Evidence for single metal two electron oxidative addition and reductive elimination at uranium.
Evidence for single metal two electron oxidative addition and reductive elimination at uranium.
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DOI：
10.1038/s41467-017-01363-0
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发表时间：
2017-12-01
影响因子：
16.6
通讯作者：
Liddle ST
中科院分区：
文献类型：
--
作者：
Gardner BM;Kefalidis CE;Lu E;Patel D;McInnes EJL;Tuna F;Wooles AJ;Maron L;Liddle ST
可逆的单金属双电子氧化加成和还原消除是过渡金属常见的基本反应，是主要催化转化的基础。然而，这些反应从未在f区一起观察到，因为这些金属表现出不可逆的单电子或多电子氧化或还原反应。在这里，我们报告，偶氮苯氧化空间和电子不饱和铀（III）配合物，以提供一个铀（V）-亚胺络合物的反应，满足所有标准的单金属两电子氧化加成。该复合物的热稳定性促进了偶氮苯的挤出，其中H-/D-同位素标记发现没有同位素异构体交叉，并且氮烯陷阱的非反应性表明没有生成氮烯，因此发生了还原消除。虽然在这种情况下没有最佳平衡，但这项工作提供了证据，证明经典的d区氧化还原化学可以通过f区金属可逆地进行，并且铀因此可以模拟元素过渡金属的反应性，这可能导致发现新的f区催化。f-区配合物的反应性主要由单电子氧化和σ-键复分解来定义。在这里，Liddle及其同事提供了证据，证明铀络合物可以进行可逆的氧化加成和还原消除，证明了f区化学中的过渡金属样反应性。
Reversible single-metal two-electron oxidative addition and reductive elimination are common fundamental reactions for transition metals that underpin major catalytic transformations. However, these reactions have never been observed together in the f-block because these metals exhibit irreversible one- or multi-electron oxidation or reduction reactions. Here we report that azobenzene oxidises sterically and electronically unsaturated uranium(III) complexes to afford a uranium(V)-imido complex in a reaction that satisfies all criteria of a single-metal two-electron oxidative addition. Thermolysis of this complex promotes extrusion of azobenzene, where H-/D-isotopic labelling finds no isotopomer cross-over and the non-reactivity of a nitrene-trap suggests that nitrenes are not generated and thus a reductive elimination has occurred. Though not optimally balanced in this case, this work presents evidence that classical d-block redox chemistry can be performed reversibly by f-block metals, and that uranium can thus mimic elementary transition metal reactivity, which may lead to the discovery of new f-block catalysis. The reactivity of f-block complexes is primarily defined by single-electron oxidations and σ-bond metathesis. Here, Liddle and co-workers provide evidence that a uranium complex can undergo reversible oxidative addition and reductive elimination, demonstrating transition metal-like reactivity within f-block chemistry.
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