Substrate-Dependent Hydridic and Radical Reactivity of Triiron Hydride Clusters

Area of Science:

• Inorganic Chemistry
• Organometallic Chemistry
• Catalysis

Background:

• Iron hydride clusters are relevant to surface catalysis and biological metal cofactors.
• Understanding their reactivity is crucial for developing new catalytic systems.

Purpose of the Study:

• To investigate the reactivity of specific iron hydride clusters (Fe3H3L and (FeCO)2Fe(μ3-H)L) with a range of electrophiles.
• To elucidate reaction mechanisms and identify potential pathways relevant to biological and surface chemistry.

Main Methods:

• Synthesis and characterization of iron hydride clusters.
• Reactivity studies with Brønsted acids, organochlorides, acetyl chloride, boron trihalides, and titanium electrophiles.
• Mechanistic investigations including intermediate identification and pathway analysis.

Main Results:

• Complex 1 (Fe3H3L) exhibits hydridic reactivity with Brønsted acids, forming Fe3(OH)3L and Fe3H2Cl L.
• Both clusters react with organochlorides via a radical pathway.
• Complex 1 reacts with trityl chloride to yield Fe3HCl2L with dihydrogen elimination.
• Mixed-valent complex 2 reacts with acetyl chloride to form (FeCO)Fe2HCl L.

Conclusions:

• The studied iron hydride clusters display diverse reactivity patterns with electrophiles.
• These reactions provide models for understanding pathways in biological metal cofactors and surface catalysis.
• The findings highlight the versatility of iron hydride clusters in chemical transformations.