Density Functional Theory as a Predictive Tool for Cerium Redox Properties in Nonaqueous Solvents.

Two methods to correlate and predict experimental redox potentials for cerium complexes were evaluated. Seventeen previously reported cerium complexes were computed using DFT methods in both the Ce and Ce oxidation states with a dichloromethane solvent continuum. In the first computational approach, the ΔG(Ce/Ce) was determined for each of the compounds and these values were correlated with the experimental E values measured in dichloromethane, referenced to the ferrocene/ferrocenium couple.

Accessing relatively electron poor cerium(iv) hydrazido complexes by lithium cation promoted ligand reduction.

A series of substituted N,N'-diarylhydrazines (ArNHNHAr), Ar = 3,5-(CH3)-C6H3; -Ph; 4-Cl-C6H4; 3,5-Cl-C6H3; 3,5-(CF3)-C6H3, were reacted with Ce(iii)[N(SiMe3)2]3 and lithiated bases to explore the use of Ce(iii) as a reductant and to evaluate the impact of the ligand substitution on the electronic structure at the cerium metal centre of the resulting complexes. The N,N'-diarylhydrazido ligands were coordinated by the Li(+) cation and then reduced by a Ce(iii) cation to form Li4(Et2O)4[Ce(IV)(ArNNAr)4] complexes in all cases. Stabilization of the resulting Ce(iv) product depended on the substituents on the N,N'-diarylhydrazido ligands.

Control of cerium oxidation state through metal complex secondary structures.

A series of alkali metal cerium diphenylhydrazido complexes, M (py) [Ce(PhNNPh)], M = Li, Na, and K, = 4 (Li and Na) or 5 (K), and = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li or Na, the cerium(iii) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline.

Spin-glass behavior and incommensurate modulation in high-pressure perovskite BiCr0.5Ni0.5O3.

The BiCr(0.5)Ni(0.5)O(3) perovskite has been obtained at high pressure.

Stabilization of MIV = Ti, Zr, Hf, Ce, and Th using a selenium bis(phenolate) ligand.

We report M(iv) M = Ti, Zr, Hf, Ce, and Th, complexes of a selenium bis(phenolate) ligand, 2,2'-selenobis(4,6-di-tert-butylphenol), (H(2)(Ar)OSeO), 1. Reaction of Ti(NEt(2))(4) with two equivalents of affords Ti((Ar)OSeO)(2), 2. Salt metathesis of ZrCl(4) and HfCl(4) with two equivalents of Na(2)(Ar)OSeO produces Zr((Ar)OSeO)(2)(THF), 3, and Hf((Ar)OSeO)(2)(THF), 4, respectively.

Lanthanide(III) 2-naphthoxide complexes stabilized by interligand non-covalent interactions.

Lithium-lanthanide-2-naphthoxide complexes are found to have solvent dependent solution structures and related monomeric/dimeric solid state structures. The incorporation of tetramethylguanidium cations into lanthanide 2-naphthoxide complexes stabilizes a complex structure both in solution and the solid state through bridging hydrogen bonds between the 2-naphthoxide ligands.