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Probing for Four-Coordinate Zerovalent Iron in a π‑Acidic Ligand Field: A Functional Source of FeL4 Enabled by Labile Dinitrogen Binding

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journal contribution
posted on 10.09.2020, 12:05 by Myles J. Drance, Shuai Wang, Milan Gembicky, Arnold L. Rheingold, Joshua S. Figueroa
It has long been recognized that the first intermediate in chemical reactions mediated by Fe­(CO)5 is Fe­(CO)4. However, the extreme instability of this unsaturated, high-spin species has hampered detailed structural and stoichiometric reactivity studies. The previously reported heteroleptic complex Fe­(N2)­(CO)2(CNArTripp2)2 (ArTripp2 = 2,6-(2,4,6-(i-Pr)3C6H2)2C6H3), which is isolobal to Fe­(CO)5, is shown here to possess a labile dinitrogen ligand that allows it to perform reactions analogous to Fe­(CO)4. Specifically, Fe­(N2)­(CO)2(CNArTripp2)2 oxidatively adds dihydrogen, white phosphorus, and the Si–H bonds of triethylsilane and phenylsilane readily at room temperature and also binds tetrahydrofuran in the absence of N2. Accordingly, Fe­(N2)­(CO)2(CNArTripp2)2 effectively serves as a masked form of Fe­(CO)4, allowing for well-defined reactivity and structurally characterizable reaction products.

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