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Article: Proton-coupled electron-transfer reactions. Mechanisms of two-electron reduction of trans-dioxoruthenium(VI) to trans-aquooxoruthenium(VI) and disproportionate of trans-dioxoruthenium(V)
Title | Proton-coupled electron-transfer reactions. Mechanisms of two-electron reduction of trans-dioxoruthenium(VI) to trans-aquooxoruthenium(VI) and disproportionate of trans-dioxoruthenium(V) |
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Authors | |
Issue Date | 1990 |
Publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html |
Citation | Journal Of The American Chemical Society, 1990, v. 112 n. 13, p. 5176-5181 How to Cite? |
Abstract | The kinetics and mechanism of the reduction of trans-[Ru vI(TMC)(O) 2] 2+ to trans-[Ru Iv(TMC)O(H 2O)] 2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) in aqueous solution by outer-sphere one-electron reductants (R), trans-[Ru VI(TMC)(O) 2] 2+ + 2R + 2H + → trans-[Ru Iv(TMC)O(H 2O)] 2+ + 2R +, have been studied. The first step of the reduction is a simple outer-sphere electron-transfer process, trans-[Ru VI(TMC)(O) 2] 2+ + R → trans-[Ru v(TMC)(O) 2] + + R + with rate = k 2[Ru(VI)] [R]. The rate constants (k 2) with cis-[Ru II(NH 3) 4bpy] 2+ (bpy = 2,2′-bipyridine), [Ru II(NH 3) 5isn] 2+ (isn = isonicotinamide), and [Ru II(NH 3) 5py] 2+ (py = pyridine) have been measured and can be correlated with the Marcus cross relation. The estimated self-exchange rate constant of the trans-[Ru VI(TMC)(O) 2] 2+/ trans-[Ru v(TMC)(O) 2]+ couple is 1.5 × 10 5 mol -1 dm 3 s -1 (I = 0.1 M) at 298 K. When trans-[Ru VI(TMC)(O) 2] 2+ is in excess, the trans-[Ru V(TMC)(O) 2]+ species formed will undergo rapid disproportionation, 2trans-[Ru v(TMC)(O) 2] + + 2H + → trans-[Ru VI(TMC)(O) 2] 2+ + trans-[Ru IV(TMC)O(H 2O)] 2+. The disproportionation follows the rate law: rate = K dis[Ru(V)] 2 with K dis = 2k eK p[H +]/(1 + K p[H +]) 2. The K p and k e are referred to the equilibrium constant and rate constant for the respective reactions, trans-[Ru v(TMC)(O) 2] 2+ + H +⇄ trans-[Ru v(TMC)O(OH)] 2+ and trans-(Ru v(TMC)O(OH)] 2+ + trans-[Ru v(TMC)(O) 2] + → trans-[Ru VI(TMC)(O) 2] 2+ + trans-[Ru IV(TMC)O(OH)] +. At 299 K and I = 0.1 M, K p and k c have been determined to be 615 ± 50 mol -1 dm 3 and (2.72 ± 0.34) × 10 6 mol -1 dm 3 s -1, respectively. The self-exchange rate constant of the trans-[Ru v(TMC)O(OH)] 2+/trans-[Ru IV(TMC)O(OH)] + has been estimated to be 5 × 10 3 mol -1 dm 3 s -1 at 298 K and I = 0.1 M. |
Persistent Identifier | http://hdl.handle.net/10722/167378 |
ISSN | 2021 Impact Factor: 16.383 2020 SCImago Journal Rankings: 7.115 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Che, CM | en_US |
dc.contributor.author | Lau, K | en_US |
dc.contributor.author | Lau, TC | en_US |
dc.contributor.author | Poon, CK | en_US |
dc.date.accessioned | 2012-10-08T03:06:14Z | - |
dc.date.available | 2012-10-08T03:06:14Z | - |
dc.date.issued | 1990 | en_US |
dc.identifier.citation | Journal Of The American Chemical Society, 1990, v. 112 n. 13, p. 5176-5181 | en_US |
