Dispersion Forces,Disproportionation, and Stable High‐Valent Late Transition Metal Alkyls |
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| Authors: | Dr David J Liptrot Dr Jing‐Dong Guo Prof Shigeru Nagase Prof Philip P Power |
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| Institution: | 1. Department of Chemistry, University of California, Davis, CA, USA;2. Fukui Institute for Fundamental Chemistry, Kyoto University, Kyoto, Japan |
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| Abstract: | The transition metal tetra‐ and trinorbornyl bromide complexes, M(nor)4 (M=Fe, Co, Ni) and Ni(nor)3Br (nor=1‐bicyclo2.2.1]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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| Keywords: | density functional calculations dispersion forces high oxidation states organometallics transition metals |
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