Activation of Gas-Phase Uranyl Diacetone Alcohol Coordination Complexes by Spectator Ligand Addition

✍ Scribed by Daniel Rios; John K. Gibson

• Book ID: 102832008
• Publisher: John Wiley and Sons
• Year: 2012
• Tongue: English
• Weight: 623 KB
• Volume: 2012
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.201200024

✦ Synopsis

Abstract

Gas‐phase addition of a basic ligand to dipositive uranyl coordination complexes comprising diacetone alcohol (DAA) results in water‐elimination, which indicates aldol dehydration of DAA to produce mesityl oxide. A novel attribute of the observed gas‐phase chemistry is that a ligand exothermically associates to a coordination complex to provide the excitation required to induce chemistry in other ligands, with the added “spectator ligand” remaining intact in the product. Dehydration of DAA was observed for addition of tetrahydrofuran, acetone, and 2‐propanol to uranyl complexes [UO~2~(DAA)~2~]^2+^ and [UO~2~(DAA)(acetone)~2~]^2+^. In contrast, [UO~2~(DAA)~2~(acetone)]^2+^ did not exhibit ligand‐addition chemistry, which is attributed to a high degree of coordinative saturation at the uranium metal center.