A copper-oxygen (Cu2-O2) complex.  Crystal structure and characterization of a reversible dioxygen binding system

Jacobson, Richard R.; Tyeklár, Zoltán; Farooq, Amjad; Karlin, Kenneth D.; Liu, Shuncheng.; Zubieta, Jon

doi:10.1021/ja00219a071

Cited by 388 publications

(361 citation statements)

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“…Because no dioxygen adduct from oxygenation in solution of a tetra-N-functionalized cyclam copper(i) complex has been characterized, we have to rely on comparisons with other tetradendate systems described in the literature. In this regard, the aliphatic tetramine ligands derived from tris(2-aminoethyl)amine (tren) [7,77] or tris(2-pyridylmethyl)-A C H T U N G T R E N N U N G amine (tmpa) [5,78,79] can be considered as good models for the immobilized cyclams, although these are not macrocyclic derivatives. The average Cu···O distance is quite similar (1.86 AE 0.01 ) to the Cu À O bond lengths for copper dioxygen complexes characterized by X-ray crystallography.…”

Section: Resultsmentioning

confidence: 99%

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Brandès

David

Suspène

et al. 2007

Chemistry A European J

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We report the exceptional reactivity towards dioxygen of a nanostructured organic-inorganic hybrid material due to the confinement of copper cyclam within a silica matrix. The key step is the metalation reaction of the ligand, which can occur before or after xerogel formation through the sol-gel process. The incorporation of a Cu(II) center into the material after xerogel formation leads to a bridged Cu(I)/Cu(II) mixed-valence dinuclear species. This complex exhibits a very high affinity towards dioxygen, attributable to auto-organization of the active species in the solid. The remarkable properties of these copper complexes in the silica matrix demonstrate a high cooperative effect for O(2) adsorption; this is induced by close confinement of the two copper ions leading to end-on mu-eta(1):eta(1)-peroxodicopper(II) complexes. The anisotropic packing of the tetraazamacrocycle in a lamellar structure induces an exceptional reactivity of these copper complexes. We show for the first time that the organic-inorganic environment of copper complexes in a silica matrix fully model the protecting role of protein in metalloenzymes. For the first time an oxygenated dicopper(II) complex can be isolated in a stable form at room temperature, and the reduced Cu(2) (I,I) species can be regenerated after several adsorption-desorption cycles. These data also demonstrate that the coordination scheme and reactivity of the copper cyclams within the solid are quite different from that observed in solution.

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Section: Resultsmentioning

confidence: 99%

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Brandès

David

Suspène

et al. 2007

Chemistry A European J

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“…12,19 Best characterized experimentally (because they have been observed for many different supporting ligand sets) are the side-on µ-η 2 :η 2 peroxo and the bis(µ-oxo). The trans end-on µ-η 1 :η 1 peroxo motif was first described by Jacobson et al 20 This binding mode is preferred when the copper atoms are supported by tripodal tetradentate ligands, [21][22][23][24][25] although when such ligands become too sterically demanding for trigonal bipyramidal coordination of copper a preference for the bis(µ-oxo) motif with concomitant loss of two ligand-copper interactions has been documented. 26 Only rare examples of the other three cases shown in Figure 1 have been documented or proposed.…”

Section: Introductionmentioning

confidence: 99%

Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu₂O₂ Models

et al. 2006

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The relative energetics of µ-η 1 :η 1 (trans end-on) and µ-η 2 :η 2 (side-on) peroxo isomers of Cu 2 O 2 fragments supported by 0, 2, 4, and 6 ammonia ligands have been computed with various density functional, coupledcluster, and multiconfigurational protocols. There is substantial disagreement between the different levels for most cases, although completely renormalized coupled-cluster methods appear to offer the most reliable predictions. The significant biradical character of the end-on peroxo isomer proves problematic for the density functionals, while the demands on active space size and the need to account for interactions between different states in second-order perturbation theory prove challenging for the multireference treatments. In the latter case, it proved impossible to achieve any convincing convergence.

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“…This is the price to pay for the low computational scaling with the number of active orbitals of the current algorithm. 36,39,[65][66][67][68][69][70][71][72][73][74] In the course of this work, a series of projected DMRG-SC-NEVPT2 calculations were conducted on "structure 7" from Ref. 74 that features an O-O bond distance of 1.60 Å.…”

Section: A the N 2 Moleculementioning

confidence: 99%

A projected approximation to strongly contracted N-electron valence perturbation theory for DMRG wavefunctions

Roemelt

Guo

Chan

2016

The Journal of Chemical Physics

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A novel approach to strongly contracted N-electron valence perturbation theory (SC-NEVPT2) as a means of describing dynamic electron correlation for quantum chemical density matrix renormalization group (DMRG) calculations is presented. In this approach the strongly contracted perturber functions are projected onto a renormalized Hilbert space. Compared to a straightforward implementation of SC-NEVPT2 with DMRG wavefunctions, the computational scaling and storage requirements are reduced. This favorable scaling opens up the possibility of calculations with larger active spaces. A specially designed renormalization scheme ensures that both the electronic ground state and the perturber functions are well represented in the renormalized Hilbert space.

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A copper-oxygen (Cu2-O2) complex. Crystal structure and characterization of a reversible dioxygen binding system

Cited by 388 publications

References 0 publications

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu₂O₂ Models

A projected approximation to strongly contracted N-electron valence perturbation theory for DMRG wavefunctions

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A copper-oxygen (Cu2-O2) complex. Crystal structure and characterization of a reversible dioxygen binding system

Cited by 388 publications

References 0 publications

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Exceptional Affinity of Nanostructured Organic–Inorganic Hybrid Materials towards Dioxygen: Confinement Effect of Copper Complexes

Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu2O2 Models

A projected approximation to strongly contracted N-electron valence perturbation theory for DMRG wavefunctions

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Theoretical Characterization of End-On and Side-On Peroxide Coordination in Ligated Cu₂O₂ Models