Reactivity of Copper(I) Complexes Towards Dioxygen

Schindler, Siegfried

doi:10.1002/1099-0682(200011)2000:11<2311::aid-ejic2311>3.3.co;2-z

Cited by 12 publications

(11 citation statements)

References 65 publications

(101 reference statements)

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“…These include tris(2-pyridylmethyl)amine (TMPA) and analogues or derivatives. 9,30 This is also true for the classic tripodal tren ligand, tris(2-aminoethyl)amine; tren derivatives and copper–dioxygen chemistry have been especially studied by the research groups of Schindler 21,37–39 and Suzuki, 40 providing extensive insights into ligand–Cu I /O 2 reactivity and kinetics, as well as formation of Cu II –(O 2 •− ) species (with an as-mentioned X-ray structure), 21 and dicopper(II)–peroxo species, the latter also with an X-ray structure known from Suzuki. 40 …”

Section: Introductionmentioning

confidence: 99%

Spectroscopic and computational characterization of CuII–OOR (R = H or cumyl) complexes bearing a Me6-tren ligand

et al. 2011

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A copper(II)–hydroperoxo complex, [Cu(Me6-tren)(OOH)]+ (2), and a copper(II)–cumylperoxo complex, [Cu(Me6-tren)(OOC(CH3)2Ph)]+ (3), were synthesized by reacting [Cu(Me6-tren)(CH3CN)]2+ (1) with H2O2 and cumyl-OOH, respectively, in the presence of triethylamine. These intermediates, 2 and 3, were successfully characterized by various physicochemical methods such as UV-vis, ESI-MS, resonance Raman and EPR spectroscopies, leading us to propose structures of the Cu(II)–OOR species with a trigonal-bipyramidal geometry. Density functional theory (DFT) calculations provided geometric and electronic configurations of 2 and 3, showing trigonal bipyramidal copper(II)–OOR geometries. These copper(II)–hydroperoxo and –cumylperoxo complexes were inactive in electrophilic and nucleophilic oxidation reactions.

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Section: Introductionmentioning

confidence: 99%

Spectroscopic and computational characterization of CuII–OOR (R = H or cumyl) complexes bearing a Me6-tren ligand

et al. 2011

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“…[1,2] From these findings, it has been inferred [3,4] that Cu II -O-Cu II or Cu II -O-Cu III entities are perhaps the most likely candidates for the methane-oxidizing species in the active site of particulate methanemonoxygenase, [5,6] which also contains a dicopper unit. [8][9][10][11][12] However, compounds containing copper(I) in siloxide coordination spheres, which -with regard to the abovementioned zeolite work -may be regarded as surface mimics are rather rare. Subsequent treatment of these complexes with O 2 often led to functional systems that oxidized the ligand systems, or even external substrates, in a biomimetic fashion.…”

Section: Introductionmentioning

confidence: 99%

Copper(I) Siloxides – Aggregated Solid‐State Structures, Cu–Cu Interactions and Dynamic Solution Behavior

2012

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Reaction of the siloxane‐diols HO(Ph2SiO)2H, 1,1,3,3‐tetraphenyldisiloxane‐1,3‐diol (L1H2), HO(iPr2SiO)2H, 1,1,3,3‐tetraisopropyldisiloxane‐1,3‐diol (L2H2), and HO(Ph2SiO)3H, 1,1,3,3,5,5‐hexaphenyltrisiloxane‐1,5‐diol (L3H2) with two equivalents of CunMesn led to octanuclear compounds [Cu8L14] (1), [Cu8L24] (2), and [Cu8L12L*2] [L* = O(Ph2SiO)4] (3), which were characterized by single‐crystal X‐ray diffraction analysis as well as by solution NMR spectroscopy. The crystal structures revealed that all the compounds are composed of Cu4O4 moieties featuring short Cu–Cu distances that can be discussed in terms of cuprophilic interactions. Two such units are linked via four disiloxane units in 1 and 2, in 3 they are connected by two equivalents of (L1)2–. Formation of 3 required disproportion of a trisiloxane‐1,5‐diolate to give a disiloxane‐1,3‐diolate and a tetrasiloxane‐1,7‐diolate, and thus indicates that siloxane units are not inert under the synthetic conditions employed. NMR spectroscopic investigations of the structure of 1 in solution revealed an equilibrium, presumably with [Cu4L22] fragments. Crystallization of a structural isomer of 3 indicates a shallow potential energy surface for this compound.

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“…Despite these complications, copper catalysis has been employed successfully for decades in a variety of methods including carbon–heteroatom bond formation (5), carbon–carbon bond formation (6), oxidative processes (7, 8), and, most recently, dipolar cycloadditions (Fig. 1A, (9-12)).…”

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confidence: 99%

Direct Evidence of a Dinuclear Copper Intermediate in Cu(I)-Catalyzed Azide-Alkyne Cycloadditions

Worrell

Malik

Fokin

2013

Science

731

564

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The copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) has become a commonly employed method for the synthesis of complex molecular architectures under challenging conditions. Despite the widespread use of copper-catalyzed cycloaddition reactions, the mechanism of these processes has remained difficult to establish due to the involvement of multiple equilibria between several reactive intermediates. Real-time monitoring of a representative cycloaddition process via heat flow reaction calorimetry revealed that monomeric copper acetylide complexes are not reactive toward organic azides unless an exogenous copper catalyst is added. Furthermore, crossover experiments with an isotopically enriched exogenous copper source illustrated the stepwise nature of the C–N bond-forming events and the equivalence of the two copper atoms within the cycloaddition steps.

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Reactivity of Copper(I) Complexes Towards Dioxygen

Cited by 12 publications

References 65 publications

Spectroscopic and computational characterization of CuII–OOR (R = H or cumyl) complexes bearing a Me6-tren ligand

Spectroscopic and computational characterization of CuII–OOR (R = H or cumyl) complexes bearing a Me6-tren ligand

Copper(I) Siloxides – Aggregated Solid‐State Structures, Cu–Cu Interactions and Dynamic Solution Behavior

Direct Evidence of a Dinuclear Copper Intermediate in Cu(I)-Catalyzed Azide-Alkyne Cycloadditions

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