Isolation of a Homoleptic Non-Oxo Mo(V) Alkoxide Complex: Synthesis, Structure and Electronic Properties of Penta-tert-Butoxymolybdenum,Journal of the American Chemical Society

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Isolation of a Homoleptic Non-Oxo Mo(V) Alkoxide Complex: Synthesis, Structure and Electronic Properties of Penta-tert-Butoxymolybdenum
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-08-27 , DOI: 10.1021/jacs.0c07073
Julius Hillenbrand ₁ , Maurice van Gastel ₁ , Eckhard Bill ₂ , Frank Neese ₁ , Alois Fürstner ₁

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Treatment of [MoCl4(THF)2] with MOtBu (M = Na, Li) does not result in simple metathetic ligand exchange but entails disproportionation with formation of the well-known dinuclear complex [(tBuO)3Mo≡Mo(OtBu)3] and a new paramagnetic compound, [Mo(OtBu)5]. This particular five-coordinate species is the first monomeric, homoleptic, all-oxygen-ligated but non-oxo 4d1 Mo(V) complex known to date; as such, it proves that the dominance of the Mo=O group over (high-valent) molybdenum chemistry can be challenged. [Mo(OtBu)5] was characterized in detail by a combined experimental/computational approach using X-ray diffraction; UV/vis, MCD, IR, EPR, and NMR spectroscopy; and quantum chemistry. The recorded data confirm a Jahn–Teller distortion of the structure, as befitting a d1 species, and show that the complex undergoes Berry pseudorotation. The alkoxide ligands render the disproportionation reaction, leading the formation of [Mo(OtBu)5] to be particularly facile, even though the parent complex [MoCl4(THF)2] itself was also found to be intrinsically unstable; remarkably, this substrate converts into a crystalline material, in which the newly formed Mo(III) and Mo(V) products cohabitate the same unit cell.

中文翻译：

均质非氧代 Mo(V) 醇盐配合物的分离：五叔丁氧基钼的合成、结构和电子特性

用 MOtBu (M = Na, Li) 处理 [MoCl4(THF)2] 不会导致简单的复分解配体交换，但需要歧化形成众所周知的双核络合物 [(tBuO)3Mo≡Mo(OtBu)3]和一种新的顺磁性化合物 [Mo(OtBu)5]。这种特殊的五配位物质是迄今为止已知的第一个单体、均质、全氧连接但非氧合的 4d1 Mo(V) 复合物；因此，它证明可以挑战 Mo=O 基团在（高价）钼化学中的主导地位。[Mo(OtBu)5] 通过结合实验/计算的方法使用 X 射线衍射进行了详细表征；UV/vis、MCD、IR、EPR 和 NMR 光谱；和量子化学。记录的数据证实了结构的 Jahn-Teller 失真，适合 d1 物种，并表明复合物经历了 Berry 假旋转。醇盐配体导致歧化反应，导致 [Mo(OtBu)5] 的形成特别容易，即使母体配合物 [MoCl4(THF)2] 本身也被发现本质上是不稳定的；值得注意的是，该基板转化为结晶材料，其中新形成的 Mo(III) 和 Mo(V) 产物共存于同一个晶胞中。

更新日期：2020-08-27

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