The effect of electron correlation on the metal-ligand interaction in iron pentacarbonyl (Fe(CO)5)

Luethi, Hans P.; Siegbahn, Per E. M.; Almloef, Jan

doi:10.1021/j100257a006

Cited by 73 publications

(26 citation statements)

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“…One well‐documented critical case is that of metal‐CO complexes. At the HF level, the metal‐CO distances are calculated to be too long (Lüthi, Siegbahn, & Almlöf, 1985; Barandiaran et al, 1986) indicating that electron‐correlation effects are very important. However, in a study on Cr(CO) 6 complexes carried out by Barnes, Liu, & Lindh (1993) it was found that the inclusion of electron‐correlation effects yield CrCO distances still too long as compared with the experimental values.…”

Section: Performance Of the Modelmentioning

confidence: 99%

Computational chemistry: A useful (sometimes mandatory) tool in mass spectrometry studies

Alcamı́¹,

Mó²,

Yáñez³

2001

Mass Spectrometry Reviews

170

144

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In this review, we present a brief summary of the theoretical methods most frequently used in gas-phase ion chemistry. In subsequent sections, the performance of these methods is analyzed, paying attention to the reliability of geometries, vibrational frequencies, energies, and entropies. The possible pathologies of the different methods, in the form of instabilities of the wave function or spin contamination problems, are discussed. Several examples are presented to illustrate the usefulness of ab initio or density functional theory (DFT) methods to predict the existence of elusive molecules and/or to characterize non-conventional structures, and to rationalize the charge redistributions normally associated with ion-molecule interactions and which result in bond-weakening or bond-reinforcement effects. Finally, the role of non-classical structures in ion-molecule interactions is also illustrated with different examples.

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Section: Performance Of the Modelmentioning

confidence: 99%

Computational chemistry: A useful (sometimes mandatory) tool in mass spectrometry studies

Alcamı́¹,

Mó²,

Yáñez³

2001

Mass Spectrometry Reviews

170

144

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show abstract

“…A correct treatment of the correlation has been shown to be crucial for the geometry of first-row open-shell transition metal complexes (Langhoff & Bauschlicher, 1988, Lüthi et al, 1985, and it turned out to be equally important also for zinc complexes. When the Zn-S bond lengths were optimised at the MP2 level, the Zn-S bond lengths decreased by 6.8 pm to 241.5 pm.…”

Section: Influence Of the Ligand Choice Basis Set And Correlation Omentioning

confidence: 99%

The coordination chemistry of the structural zinc ion in alcohol dehydrogenase studied by ab initio quantum chemical calculations

Ryde

1996

Eur Biophys J

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The coordination chemistry of the structural zinc ion in alcohol dehydrogenase studied by ab initio quantum chemical calculations General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights.• Users may download and print one copy of any publication from the public portal for the purpose of private study or research.• You may not further distribute the material or use it for any profit-making activity or commercial gain • You may freely distribute the URL identifying the publication in the public portal shown that all the four cysteine ligands are deprotonated in the enzyme, not only two of them as has been suggested. The Zn-S bond lengths are very sensitive to the theoretical treatment; in vacuum they are predicted to be 15 pm longer than in the crystal structure.Half of this discrepancy is due to electronic correlation, the rest can be attributed to screening of the negative sulphide charges by the enzyme, in particular by N-H … S hydrogen bonds. The potential surface is rather flat, so the large difference in geometry between the crystal and the vacuum structure corresponds to an energy change of less than 35 kJ/mole. The crystal bond lengths can be reproduced only with methods that accounts explicitly for the enzyme. A dielectric continuum model gives too long bond lengths, indicating that the enzyme solvates the coordination sphere better than water. Thus, the structural zinc ion can be used as a sensitive test of methods trying to model the surrounding medium in quantum chemical computations.3

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“…One of the ®rst persons to point out these diculties was Jan AlmloÈ f, to whom this issue of the journal is dedicated. In a set of careful studies, mainly on ferrocene [10±12] and iron pentacarbonyl [13], he showed, at a time when calculations on this size of systems was extremely dicult, that electron correlation is of fundamental importance for these systems and also that very large basis sets are required even for a qualitatively correct description of structures. The direct SCF technique [14], invented and developed by Jan AlmloÈ f, was used extensively in these studies.…”

Section: Introductionmentioning

confidence: 99%

A comparative study of high-spin manganese and iron complexes

Blomberg

Siegbahn

1997

Theoretical Chemistry Accounts: Theory, Computation, and Modeli

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Dierent metal complexes of the general form M(OH) n (H 2 O) 6±n have been studied for manganese and iron. Oxidation states considered for manganese are Mn(III), Mn(IV) and Mn(V) and for iron Fe(II), Fe(III) and Fe(IV). Oxygen containing ligands are used throughout with varying numbers of hydroxyl and water ligands. Some metal-oxo and some charged complexes were also studied. Large Jahn-Teller distortions were found for the Mn(III) and Fe(IV) complexes. Consequences of these distortions are that water ligands have to be placed along the weak JT-axis and that ®ve-coordination by a loss of one of these water ligands is quite competitive with six-coordination in particular for manganese. For Fe(II) and Fe(III) lower coordinations than six are preferred due to the presence of two repulsive e g electrons. For the metal-oxo complexes ®ve-coordination is also preferred due to the strong trans eect from the oxo ligand. All complexes studied have high-spin ground states. An interesting eect is that the spin is much more delocalized on the ligands for the iron complexes than for the manganese complexes. This eect, which is chemically important for certain iron enzymes, is rationalized by the large number of 3d electrons on iron. For manganese with only ®ve 3d electrons no spin delocalization is needed to obtain the proper high-spin states.

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The effect of electron correlation on the metal-ligand interaction in iron pentacarbonyl (Fe(CO)5)

Cited by 73 publications

References 0 publications

Computational chemistry: A useful (sometimes mandatory) tool in mass spectrometry studies

Computational chemistry: A useful (sometimes mandatory) tool in mass spectrometry studies

The coordination chemistry of the structural zinc ion in alcohol dehydrogenase studied by ab initio quantum chemical calculations

A comparative study of high-spin manganese and iron complexes

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