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Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

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Abstract

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 display 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.

Graphical abstract: Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

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Article information


Submitted
18 Oct 2019
Accepted
04 Feb 2020
First published
05 Feb 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Probing a variation of the inverse-trans-influence in americium and lanthanide tribromide tris(tricyclohexylphosphine oxide) complexes

C. J. Windorff, C. Celis-Barros, J. M. Sperling, N. C. McKinnon and T. E. Albrecht-Schmitt, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC05268B

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