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Side-On N₂ Binding and Reduction by a Heterotetrametallic Zr₂Co₂ Cluster

Adwitiya Singh¹, Curtis E Moore¹, Christine M Thomas¹

¹Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.

Journal of the American Chemical Society

|October 25, 2025

Abstract

None:

In multimetallic compounds, N₂ typically bridges late transition metals in an end-on (η¹:η¹) fashion while early transition metals often bind N₂ side-on (η²), with the latter resulting in more significant N-N bond elongation. Herein, N₂ fixation is accomplished by using a well-defined scaffold featuring a heterobimetallic combination of Zr and Co. We report a heterotetrametallic Zr₂Co₂ cluster in which N₂ is bound side-on to the two Co centers and end-on to Zr in a μ₃-η¹:η²:η² binding mode that defies established paradigms for N₂ binding. The heterometallic approach is shown to facilitate catalytic reductive silylation of N₂ with turnover numbers far exceeding those of reported cobalt catalysts.

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