Formaldehyde activation by Cu(I) and Ag(I) sites in ZSM-5: ETS-NOCV analysis of charge transfer processes

Brocławik, Ewa; Załucka, J.; Kozyra, Paweł; Mitoraj, Mariusz P.; Dátka, Jerzy

doi:10.1016/j.cattod.2010.08.020

Cited by 20 publications

(32 citation statements)

References 43 publications

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“…As we have shown in this contribution and postulated previously for other molecules [28][29][30], in order to fully understand the nature of electron transfer between the active site and a ligand total differential density must be resolved into independent electron transfer channels since various symmetries and transfer directions may coexist, either corroborating or opposing activation. All the more for the NO ligand, which due to its specific open-shell electronic structure is a special case, and thus requires NOCV analysis with spin-resolution and careful selection of initial fragment density, prerequisite for defining proper deformation density.…”

Section: Discussionmentioning

confidence: 73%

“…On the other hand, it was suggested, after analyzing atomic population changes upon ligand adsorption on a bare cation versus the cation embedded in a model environment that the unusual catalytic activity of transition-metal exchanged zeolites should be due to the activation of the transition-metal ion by the zeolite framework which functions as a specific ligand. Theoretical studies devoted to the interaction of small ligands with multiple bonds bound by zeolitic sites clearly indicated that the charge flow upon adsorption involves several transfer channels, strongly dependent on a zeolite framework type and a cation position [23,[26][27][28][29][30]. Populations within orbital resolution and devised selection schemes, frequently supported by topological analyses of electron density, were able to discriminate distinct electron transfers for a model metal-ligand bond [23,26,27].…”

Section: Introductionmentioning

confidence: 99%

“…This method may also serve to follow changes in electron transfer processes imposed by metal environment. ETS-NOCV methodology has already been applied by us with flexible strategy of dividing multicomponent zeolitic active site into fragments and shown to perform well for copper (I) sites interacting with closed-shell ligands like ethene, ethyne, benzene, or formaldehyde [28][29][30]35].…”

Section: Introductionmentioning

confidence: 99%

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On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites

et al. 2012

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Electronic factors essential for NO activation by Cu(I) sites in zeolites are investigated within spin-resolved analysis of electron transfer channels (natural orbitals for chemical valence). NOCV analysis is performed for three DFT-optimized models of Cu(I)-NO site in ZSM-5: [CuNO] ? , (T1)CuNO, and (M7)CuNO. NO as a non-innocent, openshell ligand reveals significant differences between independent deformation density components for a and b spins. Four distinct components are identified: (i) unpaired electron donation from NO p k * antibonding orbital to Cu s,d ; (ii) backdonation from copper d yz to p \ * antibonding orbital; (iii) donation from occupied p k and Cu d xz to bonding region, and (iv) donation from nitrogen lone-pair to Cu s,d . Channel (i), corresponding to one-electron bond, shows-up solely for spin majority and is effective only in the interaction of NO with naked Cu ? . Channel (ii) dominates for models b and c: it strongly activates NO bond by populating antibonding p* orbital and weakens the N-O bond in contrast to channel (i), depopulating the antibonding orbital and strengthening N-O bond. This picture perfectly agrees with IR experiment: interaction with naked Cu ? imposes small blue-shift of NO stretching frequency while it becomes strongly red-shifted for Cu(I) site in ZSM-5 due to enhanced backdonation.

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Section: Discussionmentioning

confidence: 73%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites

et al. 2012

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“…ETS‐NOCV calculations were performed by employing the B3LYP‐D3(BJ)/TZ2P level of theory as implemented in the Amsterdam density functional (ADF) . The relativistic effects of gold were accounted for by the zero‐order regular approximation (ZORA) .…”

Section: Methodsmentioning

confidence: 99%

Understanding Thermal and Photochemical Aryl–Aryl Cross‐Coupling by the Au^I/Au^III Redox Couple

Bhattacharjee

Datta

2018

Chemistry A European J

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Systematic mechanistic investigations of the gold(I)/gold(III) redox-controlled aryl-aryl cross-coupling reaction have been performed by using both a thermal and photochemical approach. Electron-deficient and electron-rich arenes were considered as the coupling partners of the reaction. Based on transition-state modeling and distortion/interaction analyses, it is shown that Au prefers to react with electron-deficient arenes whereas Au likes to activate electron-rich arenes. This orthogonal reactivity of gold makes it an efficient catalyst for the aryl-aryl cross-coupling reaction. The crucial role of the carboxylate ligand in the reaction has been elucidated through analysis of the transition states. It is shown that due to the presence of two coordination sites, a carboxylate ligand can stabilize the transition state more efficiently than other monodentate ligands such as chloride (Cl ). Moreover, carbon-boron transmetalation is shown to be favorable over direct C-H metalation, hence reactions initialized by C-B transmetalation are expected to be much faster and selective. Additionally, a dual photoredox/gold catalyst was employed to access the Au /Au catalytic cycle for the cross-coupling reaction. [Ru(bpy) ] was used as the photoredox catalyst for the reaction, which, on excitation, transfers an electron to one of the coupling partners, namely a diazonium salt (ArN ), and initializes the cycle.

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“…For example iron, cobalt, vanadium, and titanium‐exchanged zeolites have been synthesized and characterized. Owing to the growing importance of transition‐metal‐exchanged zeolites, a large number of theoretical studies concerning transition‐metal‐exchanged zeolites have appeared …”

Section: Introductionmentioning

confidence: 99%

Exploring Scaling Relations for Chemisorption Energies on Transition‐Metal‐Exchanged Zeolites ZSM‐22 and ZSM‐5

et al. 2016

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Copper exchange on all the different T sites of ZSM‐22 and ZSM‐5 is considered and the chemisorption energies of dioxygen, OH, and O species are studied. We show that for different T sites the adsorption energies vary significantly. The oxygen adsorption energy on copper‐exchanged zeolites is quite similar to those of the most selective catalysts for oxidation reactions, that is, Ag and Au surfaces. The chemisorption energies of oxygen, carbon‐, and nitrogen‐containing species on different transition metals exchanged in ZSM‐22 are also investigated. The study covers three different oxidation states, that is, 1+, 2+, and 3+ for the transition‐metal exchanges. Scaling relations are presented for the corresponding species. Chemisorption of O scales with chemisorption of OH for all three considered exchanges, whereas there are essentially rough correlations for NH2 and N as well as CH3 and C.

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Formaldehyde activation by Cu(I) and Ag(I) sites in ZSM-5: ETS-NOCV analysis of charge transfer processes

Cited by 20 publications

References 43 publications

On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites

On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites

Understanding Thermal and Photochemical Aryl–Aryl Cross‐Coupling by the Au^I/Au^III Redox Couple

Exploring Scaling Relations for Chemisorption Energies on Transition‐Metal‐Exchanged Zeolites ZSM‐22 and ZSM‐5

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Formaldehyde activation by Cu(I) and Ag(I) sites in ZSM-5: ETS-NOCV analysis of charge transfer processes

Cited by 20 publications

References 43 publications

On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites

On the nature of spin- and orbital-resolved Cu+–NO charge transfer in the gas phase and at Cu(I) sites in zeolites

Understanding Thermal and Photochemical Aryl–Aryl Cross‐Coupling by the AuI/AuIII Redox Couple

Exploring Scaling Relations for Chemisorption Energies on Transition‐Metal‐Exchanged Zeolites ZSM‐22 and ZSM‐5

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Understanding Thermal and Photochemical Aryl–Aryl Cross‐Coupling by the Au^I/Au^III Redox Couple