期刊
NATURE CHEMISTRY
卷 6, 期 5, 页码 387-392出版社
NATURE RESEARCH
DOI: 10.1038/NCHEM.1896
关键词
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资金
- Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, Office of Science, Heavy Elements Chemistry Program, US Department of Energy [DE-SC0002215, DE-FG02-13ER16414, DE-SC002183, DE-AC02-06CH11357]
- National Science Foundation [DMR-0955353]
- Helmholtz Association [VH-NG-815]
- Direct For Mathematical & Physical Scien
- Division Of Materials Research [0955353] Funding Source: National Science Foundation
The participation of the valence orbitals of actinides in bonding has been debated for decades. Recent experimental and computational investigations demonstrated the involvement of 6p, 6d and/or 5f orbitals in bonding. However, structural and spectroscopic data, as well as theory, indicate a decrease in covalency across the actinide series, and the evidence points to highly ionic, lanthanide-like bonding for late actinides. Here we show that chemical differentiation between californium and lanthanides can be achieved by using ligands that are both highly polarizable and substantially rearrange on complexation. A ligand that suits both of these desired properties is polyborate. We demonstrate that the 5f, 6d and 7p orbitals are all involved in bonding in a Cf(III) borate, and that large crystal-field effects are present. Synthetic, structural and spectroscopic data are complemented by quantum mechanical calculations to support these observations.
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