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Substrate-Dependent Hydridic and Radical Reactivity of Triiron Hydride Clusters
Brian J Knight1, Kevin J Anderton1, Juan F Torres1
1Center for Catalysis and Florida Center for Heterocyclic Chemistry, Department of Chemistry, University of Florida, Gainesville, Florida 32611, United States.
None:
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 Fe3H3L (1) and (FeCO)2Fe(μ3-H)L (2) (where L3- is a tris(β-diketiminate)cyclophanate) with Brønsted acids, organochlorides, acetyl chloride, boron trihalides, and titanium electrophiles is reported. Complex 1 reacts with Brønsted acids H2O and [Et3NH][Cl] to afford Fe3(OH)3L (3) and Fe3H2ClL (4), respectively, consistent with hydridic reactivity. Clusters 1 and 2 react readily with organochlorides, such as CCl4, CHCl3, and CH2Cl2, with identified intermediates supporting a radical pathway. Complex 1 reacts with trityl chloride (2 equiv) to selectively afford Fe3HCl2L (5) with reductive elimination of dihydrogen observed. Mixed-valent complex 2 reacts with AcCl to afford (FeCO)Fe2HClL (9). The scope of reactivity displayed implicates possible pathways accessible to larger clusters in biology or on metal surfaces.
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