S2CNEt2)2 leads to transfer of NS and formation of a species concluded to be Fe(S2CNEt2)2(NS) based on its EPR spectrum. Analogous photolysis of 1 in the presence of added NO leads to clean formation of the nitrosyl complex Cr(CH3CN)5(NO)2+ (2) presumably by NO capture of the photoproduct Cr(CH3CN)62+ (3). When 1 was photolyzed in aerated acetonitrile solution, the reactive species 3 is trapped, thus leading to net photochemical transformations with excitation wavelength dependent quantum yields of 0.3-1.0 mol/Einstein. Mass spectroscopic studies of the product solutions demonstrate formation of S8, presumably from the decomposition of NS. The quantitative photochemical behaviors of 1 and the nitrosyl analog 2 are compared. Udgivelsesdato: Jan.

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