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单齿咔唑基配体稳定氢化锶及其反应活性

Stabilisation of a Strontium Hydride with a Monodentate Carbazolyl Ligand and its Reactivity.

作者信息

Winkler Lucas, Hinz Alexander

机构信息

Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry (AOC), Engesserstr. 15, Geb. 30.45, Karlsruhe, Germany.

出版信息

Angew Chem Int Ed Engl. 2025 Jan 27;64(5):e202418558. doi: 10.1002/anie.202418558. Epub 2024 Dec 10.

Abstract

The molecular strontium hydride 2 [(Cbz)SrH(L)] (L=benzene, toluene) was isolated and stabilized by employing a sterically demanding carbazole ligand (Cbz=1,8-bis(3,5-ditertbutylphenyl)-3,6-ditertbutylcarbazolyl). Compound 2 was synthesized via phenylsilane metathesis with the corresponding amide (Cbz)SrN(SiMe) and characterized by H NMR, XRD and vibrational spectroscopy methods. We further investigated the stoichiometric reactivity of 2 towards carbon monoxide, azobenzene and trimethylsilylacetylene, showing three distinct reactivity pathways: addition, reduction and deprotonation. The reaction of 2 with carbon monoxide yields the ethenediolate complex 4 via addition, while with azobenzene reduction of the N-N double bond and release of hydrogen were observed, affording a heteroleptic strontium complex with a radical azobenzenyl ligand (5). The terminal alkyne is deprotonated by the hydride moiety to give the acetylide complex 6.

摘要

通过使用空间位阻较大的咔唑配体(Cbz = 1,8 - 双(3,5 - 二叔丁基苯基)- 3,6 - 二叔丁基咔唑基)分离并稳定了分子氢化锶2 [(Cbz)SrH(L)](L = 苯、甲苯)。化合物2通过苯基硅烷复分解反应与相应的酰胺(Cbz)SrN(SiMe)合成,并通过核磁共振氢谱、X射线衍射和振动光谱方法进行了表征。我们进一步研究了2与一氧化碳、偶氮苯和三甲基硅乙炔的化学计量反应性,展示了三种不同的反应途径:加成、还原和去质子化。2与一氧化碳反应通过加成生成乙二酸盐配合物4,而与偶氮苯反应则观察到N - N双键的还原和氢气的释放,得到一种具有自由基偶氮苯配体的杂配锶配合物(5)。末端炔烃被氢化物部分去质子化,生成乙炔化物配合物6。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/05d0/11773309/010bec96046d/ANIE-64-e202418558-g007.jpg

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