On the existence of novel nitrides and oxides of copper; CuN, CuO2 and CuNO

Sülzle, Detlev; Schwarz, Helmut; Moock, Klaus H.; Terlouw, Johan K.

doi:10.1016/0168-1176(91)85039-o

Cited by 37 publications

(33 citation statements)

References 32 publications

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“…The situation is even more involved for the complex with the nitric oxide (see Figure 3 and Table 4). Schwarz and coworkers 19 have presented some evidence for the existence of the neutral CuNO species in the gas phase. They suggested that the observed species could correspond either to a single side-on complex or to the different end-on complexes (CuNO and CuON) engaged in a very fast interconversion.…”

Section: Resultsmentioning

confidence: 98%

“…The structure and energetics of neutral CuO 2 are well documented experimentally. [17][18][19]78,80 In particular, Mitchell has determined that the bond dissociation energy is 15 ( 5 kcal/mol, 17 while EPR experiments 18,19 have been interpreted in terms of an end-on coordination (see Figure 3). On the other hand, MCPF and CCSD[T] computations 43 Table 3 and BSSE (0.5 kcal/ mol).…”

Section: Resultsmentioning

confidence: 98%

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Validation of Hybrid Density Functional/Hartree−Fock Approaches for the Study of Homogeneous Catalysis

Barone

Adamo

1996

J. Phys. Chem.

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The potentialities of a hybrid density functional/Hartree-Fock approach in the study of homogeneous catalysis have been investigated by a comprehensive study of binary adducts of copper atom characterized by strong (Cu 2 , CuH, CuCH 3 ) or weak (CuCO, CuNO, CuO 2 , CuC 2 H 2 ) metal-ligand interactions. The results confirm that this approach describes with good accuracy several properties of transition metal complexes, giving in particular binding energies close to the best available post-Hartree-Fock and experimental results. Besides the reasonable computation times, the possibility of avoiding high angular momentum basis functions, and the negligible basis set superposition error, the strength of hybrid approaches is their remarkably constant accuracy for closed-and open-shell systems and for strong covalent or weak donor-acceptor interactions. Furthermore, the ease of interpretation of single-determinant methods is retained. This allows the use of powerful energy decomposition tools for gaining further insight into the origin of different bonding patterns.

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Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 98%

Validation of Hybrid Density Functional/Hartree−Fock Approaches for the Study of Homogeneous Catalysis

Barone

Adamo

1996

J. Phys. Chem.

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“…The potential-energy surface of neutral Cu(O 2 ) is extremely¯at, however, and a de®nitive assignment as either structure I or II cannot be made with the information available [103]. For the cationic species, experimental evidence for structure III has been provided [105], and the co-existence of isomeric Cu(O 2 )…”

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confidence: 97%

Characterization, Orbital Description, and Reactivity Patterns of Transition-Metal Oxo Species in the Gas Phase

Schröder

Schwarz

Shaik

2000

Structure and Bonding

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131

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Metal-oxo and -peroxo species play key roles in catalytic oxidations using transition metals. This contribution addresses gas-phase studies of diatomic metal-oxo species and their properties which turn out to be of prime importance for the understanding of the observed reactivity patterns. A second topic concerns higher transition-metal oxides such as di-and trioxides. For these species there exists a structural dichotomy with the corresponding dioxygen complexes, e.g., MO 2 2 3 M(O 2 ). Most of the metal-based oxidations described involve crossings between surfaces of different spin as crucial steps, and the violation of spin conservation is proposed to determine the reactivity of the late transition-metal oxides. The ability of transition metals to mediate surface crossings via spin-orbit coupling is introduced as a key aspect in oxidation catalysis which has as yet not been fully appreciated. It is further outlined how these fundamental properties may relate to the properties of metal-oxo catalysts in the condensed phase.

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“…[7][8][9] Ground state Cu atom forms a molecular complex with O 2 , which takes on a bent CuOO ͑C s ͒ structure. [10][11][12] Upon photolysis of a Cu/O 2 matrix, a new form of CuO 2 is formed with distinct spectroscopic characteristics that are different from that of the Cu͑O 2 ͒ complex.…”

mentioning

confidence: 99%

“…[10][11][12] However, there are few studies on the copper dioxide molecule, 9,13 and its structure is not firmly established. The electronic structure and low-lying excited states for both isomers are not well known.…”

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confidence: 99%

Two isomers of CuO2: The Cu(O2) complex and the copper dioxide

Desai

Wang

1995

The Journal of Chemical Physics

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Photoelectron spectroscopy of CuO−2 has been studied at three detachment wavelengths: 532 nm, 355 nm, and 266 nm. Vibrationally resolved spectra for two distinct isomers are observed: the Cu(O2) complex and the copper dioxide molecule. The Cu(O)2 complex has an electron affinity (EA) of 1.503 (10) eV with a ground state vibrational frequency of 530 (50) cm−1. Its first electronic excited state is 7400 (300) cm−1 above the ground state. The Cu(O2)− anion is also observed to undergo photodissociation to Cu−+O2 at both 532 nm and 355 nm detachment wavelengths. The copper dioxide molecule is found to have a high EA of 3.46 (4) eV. Three low-lying excited states are observed within 1 eV above the ground state. The first two excited states of the copper dioxide molecule both possess a totally symmetric vibrational frequency of 640 (60) cm−1.

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On the existence of novel nitrides and oxides of copper; CuN, CuO2 and CuNO

Cited by 37 publications

References 32 publications

Validation of Hybrid Density Functional/Hartree−Fock Approaches for the Study of Homogeneous Catalysis

Validation of Hybrid Density Functional/Hartree−Fock Approaches for the Study of Homogeneous Catalysis

Characterization, Orbital Description, and Reactivity Patterns of Transition-Metal Oxo Species in the Gas Phase

Two isomers of CuO2: The Cu(O2) complex and the copper dioxide

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