Issue 3, 2025

pKa of alcohols dictates their reactivity with reduced uranium-substituted thiomolybdate clusters

Abstract

The uranium-substituted thiomolybdate cluster, (Cp*3Mo3S4)UCp*, has been demonstrated as a model for water reduction by single uranium atoms supported on a molybdenum sulfide surface (U@MoS2). In this study, the scope of O–H bond activation is expanded through the investigation of the reactivity of various alcohols with differing pKa values for the –OH proton. The reaction of (Cp*3Mo3S4)UCp* with stoichiometric amounts of methanol, phenol, 2,6-dichlorophenol, and nonafluoro-tert-butyl alcohol affords the corresponding mono-alkoxide species, (Cp*3Mo3S4)Cp*U(OR), via a uranium-metalloligand cooperative activation of the O–H bond. This observed reactivity is analogous to the O–H bond activation reported by (Cp*3Mo3S4)UCp* in the presence of water. However, addition of tert-butanol induces protonolysis of the Cp* ligand on uranium, resulting in the formation of a uranium tris-tert-butoxide cluster, (Cp*3Mo3S4)U(OtBu)3. Independent synthesis of (Cp*3Mo3S4)Cp*U(OtBu) was possible via an alternative pathway, eliminating sterics as a justification for the observed discrepancy in reactivity. These results offer insight into the role the –OH proton pKa plays in dictating the mechanism of O–H bond activation of alcohols by the uranium-substituted thiomolybdate cluster.

Graphical abstract: pKa of alcohols dictates their reactivity with reduced uranium-substituted thiomolybdate clusters

Supplementary files

Article information

Article type
Paper
Submitted
06 Oct 2024
Accepted
20 Nov 2024
First published
21 Nov 2024

Dalton Trans., 2025,54, 966-976

pKa of alcohols dictates their reactivity with reduced uranium-substituted thiomolybdate clusters

K. Patra, W. W. Brennessel and E. M. Matson, Dalton Trans., 2025, 54, 966 DOI: 10.1039/D4DT02803A

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