dc.identifier.issn | 0002-7863 | en_US |
dc.identifier.uri | http://hdl.handle.net/10722/167378 | - |
dc.description.abstract | The kinetics and mechanism of the reduction of trans-[Ru vI(TMC)(O) 2] 2+ to trans-[Ru Iv(TMC)O(H 2O)] 2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) in aqueous solution by outer-sphere one-electron reductants (R), trans-[Ru VI(TMC)(O) 2] 2+ + 2R + 2H + → trans-[Ru Iv(TMC)O(H 2O)] 2+ + 2R +, have been studied. The first step of the reduction is a simple outer-sphere electron-transfer process, trans-[Ru VI(TMC)(O) 2] 2+ + R → trans-[Ru v(TMC)(O) 2] + + R + with rate = k 2[Ru(VI)] [R]. The rate constants (k 2) with cis-[Ru II(NH 3) 4bpy] 2+ (bpy = 2,2′-bipyridine), [Ru II(NH 3) 5isn] 2+ (isn = isonicotinamide), and [Ru II(NH 3) 5py] 2+ (py = pyridine) have been measured and can be correlated with the Marcus cross relation. The estimated self-exchange rate constant of the trans-[Ru VI(TMC)(O) 2] 2+/ trans-[Ru v(TMC)(O) 2]+ couple is 1.5 × 10 5 mol -1 dm 3 s -1 (I = 0.1 M) at 298 K. When trans-[Ru VI(TMC)(O) 2] 2+ is in excess, the trans-[Ru V(TMC)(O) 2]+ species formed will undergo rapid disproportionation, 2trans-[Ru v(TMC)(O) 2] + + 2H + → trans-[Ru VI(TMC)(O) 2] 2+ + trans-[Ru IV(TMC)O(H 2O)] 2+. The disproportionation follows the rate law: rate = K dis[Ru(V)] 2 with K dis = 2k eK p[H +]/(1 + K p[H +]) 2. The K p and k e are referred to the equilibrium constant and rate constant for the respective reactions, trans-[Ru v(TMC)(O) 2] 2+ + H +⇄ trans-[Ru v(TMC)O(OH)] 2+ and trans-(Ru v(TMC)O(OH)] 2+ + trans-[Ru v(TMC)(O) 2] + → trans-[Ru VI(TMC)(O) 2] 2+ + trans-[Ru IV(TMC)O(OH)] +. At 299 K and I = 0.1 M, K p and k c have been determined to be 615 ± 50 mol -1 dm 3 and (2.72 ± 0.34) × 10 6 mol -1 dm 3 s -1, respectively. The self-exchange rate constant of the trans-[Ru v(TMC)O(OH)] 2+/trans-[Ru IV(TMC)O(OH)] + has been estimated to be 5 × 10 3 mol -1 dm 3 s -1 at 298 K and I = 0.1 M. | en_US |
dc.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html | en_US |
dc.relation.ispartof | Journal of the American Chemical Society | en_US |
dc.title | Proton-coupled electron-transfer reactions. Mechanisms of two-electron reduction of trans-dioxoruthenium(VI) to trans-aquooxoruthenium(VI) and disproportionate of trans-dioxoruthenium(V) | en_US |
dc.type | Article | en_US |
dc.identifier.email | Che, CM:cmche@hku.hk | en_US |
dc.identifier.authority | Che, CM=rp00670 | en_US |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ja00169a027 | - |
dc.identifier.scopus | eid_2-s2.0-0003444185 | en_US |
dc.identifier.volume | 112 | en_US |
dc.identifier.issue | 13 | en_US |
dc.identifier.spage | 5176 | en_US |
dc.identifier.epage | 5181 | en_US |
dc.identifier.isi | WOS:A1990DK85500027 | - |
dc.publisher.place | United States | en_US |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_US |
dc.identifier.scopusauthorid | Lau, K=55025754200 | en_US |
dc.identifier.scopusauthorid | Lau, TC=7102222310 | en_US |
dc.identifier.scopusauthorid | Poon, CK=7202673504 | en_US |
dc.identifier.issnl | 0002-7863 | - |