Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase

Abergel, Rebecca J.; de Jong, Wibe A.; Deblonde, Gauthier J. -P.; Dau, Phuong D.; Captain, Ilya; Eaton, Teresa M.; Jian, Jiwen; van Stipdonk, Michael J.; Martens, Jonathan; Berden, Giel; Oomens, Jos; Gibson, John K.

doi:10.1021/acs.inorgchem.7b01720

Title: Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase

Journal Article · Wed Oct 11 00:00:00 EDT 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b01720· OSTI ID:1436648

^[1];

^[1]; Deblonde, Gauthier J. -P. ^[1]; Dau, Phuong D. ^[1]; Captain, Ilya ^[1]; Eaton, Teresa M. ^[1]; Jian, Jiwen ^[1]; van Stipdonk, Michael J. ^[2];

^[3];

^[4];

^[1]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Duquesne Univ., Pittsburgh, PA (United States)
Radboud Univ., Nijmegen (The Netherlands)
Radboud Univ., Nijmegen (The Netherlands); Univ. of Amsterdam, Amsterdam (The Netherlands)

Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U⁶⁺ chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidence d by CID, using deuterium and ¹⁸O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy. Density functional theory (DFT) computations predict that the overall reaction requires only 132 kJ/mol, with the first oxygen activation entailing about 107 kJ/mol. Here, combined with analysis of similar, but unreactive ligands, these results shed light on the chelation-driven mechanism of uranyl oxo bond cleavage, demonstrating its dependence on the presence of ligand hydroxyl protons available for direct interactions with the uranyl oxygens.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1436648

Journal Information:: Inorganic Chemistry, Vol. 56, Issue 21; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 18 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Uranyl activation
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Gas-phase chemistry
Collision induced dissociation
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