Dinitrogen Insertion and Cleavage by a Metal-Metal Bonded Tricobalt(I) Cluster.

ABSTRACT: 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 Co^I₃ cluster, Co₃L^Et/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 (PBE0/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

SUBMITTER: Eaton MC 

PROVIDER: S-EPMC8247452 | biostudies-literature | 2021 Apr

REPOSITORIES: biostudies-literature