Side-On N <sub>2</sub> Binding and Reduction by a Heterotetrametallic Zr <sub>2</sub> Co <sub>2</sub> Cluster
In multimetallic compounds, N<sub>2</sub> typically bridges late transition metals in an end-on (η<sup>1</sup>:η<sup>1</sup>) fashion while early transition metals often bind N<sub>2</sub> side-on (η<sup>2</sup>), with the latter resulting in more significant N-N bond elongation. Herein, N<sub>2</sub> fixation is accomplished by using a well-defined scaffold featuring a heterobimetallic combination of Zr and Co. We report a heterotetrametallic Zr<sub>2</sub>Co<sub>2</sub> cluster in which N<sub>2</sub> is bound side-on to the two Co centers and end-on to Zr in a μ<sub>3</sub>-η<sup>1</sup>:η<sup>2</sup>:η<sup>2</sup> binding mode that defies established paradigms for N<sub>2</sub> binding. The heterometallic approach is shown to facilitate catalytic reductive silylation of N<sub>2</sub> with turnover numbers far exceeding those of reported cobalt catalysts.
Authors
- Christine M. Thomas (ORCID: https://orcid.org/0000-0001-5009-0479)
- Curtis E. Moore (ORCID: https://orcid.org/0000-0002-3311-7155)
- Adwitiya Singh
Institutions
- The Ohio State University (US)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2025-10-25
- DOI
- https://doi.org/10.1021/jacs.5c14342
- Citations
- 1
- Primary Topic
- Ammonia Synthesis and Nitrogen Reduction
- Type
- article
- Field-Weighted Citation Impact
- 0.39