Studies of metal-ligand covalency are an essential aspect of the chemistry of the f-block. In general, the larger radial extent of the 5f/6d orbitals creates the expectation that actinide complexes will exhibit larger covalency than lanthanide ones. We have been developing the chemistry of metal-imido complexes for cerium that enable direct comparisons with thorium ones. Metal-ligand multiple bonds provide a rich playground for exploring and comparing bonding. In general, our results of these imidos demonstrate that cerium(IV)-imidos bear hallmarks of larger covalency based on bonding, reactivity, and spectroscopy studies. These results require a rethinking of the 4f/5f paradigms and prompt further consideration of the properties of cerium related the the group 4 metals, lanthanides, and actinides.

Comparing cerium complexes with thorium ones: Lessons on covalency between multiply-bonded 4f versus 5f elements

ACS Spring Meeting 2021

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