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Characterizing Lewis Pairs Using Titration Coupled with In Situ Infrared Spectroscopy
Published on: February 20, 2020
Dispersion Forces, Disproportionation, and Stable High-Valent Late Transition Metal Alkyls
David J Liptrot1, Jing-Dong Guo2, Shigeru Nagase2
1Department of Chemistry, University of California, One Shields Avenue, Davis, CA, 95616, USA.
Abstract:
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.
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