Covalent Bonding and the Trans Influence in Lanthanide Compounds

A pair of mer-octahedral lanthanide chalcogenolate coordination complexes [(THF)3Ln(EC6F5)3 (Ln = Er, E = Se; Ln = Yb, E = S)] have been isolated and structurally characterized. Both compounds show geometry-dependent bond lengths, with the Ln−E bonds trans to the neutral donor tetrahydrofuran (THF)...

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Veröffentlicht in:Inorganic chemistry 2010-01, Vol.49 (2), p.552-560
Hauptverfasser: Krogh-Jespersen, Karsten, Romanelli, Michael D, Melman, Jonathan H, Emge, Thomas J, Brennan, John G
Format: Artikel
Sprache:eng
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Zusammenfassung:A pair of mer-octahedral lanthanide chalcogenolate coordination complexes [(THF)3Ln(EC6F5)3 (Ln = Er, E = Se; Ln = Yb, E = S)] have been isolated and structurally characterized. Both compounds show geometry-dependent bond lengths, with the Ln−E bonds trans to the neutral donor tetrahydrofuran (THF) significantly shorter than the Ln−E bonds that are trans to negatively charged EC6F5 ligands. Density functional theory calculations indicate that the structural trans influence evidenced by the differences in these bond lengths results from a covalent Ln−E interaction involving ligand p and Ln 5d orbitals.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic901571m