Winkler Lucas, Hinz Alexander
Karlsruhe Institute of Technology (KIT), Institute of Inorganic Chemistry (AOC), Engesserstr. 15, Geb. 30.45, Karlsruhe, Germany.
Angew Chem Int Ed Engl. 2025 Jan 27;64(5):e202418558. doi: 10.1002/anie.202418558. Epub 2024 Dec 10.
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.
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。
