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Synthesis and controlled hydrolysis of organolanthanide complexes with mono- and dianionic benzimidazole-2-thiolate ligands

Dalton Transactions, ISSN: 1477-9226, Vol: 39, Issue: 45, Page: 11053-11059
2010
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Treatment of CpEr with one equivalent of benzimidazole-2-thiol (HBzimt) in THF affords the monoanionic HBzimt complex CpEr(η-HBzimt)(THF) (1). Reaction of CpYb with two equivalents of HBzimt gives complex CpYb(η-HBzimt)(THF) (2) at room temperature. Treatment of CpLn with three equivalents of HBzimt in reflux THF affords the homoleptic Ln(η-HBzimt) (THF) (Ln = Er (3), Y (4)). CpLn reacts with 0.5 equivalents of HBzimt to afford the dianionic Bzimt complexes [(CpLn)(THF)](μ-Bzimt) (Ln = Yb (5), Er (6), Dy (7), Y (8)) in good yields, in which the Bzimt ligand bridges the two metals in an μ-η:η coordination mode. Interestingly, controlled hydrolysis of complexes Cp Ln(η-HBzimt)(THF), CpLn(η -HBzimt)(THF) and [(CpLn)(THF)] (μ-Bzimt) produces the same tetranuclear complexes [CpLn(μ-OH)(μ-η:η-HBzimt)] (Ln = Yb (9), Er (10), Y (11)), indicating that the hydrolysis selectivity greatly depends on the number of coordinated cyclopentadienyl groups. All complexes were characterized by elemental analysis, spectroscopic properties and X-ray single crystal diffraction analysis. © The Royal Society of Chemistry 2010.

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