Thermal stability and kinetic lability of the metal carbonyl bond. A theoretical study on M(CO)6 (M = chromium, molybdenum, tungsten), M(CO)5 (M = iron, ruthenium, osmium), and M(CO)4 (M = nickel, palladium, platinum)

Ziegler, Tom; Tschinke, Vincenzo; Ursenbach, Charles P.

doi:10.1021/ja00250a013

Cited by 192 publications

(89 citation statements)

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“…The order for the FBDES obtained here is in agreement with that found in the earlier DFT study [22]. However, the absolute values from the earlier DFT study are smaller than those reported in Table 111.…”

Section: First Bond Dissociation Energiessupporting

confidence: 91%

“…A common feature of most practical implementations is the expansion of the orbitals ql into a basis set { xP}: (22) In the ADF program, primitive Slater-type orbitals (STOS) are used as basis functions. Each STO is centered at one particular nucleus (LCAO expansion).…”

Section: The Quasi-relativistic Energy Gradientmentioning

confidence: 99%

“…Kinetic estimates of the FBDES among the pentacarbonyls are available for all three members of the iron triad, whereas gas-phase data is restricted to DFT has also been employed in calculations on FBDES of organometallic compounds. Seven years ago, Ziegler et al [22] reported a DFT calculation on M(CO), (M = Ni, Pd, Pt), M(CO), (M = Fe, Ru, Os), and M(CO), (M = Cr, Mo, W), based on experimental geometries and the local density approximation (LDA) [23] …”

Section: Motivation and Previous Studiesmentioning

confidence: 99%

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The implementation of analytical energy gradients based on a quasi‐relativistic density functional method: The application to metal carbonyls

Schreckenbach

Ziegler

1995

Int J of Quantum Chemistry

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Section: First Bond Dissociation Energiessupporting

confidence: 91%

Section: The Quasi-relativistic Energy Gradientmentioning

confidence: 99%

Section: Motivation and Previous Studiesmentioning

confidence: 99%

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The implementation of analytical energy gradients based on a quasi‐relativistic density functional method: The application to metal carbonyls

Schreckenbach

Ziegler

1995

Int J of Quantum Chemistry

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“…Because the pyrolysis of molybdenum carbonyl will increase the molar number, from 1 to 1x, of the gases in the system, for instance. [12] higher pressure does not favor the pyrolysis reaction moving rightward. Besides, the diffusion is inversely proportional to coating pressure, as indicated in Eqn [8].…”

Section: Characterizationmentioning

confidence: 92%

“…The carbonyl gas molecules are then pyrolyzed thermally as the gas stream flows into the reaction chamber with temperatures above 175°C. The researchers [11][12][13][14][15][16][17][18] have determined the dissociation kinetics and energies of pure Mo and Cr carbonyls and their admixtures. The pyrolysis occurs on the breaking of metal/(CO) bonds, and is classified as a first-order reaction.…”

Section: Pyrolysis Of Metallic Carbonylsmentioning

confidence: 99%

Processing and properties of (Mo,Cr) oxycarbides from MOCVD

Wei

1998

Appl. Organometal. Chem.

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A review of the coating kinetics of molybdenum and chromium oxycarbides and a study on the properties of deposited films are reported. Molybdenum carbonyl, chromium carbonyl and their mixture were used to prepare coatings at temperatures between 170 and 450 °C on SS304 or SiC substrates by a process of metal‐organic chemical vapor deposition (MOCVD). The processing parameters of the coatings, such as the evaporation of precursors, coating pressure and temperature, are discussed along with the coating rates, compositions and other microstructural information, so to reveal the kinetics of the coating process on two different substrates. In addition, the chemical composition, crystalline phases and microstructure of the coatings obtained in various conditions are presented with the evidence interpreted by various electron‐microscopic and spectroscopic techniques, including XRD, EDS, EPMA and XPS. The dependence of some properties, such as hardness, adhesive strength and corrosive resistance of the coatings on SS 304, on their composition and the deposited phases, i.e. as a function of coating temperature and pressure, is reviewed. © 1998 John Wiley & Sons, Ltd.

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Molecular structure and binding energies of monosubstituted hexacarbonyls of chromium, molybdenum, and tungsten: Relativistic density functional study

Wllen

1997

J. Comput. Chem.

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Relativistic density functional calculations have been carried out for the group VI transition metal carbonyls M(CO)5L (M=Cr, Mo, W; L=OH2, NH3, PH3, PMe3, N2, CO, OC (isocarbonyl), CS, CH2, CF2, CCl2, NO+). The optimized molecular structures and M(SINGLE BOND)L bond dissociation energies, as well as the metal–carbonyl bond energy of the trans CO group, have been calculated. Besides the marked dependence of the trans M(SINGLE BOND)CO bond length on the type of ligand L, such an effect on the that bond energy is also observed. For the chromium compounds, the trans Cr(SINGLE BOND)CO bond length varies from 184 to 199 pm and its bond energy from 242 to 150 kJ/mol. For the molybdenum compounds, the range is 197 to 216 pm and 253 to 128 kJ/mol and, for tungsten, 198 to 214 pm and 293 to 159 kJ/mol. The observed trends can be explained with the π acceptor strength of the L ligand. © 1997 John Wiley & Sons, Inc. J Comput Chem 18: 1985–1992, 1997

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Thermal stability and kinetic lability of the metal carbonyl bond. A theoretical study on M(CO)6 (M = chromium, molybdenum, tungsten), M(CO)5 (M = iron, ruthenium, osmium), and M(CO)4 (M = nickel, palladium, platinum)

Cited by 192 publications

References 0 publications

The implementation of analytical energy gradients based on a quasi‐relativistic density functional method: The application to metal carbonyls

The implementation of analytical energy gradients based on a quasi‐relativistic density functional method: The application to metal carbonyls

Processing and properties of (Mo,Cr) oxycarbides from MOCVD

Molecular structure and binding energies of monosubstituted hexacarbonyls of chromium, molybdenum, and tungsten: Relativistic density functional study

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