A Four-Coordinate Pr Imidophosphorane Complex.

The imidophosphorane ligand, [NPBu] (Bu=tert-butyl), enables isolation of a pseudo-tetrahedral, tetravalent praseodymium complex, [Pr(NPBu)] (1-Pr), which is characterized by a suite of physical characterization methods including single-crystal X-ray diffraction, electron paramagnetic resonance, and L-edge X-ray near-edge spectroscopies. Variable-temperature direct-current magnetic susceptibility data, supported by multiconfigurational quantum chemical calculations, demonstrate that the electronic structure diverges from the isoelectronic Ce analogue, driven by increased crystal field. The four-coordinate environment around Pr in 1-Pr, which is unparalleled in reported extended solid systems, provides a unique opportunity to study the interplay between crystal field splitting and spin-orbit coupling in a molecular tetravalent lanthanide within a pseudo-tetrahedral coordination geometry.

Intervalence Charge Transfer in Nonbonding, Mixed-Valence, Homobimetallic Ytterbium Complexes.

There are several reports of compounds containing lanthanide ions in two different formal oxidation states; however, there are strikingly few examples of intervalence charge transfer (IVCT) transitions observed for these complexes, with those few occurrences limited to extended solids rather than molecular species. Herein, we report the synthesis, characterization, and computational analysis for a series of ytterbium complexes including a mixed-valence Yb complex featuring a remarkably short Yb···Yb distance of 2.9507(8) Å.

Metal-Metal Bond in Heterometallic Extended Metal Atom Chains.

Understanding the fundamental properties governing metal-metal interactions is crucial to understanding the electronic structure and thereby applications of multimetallic systems in catalysis, material science, and magnetism. One such property that is relatively underexplored within multimetallic systems is metal-metal bond polarity, parameterized by the electronegativities (χ) of the metal atoms involved in the bond. In heterobimetallic systems, metal-metal bond polarity is a function of the donor-acceptor (Δχ) interactions of the two bonded metal atoms, with electropositive early transition metals acting as electron acceptors and electronegative late transition metals acting as electron donors.

Electronic Structure of Ru Complexes with Electron-Rich Anilinopyridinate Ligands.

Diruthenium paddlewheel complexes supported by electron-rich anilinopyridinate (Xap) ligands were synthesized in the course of the first in-depth structural and spectroscopic interrogation of monocationic [Ru(Xap)Cl] species in the Ru oxidation state. Despite paramagnetism of the compounds, H NMR spectroscopy proved highly informative for determining the isomerism of the Ru and Ru compounds. While most compounds are found to have the polar (4,0) geometry, with all four Xap ligands in the same orientation, some synthetic procedures resulted in a mixture of (4,0) and (3,1) isomers, most notably in the case of the parent compound Ru(ap)Cl.

Electronic Structure of Anilinopyridinate-Supported Ru Paddlewheel Compounds.

The electronic structures of the diruthenium compounds Ru(ap)Cl (1, ap = 2-anilinopyridinate) and Ru(ap)OTf (2) were investigated with UV-vis, resonance Raman, and magnetic circular dichroism (MCD) spectroscopies; SQUID magnetometry; and density functional theory (DFT) calculations. Both compounds have quartet spin ground states with large axial zero-field splitting of ∼60 cm that is characteristic of Ru compounds having a (π*, δ*) electron configuration and a Ru-Ru bond order of ∼2.5.