Work

Substrate-Dependent Hydridic and Radical Reactivity of Triiron Hydride Clusters

Year: 2025

Type: article

Abstract: 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 Fe 3 H 3 L ( 1 ) and (FeCO) 2 Fe(μ 3 –H) L ( 2 ) (where L 3– 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 H 2 O and [Et 3 NH][Cl] to afford Fe 3 (OH) 3 L ( 3 ) and Fe 3 H 2 Cl L ( 4 ), respectively, consistent with hydridic reactivity. Clusters 1 and 2 react readily with organochlorides, such as CCl 4, CHCl 3, and CH 2 Cl 2, with identified intermediates supporting a radical pathway. Complex 1 reacts with trityl chloride (2 equiv) to selectively afford Fe 3 HCl 2 L ( 5 ) with reductive elimination of dihydrogen observed. Mixed-valent complex 2 reacts with AcCl to afford (FeCO)Fe 2 HCl L ( 9 ). The scope of reactivity displayed implicates possible pathways accessible to larger clusters in biology or on metal surfaces.

Source: Inorganic Chemistry

DOI: 10.1021/acs.inorgchem.5c00071

Authors: Brian J. Knight, Kevin J. Anderton, Juan F. Torres, Vincent J. Catalano, Ricardo Garcia-Serres, Leslie J. Murray