Stoichiometric control: 8- and 10-coordinate Ln(hfac) 3 (bpy) and Ln(hfac) 3 (bpy) 2 complexes of the early lanthanides La-Sm

The coordination sphere of early lanthanide(iii) ions is highly versatile, exhibiting the ability to form 8-, 9-, and 10-coordinate complexes with the same ligand set. The ability to isolate 10-coordinate complexes decreases across the period, and the late lanthanides typically cannot support a coor...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2018-11, Vol.47 (45), p.16232-16241
Main Authors: Fatila, Elisabeth M, Maahs, Adam C, Hetherington, Erin E, Cooper, Brandon J, Cooper, Riley E, Daanen, Nick N, Jennings, Michael, Skrabalak, Sara E, Preuss, Kathryn E
Format: Article
Language:English
Subjects:
Cerium
Coordination compounds
Coordination numbers
Crystallography
Lanthanides
Lanthanum
Ligands
Melting points
Praseodymium
Samarium
Stoichiometry
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Summary:The coordination sphere of early lanthanide(iii) ions is highly versatile, exhibiting the ability to form 8-, 9-, and 10-coordinate complexes with the same ligand set. The ability to isolate 10-coordinate complexes decreases across the period, and the late lanthanides typically cannot support a coordination number higher than eight. Using two common, commercially available ligands, hfac (1,1,1,5,5,5-hexafluoroacetylacetonato-) and bpy (2,2'-bipyridine), the 8- and 10-coordinate series Ln(hfac)3(bpy) and Ln(hfac)3(bpy)2 (Ln = La-Sm) are compiled in a single investigation, demonstrating that the desired coordination number can be targeted through stoichiometry. Solvent-free syntheses of Ln(hfac)3(bpy) and Ln(hfac)3(bpy)2 complexes from Ln(hfac)3(H2O)3 precursors are investigated using a mechanochemical approach. Structural and spectroscopic properties as well as melting point trends are reported for the series.
ISSN:1477-9226
1477-9234
DOI:10.1039/c8dt03286f