Issue 8, 2015

Structural variation in cerium aryloxide complexes templated by hemilabile K+–amine interactions

Abstract

A series of complexes with the formula K[Ce(OAr)(bdmmp)3] (Ar = –C6H5 (–Ph), –C10H7 (–Naph), –2,4-tBu-C6H3 (–dtbp) and –2,6-Ph-C6H3 (–dpp)) and K[Ce(OAr)2(bdmmp)2] (Ar = –2,6-iPr-C6H3 (–dipp)) (bdmmp = (bis(dimethylamino)methyl-4-phenolate)) are presented. The complexes were obtained through metathesis and protonolysis reactions from K[Ce(OTf)(bdmmp)3] or K[Ce(OtBu)(bdmmp)3] respectively. X-ray diffraction studies provide insight into the effect of the steric profile of the aryloxide ligand on perturbing the templating effect of the K+ ion with the pendent tertiary amine groups of the bdmmp ligands. Characterization of the various aryloxide derivatives through cyclic voltammetry and variable temperature 1H NMR studies demonstrate the impact of the substituents on the solution dynamics and redox properties. Additionally, an unusual example of a terminal cerium(III) hydroxide complex was isolated and characterized in solid state and in solution using the bdmmp framework.

Graphical abstract: Structural variation in cerium aryloxide complexes templated by hemilabile K+–amine interactions

Supplementary files

Article information

Article type
Paper
Submitted
06 Apr 2015
Accepted
26 May 2015
First published
26 May 2015

New J. Chem., 2015,39, 6076-6084

Structural variation in cerium aryloxide complexes templated by hemilabile K+–amine interactions

J. E. Kim, P. J. Carroll and E. J. Schelter, New J. Chem., 2015, 39, 6076 DOI: 10.1039/C5NJ00848D

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