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Effects of 2,6-Dichlorophenyl Substituents on the Coordination Chemistry of Pyridine Dipyrrolide Iron Complexes
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2021-06-19 , DOI: 10.1002/zaac.202100117 Brett M. Hakey 1 , Dylan C. Leary 1 , Jose G. Rodriguez 1 , Jordan C. Martinez 1 , Nicholas B. Vaughan 1 , Jonathan M. Darmon 2 , Novruz G. Akhmedov 1 , Jeffrey L. Petersen 1 , Brian S. Dolinar 1 , Carsten Milsmann 1
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2021-06-19 , DOI: 10.1002/zaac.202100117 Brett M. Hakey 1 , Dylan C. Leary 1 , Jose G. Rodriguez 1 , Jordan C. Martinez 1 , Nicholas B. Vaughan 1 , Jonathan M. Darmon 2 , Novruz G. Akhmedov 1 , Jeffrey L. Petersen 1 , Brian S. Dolinar 1 , Carsten Milsmann 1
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A series of iron complexes featuring the pyridine dipyrrolide (PDP) pincer ligand [Cl2PhPDPPh]2−, obtained via deprotonation of 2,6-bis(5-(2,6-dichlorophenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine, H2Cl2PhPDPPh, is reported and structurally and spectroscopically characterized. While the bis-pyridine adduct (Cl2PhPDPPh)Fe(py)2 exhibits nearly identical features as previously reported (MesPDPPh)Fe(py)2 (H2MesPDPPh=2,6-bis(5-(2,4,6-trimethylphenyl)-3-phenyl-1H-pyrrol-2-yl)pyridine), the diethyl ether and tetrahydrofuran adducts (Cl2PhPDPPh)Fe(OEt2) and (Cl2PhPDPPh)Fe(thf) show additional weak Fe−Cl interactions that impact the overall coordination geometries and result in strong deviations from planar coordination environments. The reaction of (Cl2PhPDPPh)Fe(thf) with 1-adamantyl azide provided the isolable iron imido complex (Cl2PhPDPPh)Fe(N1Ad), highlighting the improved stability of [Cl2PhPDPPh]2− towards intramolecular nitrene group transfer from the high-valent iron-imido unit. The electronic structure of (Cl2PhPDPPh)Fe(N1Ad) was investigated by density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations. These computational studies suggest energetically close-lying diamagnetic and paramagnetic states and help to conceptualize the unusual magnetic properties of the complex observed by variable-temperature 1H NMR spectroscopy.
中文翻译:
2,6-二氯苯基取代基对吡啶二吡咯铁配合物配位化学的影响
通过 2,6-双(5-(2,6-二氯苯基)-3-苯基-1 H-吡咯的去质子化获得的一系列具有吡啶二吡咯烷 (PDP) 钳状配体 [ Cl2Ph PDP Ph ] 2−的铁配合物-2-基)吡啶,H 2 Cl2Ph PDP Ph被报道并在结构和光谱上表征。虽然双吡啶加合物 ( Cl2Ph PDP Ph )Fe(py) 2表现出与先前报道的几乎相同的特征 ( Mes PDP Ph )Fe(py) 2 (H 2 Mes PDP Ph =2,6-bis(5-(2 ,4,6-三甲基苯基)-3-苯基-1H -pyrrol-2-yl)pyridine)、乙醚和四氢呋喃加合物 ( Cl2Ph PDP Ph )Fe(OEt 2 ) 和 ( Cl2Ph PDP Ph )Fe(thf) 表现出额外的弱 Fe-Cl 相互作用,影响整体配位几何并导致与平面协调环境的强烈偏差。( Cl2Ph PDP Ph )Fe(thf) 与 1-金刚烷基叠氮化物的反应提供了可分离的亚胺铁配合物 ( Cl2Ph PDP Ph )Fe(N 1 Ad),突出了 [ Cl2Ph PDP Ph ] 2−稳定性的提高从高价铁-亚氨基单元向分子内氮烯基转移。通过密度泛函理论(DFT)和完全活性空间自洽场(CASSCF)计算研究了(Cl2Ph PDP Ph)Fe(N 1 Ad)的电子结构。这些计算研究表明,在能量上存在紧密的反磁性和顺磁性状态,并有助于将变温1 H NMR 光谱观察到的复合物的异常磁性概念化。
更新日期:2021-07-14
中文翻译:
![](https://scdn.x-mol.com/jcss/images/paperTranslation.png)
2,6-二氯苯基取代基对吡啶二吡咯铁配合物配位化学的影响
通过 2,6-双(5-(2,6-二氯苯基)-3-苯基-1 H-吡咯的去质子化获得的一系列具有吡啶二吡咯烷 (PDP) 钳状配体 [ Cl2Ph PDP Ph ] 2−的铁配合物-2-基)吡啶,H 2 Cl2Ph PDP Ph被报道并在结构和光谱上表征。虽然双吡啶加合物 ( Cl2Ph PDP Ph )Fe(py) 2表现出与先前报道的几乎相同的特征 ( Mes PDP Ph )Fe(py) 2 (H 2 Mes PDP Ph =2,6-bis(5-(2 ,4,6-三甲基苯基)-3-苯基-1H -pyrrol-2-yl)pyridine)、乙醚和四氢呋喃加合物 ( Cl2Ph PDP Ph )Fe(OEt 2 ) 和 ( Cl2Ph PDP Ph )Fe(thf) 表现出额外的弱 Fe-Cl 相互作用,影响整体配位几何并导致与平面协调环境的强烈偏差。( Cl2Ph PDP Ph )Fe(thf) 与 1-金刚烷基叠氮化物的反应提供了可分离的亚胺铁配合物 ( Cl2Ph PDP Ph )Fe(N 1 Ad),突出了 [ Cl2Ph PDP Ph ] 2−稳定性的提高从高价铁-亚氨基单元向分子内氮烯基转移。通过密度泛函理论(DFT)和完全活性空间自洽场(CASSCF)计算研究了(Cl2Ph PDP Ph)Fe(N 1 Ad)的电子结构。这些计算研究表明,在能量上存在紧密的反磁性和顺磁性状态,并有助于将变温1 H NMR 光谱观察到的复合物的异常磁性概念化。