Creation of an unexpected plane of enhanced covalency in cerium(III) and berkelium(III) terpyridyl complexes

Controlling the properties of heavy element complexes, such as those containing berkelium, is challenging because relativistic effects, spin-orbit and ligand-field splitting, and complex metal-ligand bonding, all dictate the final electronic states of the molecules. While the first two of these are currently beyond experimental control, covalent M‒L interactions could theoretically be boosted through the employment of chelators with large polarizabilities that substantially shift the electron density in the molecules. This theory is tested by ligating BkIII with 4’-(4-nitrophenyl)-2,2’:6’,2”-terpyridine (terpy*), a ligand with a large dipole. The resultant complex, Bk(terpy*)(NO3)3(H2O)·THF, is benchmarked with its closest electrochemical analog, Ce(terpy*)(NO3)3(H2O)·THF. Here, we show that enhanced Bk‒N interactions with terpy* are observed as predicted. Unexpectedly, induced polarization by terpy* also creates a plane in the molecules wherein the M‒L bonds trans to terpy* are shorter than anticipated. Moreover, these molecules are highly anisotropic and rhombic EPR spectra for the CeIII complex are reported.

The Coordination Chemistry of Imidomethanedithiolate Di-anions: A Structural Comparison with Their Dithiocarbamate Analogs

A review of the coordination chemistry along with the structural features of heavy element complexes of dithiocarbimate di-anions in the form of [(R)C=NCS2]2− for R = CN, alkyl, and aryl are described. This class of compound is far less studied compared with the well-explored dithiocarbamate mono-anions formulated as [R(R’)NCS2]− for R/R’ = H, alkyl, and aryl. The coordination chemistry of dithiocarbimate di-anions is dominated by a S,S-chelating mode; rare examples of alternative modes of coordination are evident. When comparisons are available, the structural motifs adopted by metal dithiocarbimate complexes match those found for their dithiocarbamate analogs, with only small, non-systematic variations in the M–S bond lengths.