4.8 Review

Porphyrinoid actinide complexes

Journal

CHEMICAL SOCIETY REVIEWS
Volume 51, Issue 9, Pages 3735-3758

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d2cs00107a

Keywords

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Funding

  1. Robert A. Welch Foundation [F-0018]
  2. Laboratory Directed Research and Development (LDRD) for a Glenn T. Seaborg Graduate Summer Student fellowship
  3. Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences Heavy Element Chemistry Program of the U.S. Department of Energy (DOE) at LBNL [DE-AC02-05CH11231]
  4. National Science Foundation Graduate Research Fellowship Program [DGE 1106400]

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The diverse coordination modes and electronic features of actinide complexes of porphyrins and related oligopyrrolic systems have been the subject of interest since the 1960s. Most work has focused on thorium and uranium, but the ligand environments provided by porphyrinoids have led to the stabilization of unique complexes with early actinides. This review summarizes key examples of prophyrinoid actinide complexes, with emphasis on synthesis, structure, electronic features, and reactivity patterns of representative systems.
The diverse coordination modes and electronic features of actinide complexes of porphyrins and related oligopyrrolic systems (referred to as porpyrinoids) have been the subject of interest since the 1960s. Given their stability and accessibility, most work with actinides has focused on thorium and uranium. This trend is also seen in the case of porphyrinoid-based complexation studies. Nevertheless, the diversity of ligand environments provided by porphyrinoids has led to the stabilization of a number of unique complexes with the early actinides that are often without structural parallel within the broader coordination chemical lexicon. This review summarizes key examples of prophyrinoid actinide complexes reported to date, including the limited number of porphyrinoid systems involving transuranic elements. The emphasis will be on synthesis and structure; however, the electronic features and reactivity pattern of representative systems will be detailed as well. Coverage is through December of 2021.

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