Dinitrogen Insertion and Cleavage by a Metal–Metal Bonded Tricobalt(I) Cluster
Reduction of a tricobalt(II) tri(bromide) cluster supported by a tris(β-diketiminate) cyclophane results in halide loss, ligand compression, and metal–metal bond formation to yield a 48-electron CoI3 cluster, Co3LEt/Me (2). Upon reaction of 2 with dinitrogen, all metal–metal bonds are broken, steric conflicts are relaxed, and dinitrogen is incorporated within the internal cavity to yield a formally (μ3-η1:η2:η1-dinitrogen)tricobalt(I) complex, 3. Broken symmetry DFT calculations (PBEο/def2-tzvp/D3) support an N–N bond order of 2.1 in the bound N2 with the calculated N–N stretching frequency (1743 cm–1) comparable to the experimental value (1752 cm–1). Reduction of 3 under Ar in the presence of Me3SiBr results in N2 scission with tris(trimethylsilyl)amine afforded in good yield.
American Chemical Society
Eaton, M. C., Catalano, V. J., Shearer, J., & Murray, L. J. (2021). Dinitrogen insertion and cleavage by a metal–metal bonded Tricobalt(I) cluster. Journal of the American Chemical Society, 143(15), 5649-5653. doi: 10.1021/jacs.1c01840
Journal of the American Chemical Society