Open AccessDinitrogen Insertion and Cleavage by a Metal–Metal Bonded Tricobalt(I) Cluster
Author(s) -
Mary C. Eaton,
Vincent J. Catalano,
Jason Shearer,
Leslie J. Murray
Publication year - 2021
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/jacs.1c01840
Subject(s) - chemistry , metal , trimethylsilyl , halide , cluster (spacecraft) , bond cleavage , photochemistry , crystallography , ligand (biochemistry) , steric effects , yield (engineering) , bromide , carbyne , tris , amine gas treating , inorganic chemistry , stereochemistry , medicinal chemistry , carbene , organic chemistry , catalysis , biochemistry , materials science , receptor , computer science , metallurgy , programming language
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 I 3 cluster, Co 3 L 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 (μ 3 -η 1 :η 2 :η 1 -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 N 2 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 Me 3 SiBr results in N 2 scission with tris(trimethylsilyl)amine afforded in good yield.
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