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Reversible C–C bond formation in group 4 metal complexes: nitrile extrusion via β-aryl elimination
Chemical Science ( IF 7.6 ) Pub Date : 2024-08-27 , DOI: 10.1039/d4sc02173h Pavel S Kulyabin 1 , Georgy P Goryunov 1 , Andrei N Iashin 1 , Dmitry Y Mladentsev 1 , Dmitry V Uborsky 1 , Christian Ehm 2 , Jo Ann M Canich 3 , John R Hagadorn 3 , Alexander Z Voskoboynikov 1
Chemical Science ( IF 7.6 ) Pub Date : 2024-08-27 , DOI: 10.1039/d4sc02173h Pavel S Kulyabin 1 , Georgy P Goryunov 1 , Andrei N Iashin 1 , Dmitry Y Mladentsev 1 , Dmitry V Uborsky 1 , Christian Ehm 2 , Jo Ann M Canich 3 , John R Hagadorn 3 , Alexander Z Voskoboynikov 1
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Pyridylamides of zirconium and hafnium with [C,N,N]-ligands reversibly insert nitriles into M–CAr bonds leading to an observable equilibrium between the starting [C,N,N]-complexes and newly formed [N,N,N]-complexes with a ketimide moiety in a 7-membered metallacycle. The discovered reversible insertion of nitriles into M–CAr bonds represents an unprecedented example of β-aryl elimination from a ketimide ligand in early transition metal complexes. Experimental and computational studies suggest thermodynamic and electronic reasons for this reactivity. Weak orbital overlap between the ketimide nitrogen and the metal, and an unfavorable 7-membered metallacycle destabilize the product of insertion into the M–CAr bond, while the pyridylamide moiety acts as a directing group making the reverse process viable. The influence of non-chelate spectator ligands on the metal center and substituents in nitrile on the thermodynamic stability of the [N,N,N]-complexes was also studied. Exploiting β-carbon elimination in complexes of early transition metals may extend the range of catalysts that are accessible for C–C activation processes in the future.
中文翻译：
第 4 族金属配合物中可逆的 C-C 键形成：通过 β-芳基消除进行腈挤出
锆和铪的吡啶酰胺与[C,N,N]-配体可逆地将腈插入M-C Ar键中，导致起始[C,N,N]-配合物和新形成的[N,N,N]之间出现可观察到的平衡]-在7元金属环中具有酮亚胺部分的络合物。所发现的腈可逆插入 M-C Ar键代表了早期过渡金属配合物中酮酰亚胺配体中 β-芳基消除的前所未有的例子。实验和计算研究表明了这种反应的热力学和电子原因。酮亚胺氮和金属之间的弱轨道重叠以及不利的七元金属环使插入 M-C Ar键的产物不稳定，而吡啶酰胺部分则充当导向基团，使逆过程可行。还研究了金属中心上的非螯合观察配体和腈中的取代基对[N,N,N]-配合物热力学稳定性的影响。利用早期过渡金属配合物中的β-碳消除可能会扩大未来可用于C-C活化过程的催化剂范围。
更新日期：2024-08-27
中文翻译：
第 4 族金属配合物中可逆的 C-C 键形成：通过 β-芳基消除进行腈挤出
锆和铪的吡啶酰胺与[C,N,N]-配体可逆地将腈插入M-C Ar键中，导致起始[C,N,N]-配合物和新形成的[N,N,N]之间出现可观察到的平衡]-在7元金属环中具有酮亚胺部分的络合物。所发现的腈可逆插入 M-C Ar键代表了早期过渡金属配合物中酮酰亚胺配体中 β-芳基消除的前所未有的例子。实验和计算研究表明了这种反应的热力学和电子原因。酮亚胺氮和金属之间的弱轨道重叠以及不利的七元金属环使插入 M-C Ar键的产物不稳定，而吡啶酰胺部分则充当导向基团，使逆过程可行。还研究了金属中心上的非螯合观察配体和腈中的取代基对[N,N,N]-配合物热力学稳定性的影响。利用早期过渡金属配合物中的β-碳消除可能会扩大未来可用于C-C活化过程的催化剂范围。
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