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Carbon oxygenate transformations by actinide compounds and catalysts

Nature Reviews Chemistry volume 1, Article number: 0002 (2017) Cite this article

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Abstract

Carbon oxygenates represent an increasingly important class of feedstock in the development of a sustainable chemical economy. Their catalytic transformation into value-added chemicals is a crucial target, because it would reduce our ties to fossil fuels and non-renewable resources. In this Review, we discuss the unique reactivity offered by actinide metal complexes with respect to s-, p- and d-block metals resulting from the chemical properties particular to these metals. This reactivity is governed by large ionic radii, high coordination numbers, kinetic lability, the involvement of f orbitals in bonding, and single-electron redox processes or σ-bond metathesis, which are distinct from the oxidative addition and reductive elimination pathways commonly seen for catalysts derived from d-block metals. We conclude with a discussion of the current progress in the use of these complexes towards catalytic transformations of oxygenated hydrocarbons.

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Figure 1: Key features of the reactivity of the actinide elements.
Figure 2: Reactions of carbon monoxide with actinide complexes.
Figure 3: Actinide complexes exhibit diverse reactivity towards CO2.
Figure 4: Actinide complexes catalyse ring-opening polymerization of epoxides and lactides.
Figure 5: Catalytic or stoichiometric reactions of actinide complexes with alcohols, aldehydes and ketones.

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Acknowledgements

The authors thank the Engineering and Physical Sciences Research Council (EPSRC), UK (grant numbers EP/M010554/1, EP/K014714/1 and EP/J018139/1), the European Cooperation in Science and Technology (COST) Network CM1205, and Z.R.T. thanks SCG Chemicals for funding. Z.R.T also thanks Trinity College, Oxford for a Junior Research Fellowship.

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  1. EaStCHEM School of Chemistry, University of Edinburgh, The King's Buildings, EH9 3FJ, Edinburgh, UK

    Polly L. Arnold

  2. Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford, OX1 3TA, UK

    Zoë R. Turner

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Glossary

σ-Bond metathesis

A reaction that replaces one σ-bonded ligand in M–X with another in a substrate E–X′ to form M–X′ via a four-centre transition state and without any change in formal oxidation state of the metal.

Oxidative addition

A common and widely exploited reaction in homogeneous d-block catalytic chemistry that involves the addition of the E–X bond of a substrate to a metal centre (L)nM using the two electrons from the E–X bond and two metal valence electrons, resulting in the formation of (L)nM(E)(X) and an increase in formal oxidation state of the metal by two.

Reductive elimination

Formally the reverse of oxidative addition, in which a molecule or fragment is released from a metal complex (L)nM(E)(X), returning two electrons to the metal and forming a new E–X bond. Often the key to substrate release and, therefore, turnover in redox-based homogeneous catalysis.

Cp*

(C5Me5). A cyclic aromatic monoanionic ligand that binds strongly with a moderate degree of covalency through the five-ring carbon atoms to an actinide centre. The hapto (η) prefix indicates that all ring C atoms bind to the metal. A pair provide an excellent supporting, ancillary ligand set for various organo-actinide chemistry studies at X in [(η-Cp*)2AnX2]-type complexes. The related cyclic, aromatic η-C8R8 dianions, binding through eight ring carbon atoms, are also commonly used.

Migratory insertion

The coupling of two M-bound ligands, one anionic (X; generally an alkyl, hydride, amide or alkoxide in this Review) and one neutral (L; generally CO or an ether, ketone or aldehyde in this Review, for which the initial binding may not necessarily have been an observable event) that generates a new M-bound X ligand that includes the group L.

Turnover frequency

Related to the turnover number, this is the number of substrate molecules converted per active catalyst site in a given unit time.

Turnover number

The number of substrate molecules converted per active catalyst site. Overall turnover number can be related to catalyst stability or longevity.

Markovnikov addition

Addition of HX across a C–C multiple bond with H addition at the least substituted carbon.

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Arnold, P., Turner, Z. Carbon oxygenate transformations by actinide compounds and catalysts. Nat Rev Chem 1, 0002 (2017). https://doi.org/10.1038/s41570-016-0002

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