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Dispersion Forces, Disproportionation, and Stable High‐Valent Late Transition Metal Alkyls
Author(s) -
Liptrot David J.,
Guo JingDong,
Nagase Shigeru,
Power Philip P.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201607360
Subject(s) - disproportionation , homolysis , isodesmic reaction , chemistry , dispersion (optics) , london dispersion force , transition metal , density functional theory , bromide , metal , computational chemistry , crystallography , inorganic chemistry , molecule , catalysis , organic chemistry , radical , van der waals force , physics , optics
The transition metal tetra‐ and trinorbornyl bromide complexes, M(nor) 4 (M=Fe, Co, Ni) and Ni(nor) 3 Br (nor=1‐bicyclo[2.2.1]hept‐1‐yl) and their homolytic fragmentations were studied computationally using hybrid density functional theory (DFT) at the B3PW91 and B3PW91‐D3 dispersion‐corrected levels. Experimental structures were well replicated; the dispersion correction resulted in shortened M−C bond lengths for the stable complexes, and it was found that Fe(nor) 4 receives a remarkable 45.9 kcal mol −1 stabilization from the dispersion effects whereas the tetragonalized Co(nor) 4 shows stabilization of 38.3 kcal mol −1 . Ni(nor) 4 was calculated to be highly tetragonalized with long Ni−C bonds, providing a rationale for its current synthetic inaccessibility. Isodesmic exchange evaluation for Fe(nor) 4 confirmed that dispersion force attraction between norbornyl substituents is fundamental to the stability of these species.