A systematic correlation of the properties of the f-transition metal ions

Quasi-relativistic Douglas-Kroll CASPT2 calculations are reported for the title molecules, mainly to provide primary data for a fit of double-bond covalent radii. Indeed, a well-developed sigma(2)pi(2) double bond is identified in all cases. For Eu and Yb, however, it is an excited state. The main valence orbitals of all Ln ions are 6s and 5d. In the sigma bonds, more 5d than 6s character is found at the Ln. The Ln=C bond lengths show a systematic lanthanide contraction of 13 pm from La to Lu. An agostic symmetry breaking is demonstrated for Ce but its effect on the Ln-C length is small.

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On the Misleading Interpretation of the Properties of the f‐Electron Elements

Fidelis¹

1979

Helvetica Chimica Acta

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SummaryThe aim of the paper is to elucidate the problem of the regular changes in the properties off-elements represented by the double-double effect. It is pointed out that because of the half-filled shell and double-double effects the f-element properties cannot be plotted as a linear function of the L-quantum number, as suggested bySinha reviews the various lanthanide properties and correlates them in terms of the 'inclined W' plots [ 11 [2]. This constitutes however a mislieading interpretation of the existing experimental data.Any consideration of the validity of the idea of 'inclined W' plots, should take into account (1) the half-filled shell effect [3], and (2) the double-double effect discovered in form of the 'regularities' in the separation factors or in stability constants [4]. The former effect, first demonstrated experimentally by Seaborg's group [5] using ion exchange chromatography, is based on the observation that the f6-and f7-electron elements are more similar to each other than those with the f'-and$-electron configurations.The main feature of the double-double effect is the analogy between the

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A systematic correlation of the properties of the f-transition metal ions

Cited by 35 publications

References 77 publications

Chemistry and Spectroscopy off‐Element Organometallics. Part 1: the Lanthanides

Chemistry and Spectroscopy off‐Element Organometallics. Part 1: the Lanthanides

Bonding Trends in Molecular Compounds of Lanthanides: The Double‐Bonded Carbene Cations LnCH₂⁺ (Ln=Sc, Y, La–Lu)

On the Misleading Interpretation of the Properties of the f‐Electron Elements

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A systematic correlation of the properties of the f-transition metal ions

Cited by 35 publications

References 77 publications

Chemistry and Spectroscopy off‐Element Organometallics. Part 1: the Lanthanides

Chemistry and Spectroscopy off‐Element Organometallics. Part 1: the Lanthanides

Bonding Trends in Molecular Compounds of Lanthanides: The Double‐Bonded Carbene Cations LnCH2+ (Ln=Sc, Y, La–Lu)

On the Misleading Interpretation of the Properties of the f‐Electron Elements

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Bonding Trends in Molecular Compounds of Lanthanides: The Double‐Bonded Carbene Cations LnCH₂⁺ (Ln=Sc, Y, La–Lu)