ChemRxiv
These are preliminary reports that have not been peer-reviewed. They should not be regarded as conclusive, guide clinical practice/health-related behavior, or be reported in news media as established information. For more information, please see our FAQs.
1/1
0/0

Probing the Inverse Trans Influence in Americium and Lanthanide Tribromide Tris(tricyclohexylphosphine oxide)

preprint
submitted on 16.10.2019 and posted on 21.10.2019 by Cory Windorff, Cristian Celis-Barros, Joseph Sperling, Noah Mckinnon, Thomas Albrecht-Schmitt
The synthesis, characterization, and theoretical analysis of meridional americium tribromide tris(tricyclohexylphosphine oxide), mer-AmBr3(OPcy3)3 has been achieved and is compared with its early lanthanide (La to Nd) analogs. The data show that homo trans ligands show significantly shorter bonds than the cis or hetero trans ligands. This is particularly pronounced in the americium compound. DFT along with multiconfigurational CASSCF calculations show that the contraction of the bonds relates qualitatively with overall covalency, i.e. americium shows the most covalent interactions compared to lanthanides. . However, the involvement of the 5p and 6p shells in bonding follows a different order, namely cerium > neodymium ~ americium. This study provides further insight into the mechanisms by which ITI operates in low-valent f-block complexes.

Funding

DE-FG02-13ER16414

History

Email Address of Submitting Author

cwindorff@fsu.edu

Institution

Florida State University

Country

United States of America

ORCID For Submitting Author

0000-0002-5208-9129

Declaration of Conflict of Interest

The authors declare no competing financial interest

Version Notes

Draft ready for submission

Exports