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Formation of unprecedented actinidecarbon triple bonds in uranium methylidyne molecules.
- Source :
-
Proceedings of the National Academy of Sciences of the United States of America . 11/27/2007, Vol. 104 Issue 48, p18919-18924. 6p. - Publication Year :
- 2007
-
Abstract
- Chemistry of the actinide elements represents a challenging yet vital scientific frontier. Development of actinide chemistry requires fundamental understanding of the relative roles of actinide valence-region orbitals and the nature of their chemical bonding. We report here an experimental and theoretical investigation of the uranium methylidyne molecules X3UCH (X = F, Cl, Br), F2CIUCH, and F3UCF formed through reactions of laser-ablated uranium atoms and trihalomethanes or carbon tetrafluoride in excess argon. By using matrix infrared spectroscopy and relativistic quantum chemistry calculations, we have shown that these actinide complexes possess relatively strong UC triple bonds between the U 6d-5f hybrid orbitals and carbon 2s-2p orbitals. Electron-with- drawing ligands are critical in stabilizing the U(Vl) oxidation state and sustaining the formation of uranium multiple bonds. These unique UC-bearing molecules are examples of the long-sought actinide-alkylidynes. This discovery opens the door to the rational synthesis of triple-bonded actinide-carbon compounds. [ABSTRACT FROM AUTHOR]
- Subjects :
- *URANIUM compounds
*ACTINIDE elements
*TRIHALOMETHANES
*QUANTUM chemistry
*ARGON
Subjects
Details
- Language :
- English
- ISSN :
- 00278424
- Volume :
- 104
- Issue :
- 48
- Database :
- Academic Search Index
- Journal :
- Proceedings of the National Academy of Sciences of the United States of America
- Publication Type :
- Academic Journal
- Accession number :
- 27935880
- Full Text :
- https://doi.org/10.1073/pnas.0707035104