Intramolecular Oxidative Addition Triggered by One-Electron Oxidation of Molybdenum(iii) Tris(anilide): Generation of Molybdenum(v) Imido Aryl Bis(anilide) by Autocatalysis

IF 2.9 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Organometallics Pub Date : 2025-01-21 DOI:10.1021/acs.organomet.3c00502

Albert Paparo*, Tobias Schindler, Jan van Leusen, Jessica Cook, Thomas P. Spaniol, Paul Kögerler, Manuel Temprado*, Christopher C. Cummins* and Jun Okuda*,

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Abstract

One-electron oxidation of molybdenum(iii) tris(anilide) Mo(N[^tBu]Ar)₃ (Ar: Ar^Me = 3,5-Me₂C₆H₃ and Ar^Ph = 3,5-Ph₂C₆H₃) led to intramolecular oxidative addition across the N–C_ipso bond of a ligated anilide to form the cationic Mo(vi) imido/aryl bis(anilide) complexes [Mo(N[^tBu]Ar)₂(═N^tBu)(Ar)][B(C₆F₅)₄]. One-electron reduction of [Mo(N[^tBu]Ar^Me)₂(═N^tBu)(Ar^Me)][B(C₆F₅)₄] allowed access to the neutral Mo(v) species [Mo(N[^tBu]Ar^Me)₂(═N^tBu)(Ar^Me)]. The d¹ electron configuration was confirmed through EPR spectroscopy and the Evans method. Compound [Mo(N[^tBu]Ar^Me)₂(═N^tBu)(Ar^Me)] was experimentally and theoretically shown to be stable against reductive elimination which would form the energetically less favorable Mo(N[^tBu]Ar)₃. The high activation barrier has so far prevented Mo(N[^tBu]Ar)₃ from isomerizing spontaneously to [Mo(N[^tBu]Ar^Me)₂(═N^tBu)(Ar^Me)]. An autocatalytic process was developed to access [Mo(N[^tBu]Ar^Me)₂(═N^tBu)(Ar^Me)] through reduction of [Mo(N[^tBu]Ar^Me)₂(═N^tBu)(Ar^Me)][B(C₆F₅)₄] by Mo(N[^tBu]Ar)₃, which itself was converted into the oxidizing agent. Attempts to access stable Mo(iv) cations with 4,4′-bipyridine only resulted in labile binding of 4,4′-bipyridine to one or two molybdenum(iii) tris(anilide) complexes.

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钼（iii）三苯胺单电子氧化引发的分子内氧化加成：自催化生成钼(v)亚胺芳基二苯胺

钼（iii）三苯胺)Mo(N[tBu]Ar)3 （Ar: ArMe = 3,5- me2c6h3和ArPh = 3,5- ph2c6h3）的单电子氧化导致分子内氧化加成在连接的苯胺的N - cipso键上形成阳离子Mo（vi）亚胺/芳基双苯胺配合物[Mo(N[tBu]Ar)2(= NtBu)(Ar)][B(C6F5)4]。[Mo(N[tBu]ArMe)2(= NtBu)(ArMe))][B(C6F5)4]的单电子还原可以接触到中性的Mo(v)物质[Mo(N[tBu]ArMe)2(= NtBu)(ArMe)]。通过EPR谱和Evans法确定了d1的电子构型。化合物[Mo(N[tBu]ArMe)2(= NtBu)(ArMe)]在实验和理论上都被证明是稳定的，不受还原消除的影响，还原消除会形成能量较差的Mo(N[tBu]Ar)3。到目前为止，高激活势垒阻止Mo(N[tBu]Ar)3自发异构成[Mo(N[tBu]ArMe)2(= NtBu)(ArMe)]。通过Mo(N[tBu]Ar)3还原[Mo(N[tBu]ArMe)2(= NtBu)(ArMe))][B(C6F5)4]，开发了一种自催化过程来获得[Mo(N[tBu]ArMe)2(= NtBu)(ArMe)], Mo(N[tBu]Ar)3本身被转化为氧化剂。试图用4,4 ' -联吡啶接触稳定的Mo（iv）阳离子，只导致4,4 ' -联吡啶与一个或两个钼（iii）三苯胺配合物的不稳定结合。

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来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

期刊介绍： Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.

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