Structure and Reactivity of the Oxyanions of Transition Metals.

Carrington, Alan; Symons, Martyn C. R.

doi:10.1021/cr60225a001

Cited by 125 publications

(41 citation statements)

References 69 publications

(119 reference statements)

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“…In this work, it was found ( Table 2) that the reaction rate depends on the nature of the mineral acid used as solvent. Therefore, in agreement with other authors (19)(20)(21)(22), it is possible that the protonation of the acid chromate ion will be accompanied by the incorporation of the anion form of the mineral acid used as solvent, which will considerably affect the subsequent oxidant capability of the new species of Cr(VI), according to the following equilibrium:…”

Section: Resultssupporting

confidence: 86%

Chromic oxidation of lactic acid in very strong acid media

Alvarez-Macho¹,

Montequi-Martin²

1990

Can. J. Chem.

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M A R~A PIEDAD ALVAREZ-MACHO and M A R~A ISABEL MONTEQUI-MARTIN. Can. J. Chern. 68,29 (1990). The oxidation of lactlc acid by chromic acid was studied at high concentrations of HCIO?, HN03, and H2S04 It was observed that the reaction rate depends not only on the acidity of the medium, but also on the nature of the mineral acid. The use of the Bunnett and Bunnett-Olsen criteria and the excess acidity concept allows us to propose a reaction mechanism of the A-2 type, the rate-determining step being a bimolecular process in whlch water participates as a nucleophile. The enthalpy and entropy of activation were determined; the decrease of the magnitude of these parameters when the acidity of the medium was increased I suggests the existence of a compensation effect.

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Section: Resultssupporting

confidence: 86%

Chromic oxidation of lactic acid in very strong acid media

Alvarez-Macho¹,

Montequi-Martin²

1990

Can. J. Chem.

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“…Oth er fac tors that may influe nce th e reactivity of polyc yelic, aromatic hydrocarbons toward pe riodi c acid are: (1) basicity of the hydrocarbon [49 , 50], (2) prese nce of a reactive bond or a free-valence ce nter [51,52,53], or a position of hi ghes t unpaired electro n-de nsiti es [54,55] or high unpai red spinde ns iti es [56] , (3) abilit y of periodic acid (as an e lec trophile) to form an association co mplex with a hydrocarbon, and (4) th e ionization potential of th e hydrocarbon [57 , 58]. In c reas in g reactivity toward peri od ic acid is usually parallele d by a decr easin g ioni zati on pote n tial of th e hydrocarbon , as fo Jl ows: nap hth acene (3 ) > pe ntace ne (17) > pyre ne (I ) > a nthracene (5 ) > phe nanthre ne (10) > naphth ale ne (7 ).…”

Section: General Reactivity Of Polycyclic Aromaticmentioning

confidence: 99%

“…r. spectrum of pyrene radical la is shown in figure 1 (spectrum A). The absence of the hyperfi ne s tructure for the pyrene radical cation (Ia), as compared to the seve n-lin e s pec trum of th e e quivale nt [54,66] pyre ne a nion r adi cal (splitting constant 1.09 gaus s) [67] may b e explained on the basis of a probable interac tion of the 1T-elec tron radical (Ia) originally formed with oxygen, to give a relatively s table pyre ne pe roxide (sigma) radical of type 24 ; this reac tion is probably in compe tition with the dimerization of Ia to 2. The oxygen was probably s upplie d by periodic acid, because dilution and deoxygenation (by bubbling nitroge n into the diluted solution) produced a similar one-line e.s.r.…”

Section: General Reactivity Of Polycyclic Aromaticmentioning

confidence: 99%

“…As suggested in the previous co mmunic ation [59] , the first ste p in the mecha ni s m of the oxid a tion of naphthale ne may involv e association be tween pe riodic acid (an electrophil e) and the free-vale nce cente r of th e aromati c rin g [51-53}, or with a positi on hav in g the high es t unpaired electron de ns iti es [54]; these possibilities a re in agree me nt with the basicity of the polycyclic, aromatic hydroc arbons [49 , 50].…”

Section: General Reactivity Of Polycyclic Aromaticmentioning

confidence: 99%

See 1 more Smart Citation

Periodic acid, a novel oxidant of polycyclic, aromatic hydrocarbons

Fatiadi

1968

J. RES. NATL. BUR. STAN. SECT. A.

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Ce rtain polycyc li c , aro mat ic hydrocarbons can be ox idi zed with periodi c acid in aprotic so lvent s co nta inin g a s mall p roportion of water. A uniqu e, two· fold cha rac te r of respo nse to pe riodi c acid by these hydroca rbon s has been fo und: (1) prod uc ti on of a co uplin g reac tion throu gh a radi ca l in te rme diate [co nve rsion of pyre ne into l,l ' -b ipyrene, and fluore ne into 1,2-b is(2,2' -biph e ny lylene)ethy le neJ or (2) co nvers io n into qui no nes by a two-equiv alent ox id ation mec hani s m that does not involve a radical int erm edi a te [ace naphth e ne, anthracene, a nthrone , be nz[alanthrace ne, naphthace ne, naphthalen e, a nd ph e nanthre ne]. Little or no reac ti on was observed whe n ox idati on was attempted wi th sodium me taperiodate in s tead of pe riodi c ac id .Electron-s pin reso nan ce revea led no radi cal inte rmediate in th e ox id a ti on of malonic ac id with e ither periodic acid o r sodium periodate.Key Word s: Aproti c so lvents ; aromatic hydroca rbon s; maloni c acid ; periodic acid ; pyrene radical; quinon es; reacti on mecha ni s m; sodium metape ri oda te.

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“…Colloidal MnO 2 has the advantage over water-insoluble MnO 2 that conventional UV-Vis spectrophotometers can be used to study their reactions with different types of organic and inorganic reductants [6][7][8]. The involvement of manganese(IV), formed as an intermediate in the redox reactions of permanganate with different organic reductants, has generated much debate in the past [9][10][11]. As a result, it has been accepted that one-and two-electron oxidation of different substrates by permanganate must proceed through the formation of manganese(IV) species in aqueous acidic or neutral media [12,13].…”

Section: Introductionmentioning

confidence: 99%