The transition metal-carbonyl bond

Davidson, Ernest R.; Kunze, Kathryn L.; Machado, Francisco B. C.; Chakravorty, Subhas J.

doi:10.1021/ar00036a004

Cited by 121 publications

(105 citation statements)

References 58 publications

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“…The latter effect strengthens the metal-carbon bond and accounts for the predicted trend of increasing stability of hexacarbonyls along the group 6. Despite controversial discussions in [10], a later analysis of the binding in W(CO) 6 confirmed that thebackbonding accounts for about 60% of the orbital-driven binding, whereas the sum of sigma donation accounts for 40% of which again 80% are attributed to the sigma donation into the orbital ( molecular orbital) [11,12].…”

Section: Introductionmentioning

confidence: 99%

Decomposition studies of group 6 hexacarbonyl complexes. Part 2: Modelling of the decomposition process

2016

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Abstract:The decomposition behavior of group 6 metal hexacarbonyl complexes (M(CO) 6 ) in a tubular flow reactor is simulated. A microscopic Monte-Carlo based model is presented for assessing the first bond dissociation enthalpy of M(CO) 6 complexes. The suggested approach superimposes a microscopic model of gas adsorption chromatography with a first-order heterogeneous decomposition model. The experimental data on the decomposition of Mo(CO) 6 and W(CO) 6 are successfully simulated by introducing available thermodynamic data. Thermodynamic data predicted by relativistic density functional theory is used in our model to deduce the most probable experimental behavior of the corresponding Sg carbonyl complex. Thus, the design of a chemical experiment with Sg(CO) 6 is suggested, which is sensitive to benchmark our theoretical understanding of the bond stability in carbonyl compounds of the heaviest elements.

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Section: Introductionmentioning

confidence: 99%

Decomposition studies of group 6 hexacarbonyl complexes. Part 2: Modelling of the decomposition process

2016

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“…They have been widely studied as a prototype for understanding the chemical bonds of organometallic compounds 18,19 or a model for adsorption of carbon monoxide on metal surfaces. 20 On the ionizations in the valence region, He I and He II PES, 21 x-ray PES ͑XPES͒, 22 synchrotron radiation PES ͑SRPES͒, 23,24 and PIES ͑Ref.…”

Section: Introductionmentioning

confidence: 99%

Valence ionization spectra of group six metal hexacarbonyls studied by the symmetry-adapted cluster-configuration interaction method

Fukuda

Hayaki

Nakatsuji

2009

The Journal of Chemical Physics

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The valence ionization spectra up to 20 eV of group six metal carbonyls, chromium hexacarbonyl, molybdenum hexacarbonyl, and tungsten hexacarbonyl were studied by the symmetry-adapted cluster-configuration interaction (SAC-CI) method. The assignments of the spectra are given based on reliable SAC-CI calculations. The relativistic effects including the spin-orbit effects are important for the ionization spectrum of W(CO)(6). The relation between the metal-CO distance and ionization energies was examined. The lowest ionization energies of the three metal carbonyls are approximately the same because of the energy dependence of the metal-CO length and relativistic effects. In Cr(CO)(6), the Cr-CO interaction significantly increases the lowest ionization energy in comparison with Mo(CO)(6) and W(CO)(6) because of the relatively short metal-CO bond length. The relativistic effect reduces the lowest ionization energy of W(CO)(6) because the effective core potential of 5d electrons is more efficiently screened as a result of the relativistic contraction of the inner electrons.

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“…The same conclusion has been drawn in an analysis of metal ± ligand bonding in carbonyl complexes. [37] The ). [1] Substitution of the hydrogen atom in 16 by fluorine lowers the strength of the W ± carbyne bond significantly as seen in the Fischer complexes 4 and 6.…”

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confidence: 99%

Structure and Bonding of Low‐Valent (Fischer‐Type) and High‐Valent (Schrock‐Type) Transition Metal Carbyne Complexes

Vyboishchikov

Frenking

1998

Chemistry A European J

101

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Quantum mechanical ab initio calculations are reported for 13 lowvalent (Fischer-type) and 13 high-valent (Schrock-type) tungsten carbyne complexes. The geometries have been optimized at the HF and MP2 levels of theory with relativistic effective core potentials for the heavy atoms with valence basis sets of DZP quality. Tungsten ± carbyne bond dissociation energies are predicted at CCSD(T) with MP2 optimized geometries. The electronic structure of the complexes and the metal ± ligand bonding have been analyzed with the help of the NBO method, the topological analysis of the electron-density distribution and the CDA method. The L n W ± CR bonds of the Fischer and Schrock carbyne complexes are much stronger than those of related carbene complexes. The strength of the L n W ± CR bond is strongly influenced by the nature of R.

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The transition metal-carbonyl bond

Cited by 121 publications

References 58 publications

Decomposition studies of group 6 hexacarbonyl complexes. Part 2: Modelling of the decomposition process

Decomposition studies of group 6 hexacarbonyl complexes. Part 2: Modelling of the decomposition process

Valence ionization spectra of group six metal hexacarbonyls studied by the symmetry-adapted cluster-configuration interaction method

Structure and Bonding of Low‐Valent (Fischer‐Type) and High‐Valent (Schrock‐Type) Transition Metal Carbyne Complexes

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