Dispersion Forces, Disproportionation, and Stable High-Valent Late Transition Metal Alkyls

详细信息    查看全文

• 作者：Dr. David J. Liptrot ; Dr. Jing-Dong Guo ; Prof. Shigeru Nagase and Prof. Philip P. Power
• 刊名：Angewandte Chemie
• 出版年：2016
• 出版时间：November 14, 2016
• 年：2016
• 卷：128
• 期：47
• 页码：14986-14989
• 全文大小：637K
• ISSN：1521-3757

文摘

The transition metal tetra- and trinorbornyl bromide complexes, M(nor)₄ (M=Fe, Co, Ni) and Ni(nor)₃Br (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.