Muonium Chemistry at Diiron Subsite Analogues of [FeFe]‐Hydrogenase. Issue 47 (14th October 2016)

• Record Type: Journal Article
• Authors: Wright, Joseph A.; Peck, Jamie N. T.; Cottrell, Stephen P.; Jablonskytė, Aušra; Oganesyan, Vasily S.; Pickett, Christopher J.; Jayasooriya, Upali A.
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 47(2016)
• Page Start: 14580
• Page End: 14583
• Publication Date: 2016-10-14
• Subjects: enzyme mimics -- [FeFe]-hydrogenase -- hydrogen -- muonium; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201607109
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The chemistry of metal hydrides is implicated in a range of catalytic processes at metal centers. Gaining insight into the formation of such sites by protonation and/or electronation is therefore of significant value in fully exploiting the potential of such systems. Here, we show that the muonium radical (Mu . ), used as a low isotopic mass analogue of hydrogen, can be exploited to probe the early stages of hydride formation at metal centers. Mu . undergoes the same chemical reactions as H . and can be directly observed due to its short lifetime (in the microseconds) and unique breakdown signature. By implanting Mu . into three models of the [FeFe]‐hydrogenase active site we have been able to detect key muoniated intermediates of direct relevance to the hydride chemistry of these systems. Abstract : New radicals : Interaction of muonium with {2Fe2S} cores leads to the formation of mixed‐valence adducts. Detection of these species opens a new window on the reactivity of hydride at redox‐active metal centers. The unique selectivity and timescale of muon spin spectroscopy has the potential to reveal reactivity in a wide range of catalytic intermediates.