Issue 12, 2024

Gas-phase synthesis of [O[double bond, length as m-dash]U–X]+ (X = Cl, Br and I) from a UO22+ precursor using ion-molecule reactions and an [O[double bond, length as m-dash]U[triple bond, length as m-dash]CH]+ intermediate

Abstract

Difficulty in the preparation of gas-phase ions that include U in middle oxidation states(III,IV) have hampered efforts to investigate intrinsic structure, bonding and reactivity of model species. Our group has used preparative tandem mass spectrometry (PTMS) to synthesize a gas-phase U-methylidyne species, [O[double bond, length as m-dash]U[triple bond, length as m-dash]CH]+, by elimination of CO from [UO2(C[triple bond, length as m-dash]CH)]+ [M. J. van Stipdonk, I. J. Tatosian, A. C. Iacovino, A. R. Bubas, L. Metzler, M. C. Sherman and A. Somogyi, J. Am. Soc. Mass Spectrom., 2019, 30, 796–805], which has been used as an intermediate to create products such as [OUN]+ and [OUS]+ by ion-molecule reactions. Here, we investigated the reactions of [O[double bond, length as m-dash]U[triple bond, length as m-dash]CH]+ with a range of alkyl halides to determine whether the methylidyne is a also a useful intermediate for production and study of the oxy-halide ions [OUX]+, where X = Cl, Br and I, formally U(IV) species for which intrinsic reactivity data is relatively scarce. Our experiments demonstrate that [OUX]+ is the dominant product ion generated by reaction [O[double bond, length as m-dash]U[triple bond, length as m-dash]CH]+ with neutral regents such as CH3Cl, CH3CH2Br and CH2[double bond, length as m-dash]CHCH2I.

Graphical abstract: Gas-phase synthesis of [O [[double bond, length as m-dash]] U–X]+ (X = Cl, Br and I) from a UO22+ precursor using ion-molecule reactions and an [O [[double bond, length as m-dash]] U [[triple bond, length as m-dash]] CH]+ intermediate

Supplementary files

Article information

Article type
Paper
Submitted
29 Aug 2023
Accepted
19 Feb 2024
First published
22 Feb 2024

Dalton Trans., 2024,53, 5478-5483

Gas-phase synthesis of [O[double bond, length as m-dash]U–X]+ (X = Cl, Br and I) from a UO22+ precursor using ion-molecule reactions and an [O[double bond, length as m-dash]U[triple bond, length as m-dash]CH]+ intermediate

J. Terhorst, S. Lenze, L. Metzler, A. N. Fry, A. Ihabi, T. A. Corcovilos and M. J. van Stipdonk, Dalton Trans., 2024, 53, 5478 DOI: 10.1039/D3DT02811A

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