Due to the availability of d- and f-electrons, chemical bonding in transition metal, lanthanide, and actinide compounds is more diverse and intricate compared to the compounds of the main group elements. The high nodality of the 5f-orbitals in actinides, coupled with the fact that many organoactinide complexes possess expanded electron counts, provides the opportunity for the actinide metals to engage in bonding schemes and chemistries that are not available to the d-transition metals. Aside from classical σ and π interactions, such systems may exhibit more exotic bonding modes, such as δ and even φ. In all known examples of metal–ligand (M–L) δ bonds, the 5f-orbitals of actinide are aligned to the ligand orbitals in the so-called “head-to-head” fashion, whereas the M–L φ bonds are mostly formed due to the “side-to-head” interactions. This begs the question of whether other types of the M–L δ and M–L φ interactions are possible. In my talk, I will describe the various types of the M–L interactions of an actinide center with a varying number of carbon atoms constituting the ligand that leads to unique chemical bonding motifs. Specifically, by means of electron localization techniques I will demonstrate the possibility of the “side-to-side” δ as well as “side-to-side” and “head-to-head” φ M–L interactions in the examples of recently synthesized complexes. I will also show that these new types of bonding promote better M–L covalent interaction and hold the potential implication in nuclear separation chemistry.

“Side-to-side” and “head-to-head” δ- and φ-back-donations in complexes of actinides

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.