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Title: Controlling Cation-Cation Interactions in Uranyl Coordination Dimers by Varying the Length of the Dicarboxylate Linker

Journal Article · · European Journal of Inorganic Chemistry
ORCiD logo [1];  [2];  [1]; ORCiD logo [1]; ORCiD logo [2]
  1. Université de Nantes (France)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
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The chemistry of linear uranyl(V/VI) dioxo cations, [O yl –U–O yl ] +/2+ , is dominated by coordination of uranium in the equatorial plane. Effects of this constraint were evaluated by experiment and theory for gas‐phase mixed‐valence U V/VI coordination dimers in which uranyl moieties are linked by alkyl dicarboxylates, [(UO 2 + )(UO 2 2+ )(OOC‐(CH 2 ) n‐ 2 ‐COO 2– ) 2 ] – ( n = 3–12). Faster O 2 ‐addition to dimers with short linkers n = 3 and 4, vs. n ≥ 5, suggests a structural difference. Computed structures with the shortest linkers have bridging dicarboxylates and nearly parallel, non‐interacting uranyls. Longer linkers, n = 5–7, accommodate uranyl orientations with distinct U V –U VI end‐on cation‐cation interactions (CCIs), whereby Lewis base O yl from U V coordinates to the acid U VI , denoted as U V O yl ··· U VI . The dimer structure for n = 8 has a U V –U VI side‐on diamond‐shape CCI, with U V O yl ··· U VI and U VI O yl ··· U V interactions. Addition of O 2 to the n = 4 and 5 dimers yields [(UO 2 2+ ) 2 (OOC‐(CH 2 ) n‐ 2 ‐COO 2– ) 2 (O 2 – )] – , with U V oxidized to U VI and O 2 reduced to O 2 – . Whereas O 2 can associate to and oxidize the exposed U V center for dimers with n = 3 and 4, the more crowded U V site in the CCI structures inhibits O 2 addition. The results demonstrate rational structural control of uranyl‐uranyl bonding and reactivity in small coordination complexes.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1810084
Alternate ID(s):
OSTI ID: 1786466
Journal Information:
European Journal of Inorganic Chemistry, Vol. 2020, Issue 47; ISSN 1434-1948
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
uranyl
cation-cation interaction
coordination dimer