Small‐Molecule Activation at Uranium(III). Issue 22 (2nd April 2013)

• Record Type: Journal Article
• Authors: Gardner, Benedict M.; Liddle, Stephen T.
• Other Names: Lu Connie C. sponsoringEditor.; Meyer Karsten sponsoringEditor.
• Is Part Of: European journal of inorganic chemistry. Issue 22/23(2013)
• Page Start: 3753
• Page End: 3770
• Publication Date: 2013-04-02
• Subjects: Uranium -- Subvalent compounds -- Reduction -- Multiple bonds -- ­Azides; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.201300111
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: Over the last 15 years or so, it has been shown that low‐valent, electron‐rich uranium(III) complexes exhibit a wide variety of reactivity towards small molecules. As a result, the field of uranium‐mediated small‐molecule activation chemistry has undergone significant development in recent years. The classical organometallic reactivity patterns of oxidative addition and reductive elimination that dominate the chemistry of transition‐metal complexes are much less common for uranium. Owing to the invocation of the 5f orbitals for bonding and the highly polarising nature of the actinide centre, the prevalent reactivity observed for non‐aqueous uranium compounds is that of migratory insertion, σ‐bond metathesis and redox activity, and this can account for the often unexpected chemistry encountered with these species. This microreview focuses on the activation chemistry of trivalent uranium complexes towards the important small molecules dinitrogen (N2 ), nitric oxide (NO), azide (N3 – ), carbon monoxide (CO) and carbon dioxide (CO2 ). Abstract : Low‐valent, electron‐rich U III complexes have the ability to access a wide range of novel reactivity patterns with small molecules. This microreview focuses on the activation chemistry of trivalent uranium complexes towards the industrially relevant small molecules N2, NO, N3 –, CO and CO2, outlining the often unexpected chemistry observed for these reactive U III centres.