Binding and Activation of Molecular Oxygen by Copper Complexes

Karlin, Kenneth D.; Gultneh, Yilma

doi:10.1002/9780470166369.ch3

Cited by 216 publications

(34 citation statements)

References 274 publications

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“…However, in an aqueous alkaline medium and at a high pH range employed in the study, periodate is unlikely to exist as HIO 6 4-(as present in the complex) as is evident from its involvement in the multiple equilibria [16] (2) 3-, a conclusion also supported by earlier work [9,10].…”

Section: Effect Of Temperature (T)supporting

confidence: 69%

“…It may be expected that a lower periodate complex such as monoperiodatocuptrate(III) (MPC) is more important in the reaction than the DPC in view of its participation in the reaction as given in Scheme 1. The inverse fractional order in [H 3 IO 6 2-] might also be due to this reason. Therefore, MPC might be the main reactive form of the oxidant.…”

Section: Effect Of Temperature (T)mentioning

confidence: 99%

“…Periodate and tellurate complexes of copper in its trivalent state have been extensively used in the analysis of several organic compounds [5]. The oxidation reaction usually involves the copper(II)-copper(I) couple and such aspects are detailed in different reviews [6,7]. The use of diperiodatocuprate(III) (DPC) as an oxidant in alkaline medium is new and restricted to a few cases due to the fact of its limited solubility and stability in aqueous media.…”

Section: Introductionmentioning

confidence: 99%

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Mechanistic aspects of oxidation on L-tyrosine by diperiodatocuprate(III) complex in alkali media: a kinetic model

2009

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Abstract:Oxidation of an amino acid, L-tyrosine (L-Tyr) by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of 0.1 mol dm -3 was studied spectrophotometrically at different temperatures (288.1 -313.1 K). The reaction between DPC and L-Tyr in alkaline medium exhibits 1:4 stoichiometry (L-Tyr:DPC). Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidence, a mechanism involving monoperiodatocuprate(III) (MPC) as the reactive oxidant species has been proposed. A suitable mechanism is proposed through the formation of a complex and free radical intermediate. The products were identified by spot test and characterized by spectral studies. The reaction constants involved in the different steps of the mechanism were calculated. The activation parameters with respect to slow step of the mechanism were computed and are discussed. The thermodynamic quantities were determined for different equilibrium steps. Isokinetic temperature was also calculated and found to be 252.3 K. Warsaw and Springer-Verlag Berlin Heidelberg. © Versita

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Section: Effect Of Temperature (T)supporting

confidence: 69%

Section: Effect Of Temperature (T)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Mechanistic aspects of oxidation on L-tyrosine by diperiodatocuprate(III) complex in alkali media: a kinetic model

2009

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“…4e), which in effect leads to polymerisation of discrete [Mo6I14] 2-clusters into a continuous crystal with a repeating unit [Mo6I12]n (Fig 4c,d). Such a structure is not known for any form of molybdenum iodide in the bulk form, and topologically [Mo6I12]n is much closer to the polymeric mixed molybdenum iodides/sulphides Mo6SxIy, where S-atoms substitute some of the I-atoms in the coordination sphere of Mo [35][36][37]. Therefore, the formation of [Mo6I12]n@SWNT observed in AC-HRTEM is a combined result of the knock-on effect of the e-beam and the confinement effect of the nanotube directing the growth of this unusual structure.…”

Section: Equationmentioning

confidence: 99%

Carbon Nanotubes as Electrically Active Nanoreactors for Multi-Step Inorganic Synthesis: Sequential Transformations of Molecules to Nanoclusters and Nanoclusters to Nanoribbons

