On the Electrochemical, Spectral and Photochemical Properties of Cyano-Nitrosyl Complexes. A Comparison between Iron and Ruthenium Analogues

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Title:On the Electrochemical, Spectral and Photochemical Properties of Cyano-Nitrosyl Complexes. A Comparison between Iron and Ruthenium Analogues
Creators:
Fiedler, Jan
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 58, 3, pp. 461-473

Abstract

First order rate constant of cyanide splitting from one-electron product of the nitropruside ion reduction was determined using a.c. polarography (<i>k</i> = 350 s<sup>-1</sup> in CH<sub>3</sub>CN). [Ru(CN)<sub>5</sub>(NO)]<sup>2-</sup> ion is reduced reversibly (<i>E</i><sub>1/2</sub> = -1.04 V, <i>k</i><sup>0</sup> = 4.86 . 10<sup>-3</sup> m s <sup>-1</sup> in CH<sub>3</sub>CN; <i>E</i><sub>1/2</sub> = -0.39 V in H<sub>2</sub>O) with one electron. IR and EPR study indicates dimerization of the reduction product in solution but no cyanide splitting from electrogenerated [Ru(CN)<sub>5</sub>(NO)]<sup>3-</sup> was detected. Further reduction of [Ru(CN)<sub>5</sub>(NO)]<sup>3-</sup>, with consumption of protons occurs in aqueous media. Efficient photochemical reactions of [Fe(CN)<sub>4</sub>(NO)]<sup>2-</sup> with O<sub>2</sub>, KMNO<sub>4</sub> and pyridine take place when the complex is excited at the metal-to-nitrosyl charge transfer band.

Title:On the Electrochemical, Spectral and Photochemical Properties of Cyano-Nitrosyl Complexes. A Comparison between Iron and Ruthenium Analogues
Creators:
Fiedler, Jan
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:58
Number:3
Page Range:pp. 461-473
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19930461UNSPECIFIED
ID Code:170
Item Type:Article
Deposited On:06 Feb 2009 16:58
Last Modified:06 Feb 2009 15:58

Citation

Fiedler, Jan (1993) On the Electrochemical, Spectral and Photochemical Properties of Cyano-Nitrosyl Complexes. A Comparison between Iron and Ruthenium Analogues. Collection of Czechoslovak Chemical Communications, 58 (3). pp. 461-473. ISSN 0010-0765

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