Reactions in the gas phase preclude secondary transformations and perturbations, presenting an opportunity to investigate chemistry that may be elusive in condensed phases. Endothermic fragmentation of gas-phase coordination complexes in an ion trap mass spectrometer is employed to explore new actinide chemistry. For example, elimination of the very stable CO2 molecule from actinyl carboxylates has enabled formation of An-C (An = U, Np, Pu) bonds, and CO2 elimination from actinyl isocyanates results in conversion of An-Oyl bonds to An-N bonds. Reactions of both the An-C and An-N bonds with water results in spontaneous hydrolysis to recover the stronger An-O bonds. In this collaborative project involving experiment and theory, the products of these and other transformations have been characterized by reactivity, spectroscopy, and computations. Selected examples of new chemistry for the actinides Th through Cf will be presented, along with prospects for future advances in gas-phase actinide chemistry. This work is supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Heavy Element Chemistry, at LBNL under Contract No. DE-AC02-05CH11231.

Synthesis and chemistry of novel actinide complexes in the gas phase

251st National Meeting (2016)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.