Carbene Transfer from a Pyridine Dipyrrolide Iron–Carbene Complex: Reversible Migration of a Diphenylcarbene Ligand into an Iron–Nitrogen Bond,Organometallics

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Carbene Transfer from a Pyridine Dipyrrolide Iron–Carbene Complex: Reversible Migration of a Diphenylcarbene Ligand into an Iron–Nitrogen Bond
Organometallics ( IF 2.5 ) Pub Date : 2022-08-01 , DOI: 10.1021/acs.organomet.2c00260
Brett M. Hakey ₁ , Dylan C. Leary ₁ , Jordan C. Martinez ₁ , Jonathan M. Darmon ₂ , Novruz G. Akhmedov ₁ , Jeffrey L. Petersen ₁ , Carsten Milsmann ₁

Affiliation

The reaction between the square-planar, paramagnetic iron–carbene complex (^MesPDP^Ph)Fe(CPh₂) (where [^MesPDP^Ph]^2– is the doubly deprotonated form of 2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine) and two equivalents of carbon monoxide or 2,6-dimethylphenylisocyanide, CNdmp, resulted in carbene insertion into a Fe–N_pyrrole bond of the ^MesPDP^Ph ligand. Crystallographic studies established complete scission of the Fe–N_pyrrole bond in the resulting low-spin Fe^II complexes. Experiments using 1-adamantylisocyanide, CN¹Ad, demonstrated that binding of two exogenous ligands was required to promote carbene migration and allowed the isolation of diamagnetic (^MesPDP^Ph)Fe(CPh₂)(CN¹Ad). Computational studies by density functional theory (DFT) and complete-active-space self-consistent field (CASSCF) calculations support that (^MesPDP^Ph)Fe(CPh₂)(CN¹Ad) possesses a similar electronic structure to porphyrin iron carbenes, best described as containing a neutral Fischer-type carbene coordinated to a low-spin Fe^II center. DFT calculations also suggested that carbene migration is triggered by an increase in carbene electrophilicity upon binding of a second isocyanide ligand. Thermolysis of the carbene insertion product obtained following the addition of CNdmp to (^MesPDP^Ph)Fe(CPh₂) revealed that the insertion is fully reversible and provided the ketenimine N-(2,2-diphenylethenylidene)-2,6-dimethylbenzenamine as the major product.

中文翻译：

从吡啶二吡咯内酯铁-卡宾配合物中的卡宾转移：二苯基卡宾配体可逆迁移到铁-氮键中

方形平面顺磁性铁-卡宾配合物 ( ^Mes PDP ^Ph )Fe(CPh ₂ ) 之间的反应（其中 [ ^Mes PDP ^Ph ] ^2–是 2,6-bis(5-(2,4 ,6-三甲基苯基）-3-苯基-1 H-吡咯-2-基）吡啶）和两个当量的一氧化碳或 2,6-二甲基苯基异氰化物 CNdmp 导致卡宾插入^{Mes的 Fe-N}_吡咯键PDP ^Ph配体。晶体学研究确定了在所得低自旋 Fe ^II中 Fe-N_{吡咯键的完全断裂}配合物。使用 1-金刚烷基异氰化物 CN ¹ Ad 的实验表明，需要结合两个外源配体来促进卡宾迁移并允许分离抗磁性 ( ^Mes PDP ^Ph )Fe(CPh ₂ )(CN ¹ Ad)。通过密度泛函理论 (DFT) 和完全活性空间自洽场 (CASSCF) 计算的计算研究支持 ( ^Mes PDP ^Ph )Fe(CPh ₂ )(CN ¹ Ad) 具有与卟啉铁卡宾类似的电子结构，最好描述为含有与低自旋 Fe ^II配位的中性 Fischer 型卡宾中央。DFT 计算还表明，卡宾迁移是由与第二个异氰化物配体结合后卡宾亲电性的增加引发的。将 CNdmp 添加到 ( ^Mes PDP ^Ph )Fe(CPh ₂ ) 后获得的卡宾插入产物的热解表明，插入是完全可逆的，并提供了酮亚胺N -(2,2-二苯基亚乙基)-2,6-二甲基苯胺主要产品。

更新日期：2022-08-01

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