The oxidation of hydrogen peroxide by tris(polypyridine) complexes of osmium(III), iron(III), ruthenium(III), and nickel(III) in aqueous media

Macartney, Donal H.

doi:10.1139/v86-319

Cited by 14 publications

(12 citation statements)

References 20 publications

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“…In sulphate medium, 57 58 With [Ni(tacn) 3 ] 3+ , HO − 2 is the only redoxactive species and reduction occurs only at metal centre and not at the ligand. 59 Kinetic measurements of oxidation of hydrogen peroxide by [Ni III L 2 (SO 4 )] was found to be complicated and the uncatalysed reaction may involve ligand oxidation similar to [Ni III L 1 (SO 4 )].…”

Section: Resultsmentioning

confidence: 99%

Kinetic measurements and quantum chemical calculations on low spin Ni(II)/(III) macrocyclic complexes in aqueous and sulphato medium

2015

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Cu(II) ion catalyzed kinetics of oxidation of H 2 O 2 by [Ni III L 2 ] (L 2 = 1,8-bis(2-hydroxyethyl)-1,3,6,8,10,13-hexaazacyclotetradecane) was studied in aqueous acidic medium in the presence of sulphate ion. The rate of oxidation of H 2 O 2 by [Ni III L 2 ] is faster than that by [Ni III L 1 ] (L 1 = 1,4,8,11-tetraazacyclotetradecane) in sulphate medium. DFT calculations at BP86/def2-TZVP level lead to different modes of bonding between [NiL] II/III and water ligands (L = L 1 and L 2 ). In aqueous medium, two water molecules interact with [NiL] II through weak hydrogen bonds with L and are tilted by ∼23 • from the vertical axis forming the dihydrate [NiL] 2+ .2H 2 O. However, there is coordinate bond formation between [NiL 1 ] III and two water molecules in aqueous medium and an aqua and a sulphato ligand in sulphate medium leading to the octahedral complexes [NiL 1 (H 2 O) 2 ] 3+ and [NiL 1 (SO 4 )(H 2 O)] + . In the analogous [NiL 2 ] III , the water molecules are bound by hydrogen bonds resulting in [NiL 2 ] 3+ .2H 2 O and [NiL 2 (SO 4 )] + .H 2 O. As the sulphato complex [NiL 2 (SO 4 )] + .H 2 O is less stable than [NiL 1 (SO 4 )(H 2 O)] + in view of the weak H-bonding interactions in the former it can react faster. Thus the difference in the mode of bonding between Ni(III) and the water ligand can explain the rate of oxidation of H 2 O 2 by [Ni III L] complexes.

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Section: Resultsmentioning

confidence: 99%

Kinetic measurements and quantum chemical calculations on low spin Ni(II)/(III) macrocyclic complexes in aqueous and sulphato medium

2015

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“…tions ( 5) and ( 6) are then consumed either by reaction (9) with Ni III or by the disproportionation reaction (8).…”

Section: Oxidation Of Hydrogen Peroxide By [Ni(tacn) 2 ] 3ϩmentioning

confidence: 99%

“…The oxidation of hydrogen peroxide by [Ru(bipy) 3 ] 3ϩ was also studied for direct comparison of the kinetic data with those reported by Macartney. 9 The kinetic isotope effect was also examined to confirm the interaction of HO 2 Ϫ with the amino hydrogen atom on the tacn ligand during the electron-transfer process. This provides an opportunity to investigate the reactivity of H 2 O 2 and HO 2 Ϫ ions in detail.…”

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confidence: 99%

Oxidations of hydrogen peroxide by bis(1,4,7-triazacyclononane)nickel(III), bis(1,4,7-trithiacyclononane)iron(III) and tris(2,2′-bipyridine)ruthenium(III) ions in acidic aqueous solutions ‡

Koshino¹,

Funahashi²,

Takagi³

1997

J. Chem. Soc., Dalton Trans.

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“…7,8 Oxidation of hydrogen peroxide by tris(2,2 -bipyridine) and tris(4,4 -dimethyl-2, 2 -bipyridine) complexes of osmium(III), iron(III), ruthenium(III), and nickel(III) studied in acidic and neutral aqueous media, showed an inverse acid dependence over the pH range 6.0-8.5. 14 2 are found to be reactive oxygen species (ROS) and react with [Ni III L] in absence and presence of stabilizing anions such as sulphate. 7,8 Recently, we have studied in detail the kinetics of oxidation of hydrogen peroxide by Ni(III) tetra-aza and hexa-aza macrocycles in acidic aqueous solution in the presence of sulphate ion in the pH range 1-2.5.…”

Section: Introductionmentioning

confidence: 99%

Study of behaviour of Ni(III) macrocyclic complexes in acidic aqueous medium through kinetic measurement involving hydrogen peroxide oxidation and DFT calculations

2017

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The Cu(II) ion-catalysed kinetics of oxidation of H 2 O 2 by [Ni III L] [where L = L 1 (cyclam) and L 2 (1,8-bis(2-hydroxyethyl)-1,3,6,8,10,13-hexaazacyclotetradecane)] was studied in the pH range of 3.6-5.6 in acetic acid-acetate buffer medium at 25 • C in the presence of sulphate ion. The ionic strength (I) was maintained at 0.5 M (NaClO 4). The rate constants showed an inverse acid dependence and [Ni III L 2 ] was observed to be more stable than [Ni III L 1 ]. The rate of the reaction of both complexes with hydrogen peroxide shows contrasting behaviour at pH > 2.5 when compared to the same reaction in perchloric acid medium. DFT calculations performed on the complexes [Ni III L 1 (SO 4)(OAc)] and [Ni III L 2 (SO 4)(OAc)] reveal that both the acetate and sulphate ligands are axially coordinated to the metal centre. In addition, there is strong hydrogen bonding between the axial ligand and NH hydrogen of the macrocyclic ligand. The computed covalent bond orders in the aqueous medium predict that the acetate forms stronger coordinate bond with Ni ion than the sulphate ligand. The hydroxyl group present in one of the pendant groups of L 2 forms a strong hydrogen bond with the sulphate ligand which leads to additional stability in [Ni III L 2 (SO 4)(OAc)].

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The oxidation of hydrogen peroxide by tris(polypyridine) complexes of osmium(III), iron(III), ruthenium(III), and nickel(III) in aqueous media

Cited by 14 publications

References 20 publications

Kinetic measurements and quantum chemical calculations on low spin Ni(II)/(III) macrocyclic complexes in aqueous and sulphato medium

Kinetic measurements and quantum chemical calculations on low spin Ni(II)/(III) macrocyclic complexes in aqueous and sulphato medium

Oxidations of hydrogen peroxide by bis(1,4,7-triazacyclononane)nickel(III), bis(1,4,7-trithiacyclononane)iron(III) and tris(2,2′-bipyridine)ruthenium(III) ions in acidic aqueous solutions ‡

Study of behaviour of Ni(III) macrocyclic complexes in acidic aqueous medium through kinetic measurement involving hydrogen peroxide oxidation and DFT calculations

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