The oxidation of cyclobutanol by ruthenium tetroxide and sodium ruthenate

Lee, Donald G.; Spitzer, Udo A.; Cleland, J; Olson, Merle E.

doi:10.1139/v76-304

Cited by 36 publications

(18 citation statements)

References 7 publications

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“…Consequently, the rates of reaction were usually determined by following the increase in absorbance at 320 nm as the reaction progressed. This approach, based on the assumption that the rate of formation of RuO, is equal to the rate of disappearance of Ruo4*-, is consistent with previous work which indicated ruthenate is a two-electron oxidant (15). Both kinetic methods gave very similar values for the rate constants.…”

Section: Kinetic Methodssupporting

confidence: 87%

“…Although these authors did not speculate on a possible structure for the intermediate, it seems clear from the aforementioned theoretical calculations that their "complex" is likely the adduct, 1. Since the 0x0-ruthenium species formed in reaction [15] ( H R u O~~-) is in the reactive 5+ oxidation state, a subsequent single electron transfer (reaction [16]) would probably occur before the radical could diffuse out of the solvent cage.…”

Section: Imentioning

confidence: 99%

“…Application of the steady-state approximation (31) to the intermediate 1 in reactions [14] and [15] indicates why the reaction mechanism would produce an isotope effect in spite of the fact that the a-C-H bond is cleaved prior to the rate-limiting step.…”

Section: Imentioning

confidence: 99%

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Kinetics and mechanism of the oxidation of alcohols by ruthenate and perruthenate ions

Lee¹,

Congson²

1990

Can. J. Chem.

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a number of high valent transition metal ions that can be used as oxidants in organic chemistry. In their reactions with alcohols both ions exhibit several striking similarities -concave Hammett plots, primary deuterium isotope effects, small enthalpies of activation, and large negative entropies of activation. The most likely explanation of the concave upward Haminett plots is the involvement of free radical-like transition states that could be formed by the decomposition of organometallic intermediates.

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Section: Kinetic Methodssupporting

confidence: 87%

Section: Imentioning

confidence: 99%

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Kinetics and mechanism of the oxidation of alcohols by ruthenate and perruthenate ions

Lee¹,

Congson²

1990

Can. J. Chem.

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“…with all of the experimental evidence is available if 9 is assumed to be a cyclic ruthenate(V1) diester formed by the oxidation of 7. Such a two-electron transfer reaction is consistent with the known properties of ruthenate under these conditions (15). Furthermore, it would not be unreasonable to observe a large rate constant for such a reaction; many similar electron transfer processes between transition metal oxyanions are known to occur rapidly (16).…”

Section: Introductionsupporting

confidence: 76%

“…Hence it appears as if the reaction likely involves an initial addition of the oxidant to the double bond, giving a ruthenium(V) cyclic diester, 10, as in eq. [15]. However, since there was no indication of the formation of inorganic products other than RUO$-the intermediate, 10, must undergo a subsequent reaction leading to the formation of ruthenate.…”

Section: Perruthenate Oxidationsmentioning

confidence: 98%

Oxidation of hydrocarbons. 12. Kinetics and mechanism of the oxidation of trans-cinnamic acid by ruthenate and perruthenate ions

Lee¹,

Helliwell²

1984

Can. J. Chem.

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, 1085 (1984). Recent theoretical calculations by RappC and Goddard have pointed to the importance of spectator 0x0 groups in stabilizing intermediates produced during thc reduction of high-valent transition metal oxides; intermediates which contain triply-bonded metal 0x0 groups are predicted to be unusually stable. In an attempt to test these conclusions experimentally, the rates of oxidation of cinnamate ion by ruthenate and permthenate ions have been studied. Since the most likely intermediate formed from permthenate ion (but not ruthenate ion) would contain a stabilizing, triply-bonded spectator 0x0 group, it would be expected to react faster if the calculations are correct. In agreement with these predictions, it was found that the activation energy (AG*) for the ruthenate reaction was about 7 kcal/mol higher than for the corresponding permthenate reaction. DONALD G. LEE et STUART HELLIWELL. Can. J . Chem. 62, 1085 (1984) Les recents calculs thCoriques de RappC et Goddard ont mis en Cvidence I'importance des groupes 0x0 spectateurs dans la stabilisation dcs intermediaires obtenus lors de la riduction d'oxydes de mCtaux de transition de valence ClevCe; d'apres ces calculs, les intermCdiaires qui contiennent les groupes 0x0 triplement liCs au metal seront particulierement stables. Dans le but de verifier expCrimentalement cette hypothkse, on a CtudiC les vitesses d'oxydation de I'ion cinnamate par les ions ruthenate et permthCnate. Puisque l'intermtdiaire le plus communtment form6 a partir de I'ion permthenate (mais non B partir de I'ion ruthhate) contiendrait le groupe spectateur 0x0 triplement liC, on pourrait s'attendre 21 ce qu'il soit plus rkactif si les calculs sont corrects. En accord avec ces prkvisions, on a trouvC que I'tnergie d'activation (AG*) de la rCaction du ruthhate est d'environ 7 kcal/mol plus ClevCe que celle de la rCaction correspondante du permthCnate.[Traduit par le journal] Introduction Transition metal oxides and oxyanions have been used extensively as oxidants in both inorganic and organic chemistry (1). The driving force in most such reactions is generally considered to be a lowering of the oxidation number of the oxidant, which may formally be considered as a flow of electrons into the d orbitals of the metal. Since many of the high-valent do, d l , and d2 oxidants are capable of accepting several electrons before reaching a stable oxidation state, these reactions usually proceed in several steps with the formation of a number of intermediates of greater or lesser stability. The reactions are consequently of interest from both a practical and a theoretical point of view.RappC and Goddard (2) have recently described results, obtained from a theoretical study, that are extremely useful for predicting which intermediates are most likely to be formed during the course of several of these reactions. By use of ab initio methods they found that the metal-0x0 bonds present substantially influenced the stability of an intermediate. Metal-0x0 groups which have triple bond character were f...

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Kinetic study of ruthenium(VI)-catalyzed oxidation of 2-butanol by alkaline hexacyanoferrate(III)

Mucientes

Poblete

Rodrı́guez

et al. 1999

Int. J. Chem. Kinet.

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The oxidation kinetics of 2-butanol by alkaline hexacyanoferrate(III) catalyzed by sodium ruthenate has been studied spectrophotometrically. The initial rates method was used for kinetic analysis. The reaction rate shows a fractional-order in [hexacyanoferrate(III)] and [substrate] and a first-order dependence on [Ru(VI)]. The dependence on [OH Ϫ ] is rather more complicated. The kinetic data suggest a reaction mechanism involving two active catalytic species. Each one of these species forms an intermediate complex with the substrate. The attack of these complexes by hexacyanoferrate(III), in a slow step, produces ruthenium(V) complexes which are oxidized in subsequent steps to regenerate the catalyst species.

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The oxidation of cyclobutanol by ruthenium tetroxide and sodium ruthenate

Cited by 36 publications

References 7 publications

Kinetics and mechanism of the oxidation of alcohols by ruthenate and perruthenate ions

Kinetics and mechanism of the oxidation of alcohols by ruthenate and perruthenate ions

Oxidation of hydrocarbons. 12. Kinetics and mechanism of the oxidation of trans-cinnamic acid by ruthenate and perruthenate ions

Kinetic study of ruthenium(VI)-catalyzed oxidation of 2-butanol by alkaline hexacyanoferrate(III)

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