et al. 2016

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In organic synthesis, the composition and structure of products are predetermined by the reaction conditions; however, the synthesis of well-defined inorganic nanostructures often presents a significant challenge yielding non-stoichiometric or polymorphic products. In this study, confinement in the nanoscale cavities of single-walled carbon nanotubes (SWNT) provides a new approach for multi-step inorganic synthesis where sequential chemical transformations take place within the same nanotube. In the first step, SWNT donate electrons to the reactant iodine molecules (I2) transforming them to iodide anions (I -). These then react with metal hexacarbonyls (M(CO)6, M = Mo or W) in the next step yielding anionic nanoclusters [M6I14] 2-, the size and composition of which are strictly dictated by the nanotube cavity, as demonstrated by aberration corrected high resolution transmission electron microscopy (AC-HRTEM), scanning transmission electron microscopy (STEM) and energy dispersive X-ray (EDX) spectroscopy. Atoms in the nanoclusters [M6I14] 2-are arranged in a perfect octahedral geometry and can engage in further chemical reactions within the nanotube, either reacting with each other leading to a new polymeric phase of molybdenum iodide [Mo6I12]n, or with hydrogen sulphide gas giving rise to nanoribbons of molybdenum/tungsten disulphide [MS2]n in the third step of the synthesis. Electron microscopy measurements demonstrate that the products of the multi-step inorganic transformations are precisely controlled by the SWNT nanoreactor, with complementary Raman spectroscopy revealing the remarkable property of SWNT to act as a reservoir of electrons during the chemical transformation. The electron transfer from the hostnanotube to the reacting guest-molecules is essential for stabilising the anionic metal iodide 2 nanoclusters and for their further transformation to metal disulphide nanoribbons synthesised in the nanotubes in high yield.Keywords: Carbon Nanotube, Charge Transfer, Nanoparticle, Nanoreactor, Nanoribbon Single-walled carbon nanotubes (SWNT) are among the most effective and universal containers for molecules. Provided that the internal diameter of the host-nanotube is wider than the critical diameter of the guest-molecule, the insertion of molecules into SWNT is spontaneous and, in some cases, such as fullerenes and their derivatives, irreversible due to the ubiquitous van der Waals forces dominating the host guest interactions between the nanotube and molecules [1]. Fullerenes [2,3] or organic molecules [4][5][6][7][8][9][10] encapsulated in SWNT can then be triggered to react inside the nanotube to form unusual oligomers and polymers [11][12][13], graphene nanoribbons [14][15][16], nanotubes [8,17] or extraordinary molecular nanodiamonds [9]. These examples clearly demonstrate the use of SWNT as nanoscale chemical reactors, where the structure of the macromolecular product can be precisely controlled by spatial confinement of the reactions in the nanotube channel.In contrast to organic molecules,...

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“…Because of favorable combinations of covalency and oxidation/reduction potentials, the activation of molecular oxygen by its coordination to one or two supported ͑i.e., ligated͒ Cu͑I͒ ions is common to a number of biological and inorganic catalytic processes. [26][27][28][29][30][31][32][33][34][35][36][37][38][39] In the case of monocopper species LCuO 2 , where L is a general ligand or ligands, one possible oxidation state that may be assigned to the complex is LCu͑II͒O 2 ͑−͒; thus, the copper atom has been oxidized by one electron and the O 2 fragment is formally a superoxide radical anion. Similarly, in the case of dicopper species ͑LCu͒ 2 O 2 , one possible oxidation state of the complex is formally ͓LCu͑II͔͒ 2 ͓͑O 2 ͒͑2−͔͒; in this instance, each copper atom has been oxidized by one electron and the O 2 fragment is formally a peroxide dianion.…”

Section: Application To Supported Cuo 2 and Cu 2 O 2 Systemsmentioning

confidence: 99%

The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems

Malmqvist

Pierloot

Shahi

et al. 2008

The Journal of Chemical Physics

491

532

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A multireference second-order perturbation theory using a restricted active space self-consistent field wave function as reference ͑RASPT2/RASSCF͒ is described. This model is particularly effective for cases where a chemical system requires a balanced orbital active space that is too large to be addressed by the complete active space self-consistent field model with or without second-order perturbation theory ͑CASPT2 or CASSCF, respectively͒. Rather than permitting all possible electronic configurations of the electrons in the active space to appear in the reference wave function, certain orbitals are sequestered into two subspaces that permit a maximum number of occupations or holes, respectively, in any given configuration, thereby reducing the total number of possible configurations. Subsequent second-order perturbation theory captures additional dynamical correlation effects. Applications of the theory to the electronic structure of complexes involved in the activation of molecular oxygen by mono-and binuclear copper complexes are presented. In the mononuclear case, RASPT2 and CASPT2 provide very similar results. In the binuclear cases, however, only RASPT2 proves quantitatively useful, owing to the very large size of the necessary active space.

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Binding and Activation of Molecular Oxygen by Copper Complexes

Cited by 216 publications

References 274 publications

Mechanistic aspects of oxidation on L-tyrosine by diperiodatocuprate(III) complex in alkali media: a kinetic model

Mechanistic aspects of oxidation on L-tyrosine by diperiodatocuprate(III) complex in alkali media: a kinetic model

Carbon Nanotubes as Electrically Active Nanoreactors for Multi-Step Inorganic Synthesis: Sequential Transformations of Molecules to Nanoclusters and Nanoclusters to Nanoribbons

The restricted active space followed by second-order perturbation theory method: Theory and application to the study of CuO2 and Cu2O2 systems

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