期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 118, 期 1, 页码 325-330出版社
AMER CHEMICAL SOC
DOI: 10.1021/jp4113798
关键词
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资金
- U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry, at LBNL [DE-AC02-05CH11231]
- CNRS
- French Ministere de l'Enseignement Superieur et de la Recherche
- Universita della Calabria
- National Energy Research Scientific Computing Center (NERSC)
- Office of Science of the U.S. Department of Energy [DE-AC02-05C1411231]
- GENCI-CCRT [2012-081859, 2013-081859]
The uranyl moiety, UO22+; is ubiquitous in the chemistry of uranium, the most prevalent actinide. Replacing the strong uranium-oxygen bonds in uranyl with other ligands is very challenging, having met with only limited success. We report here uranyl oxo bond activation in the gas phase to form a terminal nitrido complex, a previously elusive transformation. Collision induced dissociation of gas-phase UO2(NCO)Cl-2(-) in an ion trap produced the nitrido oxo complex, NUOCl2-, and CO2. NUOCl2- was computed by DFT to have C-s symmetry and a singlet ground state. The computed bond length and order indicate a triple U-N bond. Endothermic activation of UO2(NCO)Cl-2(-) to produce NUOCl2- and neutral CO2 was computed to be thermodynamically more favorable than NCO ligand loss. Complete reaction pathways for the CO2 elimination process were computed at the DFT level.
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