Hydrolysis and Photolysis of Tris(tetraethylammonium) Pentacyanoperoxynitritocobaltate(III): Evidence for a Novel Complex, Pentacyanonitratocobaltate(III)

Wick, Patrick K.; Kissner, Reinhard; Koppenol, Willem H.

doi:10.1002/1522-2675(20011017)84:10<3057::aid-hlca3057>3.3.co;2-x

Cited by 7 publications

(10 citation statements)

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“…7 All the evidence pointed to a mechanism whereby the rhodium nitrato species was formed by in-cage and/or out-of-cage recombination of NO the initially formed L 2 RhOONO 2+ (L 2 ) Me 6 - [14]aneN 4 ). This, and the simultaneous observation of a nitrato complex of pentacyanocobalt(III) by another group, 21 are the first cases documenting nitratometal intermediates in the NO/superoxometal chemistry, although a possibility that such species might be involved had been considered earlier. 6,11,22 We have now extended our studies to another superoxometal complex, Cr aq OO 2+ .…”

Section: Introductionmentioning

confidence: 83%

Reaction of a Superoxochromium(III) Ion with Nitrogen Monoxide: Kinetics and Mechanism

2001

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The kinetics of the rapid reaction between Cr(aq)OO(2+) and NO were determined by laser flash photolysis of Cr(aq)NO(2+) in O(2)-saturated acidic aqueous solutions, k = 7 x 10(8) M(-1) s(-1) at 25 degrees C. The reaction produces an intermediate, believed to be NO(2), which was scavenged with ([14]aneN(4))Ni(2+). With limiting NO, the Cr(aq)OO(2+)/NO reaction has a 1:1 stoichiometry and produces both free NO(3)(-) and a chromium nitrato complex, Cr(aq)ONO(2)(2+). In the presence of excess NO, the stoichiometry changes to [NO]/[Cr(aq)OO(2+)] = 3:1, and the reaction produces close to 3 mol of nitrite/mol of Cr(aq)OO(2+). An intermediate, identified as a nitritochromium(III) ion, Cr(aq)ONO(2+), is a precursor to a portion of free NO(2)(-). In the proposed mechanism, the initially produced peroxynitrito complex, Cr(aq)OONO(2+), undergoes O-O bond homolysis followed by some known and some novel chemistry of Cr(aq)O(2+) and NO(2). The reaction between Cr(aq)O(2+) and NO generates Cr(aq)ONO(2+), k > 10(4) M(-1) s(-1). Cr(aq)OO(2+) reacts with NO(2) with k = 2.3 x 10(8) M(-1) s(-1).

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Section: Introductionmentioning

confidence: 83%

Reaction of a Superoxochromium(III) Ion with Nitrogen Monoxide: Kinetics and Mechanism

2001

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“…To our knowledge, this is the first instance where a nitratometal complex has been observed directly as an intermediate in an NO/superoxometal reaction. After this work was completed, we became aware of another nitrato complex, (CN) 5 CoONO 2 3- , which was produced by isomerization of (CN) 5 CoOONO 3- …”

Section: Discussionmentioning

confidence: 99%

“…The rhodium complexes in the present work would seem to be better models for the biological systems in that the isomerization is exceedingly fast (<3 ms). Both the peroxynitrito and nitrato complexes of pentacyanocobalt(III) are long-lived. , …”

Section: Discussionmentioning

confidence: 99%

Reaction of Nitrogen Monoxide with a Macrocyclic Superoxorhodium(III) Complex Produces an Observable Nitratorhodium Intermediate

Pestovsky

Bakač

2002

J. Am. Chem. Soc.

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The rapid (k > or = 10(6) M(-1) s(-1)) reaction between NO and L(2)(H(2)O)RhOO(2+) (L(2) = meso-Me(6)-[14]ane-N(4)) generates two strongly oxidizing, scavengeable intermediates, believed to be NO(2) and L(2)(H(2)O)RhO(2+). A mechanism is proposed whereby a peroxynitrito complex L(2)(H(2)O)RhOONO(2+) is formed first. The homolysis of O-O bond produces NO(2) and L(2)(H(2)O)RhO(2+) which were trapped with ABTS(2)(-) and Ni([14]aneN(4))(2+). In the absence of scavengers, the decomposition of L(2)(H(2)O)RhOONO(2+) produces both free NO(3)(-) and a rhodium nitrato complex L(2)(H(2)O)RhONO(2)(2+), which releases NO(3)(-) in an inverse acid-dependent process. The total yield of L(2)(H(2)O)RhONO(2)(2+) is 70%. In a minor, parallel path, NO and L(2)(H(2)O)RhOO(2+) react to give nitrite and the hydroperoxo complex L(2)(H(2)O)RhOOH(2+).

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“…A few oxoperoxonitrato−metal complexes have been observed, but these were always synthesized from a superoxo−metal complex and nitrogen monoxide. For instance, Herold and co-workers have shown that nitrogen monoxide reacts with oxymyoglobin to form a oxoperoxonitrato−iron(III) intermediate. , We subsequently demonstrated that the reaction of pentacyanosuperoxocobaltate(III) with nitrogen monoxide yields an oxoperoxonitrato complex that is surprisingly stable at neutral pH and slowly isomerizes at acidic pH . Similarly synthesized transient chromium(III)− and rhodium−oxoperoxonitrato complexes have been described by Bakac and co-workers. , However, direct formation of an oxoperoxonitrato−metal complex from a reaction of oxoperoxonitrate(1−) or its protonated form with a metal ion has not yet been reported.…”

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confidence: 61%

Kinetics Evidence for a Complex between Peroxynitrous Acid and Titanium(IV)

2004

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The reaction between TiO(2+) and ONOOH in 0.9 M H(2)SO(4) provides evidence for direct formation, previously unobserved, of a HOONO-metal complex. The reaction proceeds via formation of an end-on complex (k = 3.0 x 10(2) M(-1) s(-1)) that rearranges to form a side-on complex (k approximately equal to 20 s(-1)). With ONOOH in excess, this rearrangement proceeds more slowly (k approximately equal to 0.1 s(-1)), probably because multiple hydrogen oxoperoxonitrate molecules form end-on complexes with oxotitanium(IV) and hinder rearrangement to the side-on complex. The absorption spectrum of the final product is that of TiO(2)(2+). Presumably, during the rearrangement or later, NO+ is lost.

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Hydrolysis and Photolysis of Tris(tetraethylammonium) Pentacyanoperoxynitritocobaltate(III): Evidence for a Novel Complex, Pentacyanonitratocobaltate(III)

Cited by 7 publications

References 0 publications

Reaction of a Superoxochromium(III) Ion with Nitrogen Monoxide: Kinetics and Mechanism

Reaction of a Superoxochromium(III) Ion with Nitrogen Monoxide: Kinetics and Mechanism

Reaction of Nitrogen Monoxide with a Macrocyclic Superoxorhodium(III) Complex Produces an Observable Nitratorhodium Intermediate

Kinetics Evidence for a Complex between Peroxynitrous Acid and Titanium(IV)

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