Physical and Structural Characterization of Ce(IV) β-Diketonate Complexes: Evidence for Geometrical Isomers in the Solid-State

Abstract

The Ce(IV) -diketonate complexes CeL 4 [where L is txhd (2,2,6-trimethyl-3,5-heptanedionate) 1; tmod (2,2,7-trimethyl-3,5-octanedionate) 2; tmhd (2,2,6,6-tetramethyl-3,5-heptanedionate) 3] were prepared by the interaction of the sodium salt of the diketonate with cerium(III) nitrate hexahydrate in aqueous ethanol solution. Differential scanning calorimetry and thermogravimetric analysis showed that 1 has a significantly lower sublimation temperature, but higher decomposition temperature than 3. The solid-state structures of the three complexes were determined via single crystal x-ray diffraction methods. Complex 2, which does not sublime, had significantly closer intermolecular contacts than those found for 1 and 3.

Cerium Tetrakis(tropolonate) and Cerium Tetrakis(acetylacetonate) Are Not Diamagnetic but Temperature-Independent Paramagnets

“…Both the α and decahydrate Ce­(acac) 4 complexes are reported. Line d reports the metrics for the decahydrate Ce­(acac) 4 complex. e Reference . f Reference . g Reference . h Reference . i Reference . j Reference . k Reference . l Reference . …”

Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

“…To further demonstrate the utility of the Ce/Li platform, we pursued functionalization through complementary salt metathesis routes. Access to cerium(IV) complexes from ceric ammonium nitrate (CAN) has been used to synthesize alkoxide, aryloxide, and acetylacetonato complexes. However, there are limited reports concerning metathesis from a Ce IV halide .…”

Crystallographic and Spectroscopic Investigations on Oxidative Coordination in the Heteroleptic Mononuclear Complex of Cerium and Benzoxazine Dimer

“…For the outer-sphere oxidation and auto-oxidation reaction, atmospheric oxygen [ 14 , 15 , 16 ] and/or metal-salt oxidants [ 17 , 18 ] are applied to oxidize the Ce(III) precursors, e.g., cerium(III) chloride [ 14 ] and cerium(III) acetylacetonate [ 15 ] during the introduction of ligands to form the desired Ce(IV) complexes. In the oxidation-induced ligand redistributions, the reactions take place in Ce(III) precursors under oxidizing (or aerobic) environments to generate the Ce(IV) products [ 19 , 20 ]. It is generally accepted that the designs of ligands to be applicable as good donors, which lower the oxidation potential of Ce into the range of general oxidative synthetic conditions, are crucial.…”