Knight Brian J, Anderton Kevin J, Torres Juan F, Catalano Vincent J, Garcia-Serres Ricardo, Murray Leslie J
Center for Catalysis and Florida Center for Heterocyclic Chemistry, Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.
Department of Chemistry, University of Nevada, Reno, Nevada 89557, United States.
Inorg Chem. 2025 Apr 28;64(16):8052-8063. doi: 10.1021/acs.inorgchem.5c00071. Epub 2025 Apr 16.
The reactivity of iron clusters with one of more μ-hydrides and in the weak field pertains to catalysis on surfaces and biological metal cluster cofactors. As a model, then, a reactivity survey of the weak-field ligated iron hydride clusters FeH () and (FeCO)Fe(μ-H) () (where is a tris(β-diketiminate)cyclophanate) with Brønsted acids, organochlorides, acetyl chloride, boron trihalides, and titanium electrophiles is reported. Complex reacts with Brønsted acids HO and [EtNH][Cl] to afford Fe(OH) () and FeHCl (), respectively, consistent with hydridic reactivity. Clusters and react readily with organochlorides, such as CCl, CHCl, and CHCl, with identified intermediates supporting a radical pathway. Complex reacts with trityl chloride (2 equiv) to selectively afford FeHCl () with reductive elimination of dihydrogen observed. Mixed-valent complex reacts with AcCl to afford (FeCO)FeHCl (). The scope of reactivity displayed implicates possible pathways accessible to larger clusters in biology or on metal surfaces.
铁簇与一个或多个μ-氢化物在弱场中的反应活性与表面催化和生物金属簇辅助因子有关。因此，作为一个模型，本文报道了对弱场配位的氢化铁簇FeH () 和(FeCO)Fe(μ-H) ()（其中 是三（β-二酮亚胺）环番酸盐）与布朗斯特酸、有机氯化物、乙酰氯、三卤化硼和钛亲电试剂的反应活性研究。配合物 与布朗斯特酸HO和[EtNH][Cl]反应，分别生成Fe(OH) () 和FeHCl ()，这与氢化物的反应活性一致。簇 和 很容易与有机氯化物，如CCl、CHCl和CHCl反应，已鉴定的中间体支持自由基途径。配合物 与三苯甲基氯（2当量）反应，选择性地生成FeHCl ()，并观察到有氢气的还原消除。混合价配合物 与AcCl反应生成(FeCO)FeHCl ()。所展示的反应活性范围暗示了生物学或金属表面上更大簇可能采用的途径。
