Isolated Cationic Organometallic Nickel(I) Arene Complexes.

The NiI salt [Ni(cod)2]+[Al(ORF)4]– {RF = C(CF3)3} is the starting material for ligand exchange reactions with arenes (benzene, mesitylene and hexamethylbenzene) yielding cationic and purely organometallic 19 valence electron [Ni(cod)(arene)]+ complex salts. The reactions are accompanied by fast solution color changes from yellow to intensely green. Single crystal X‐ray structure analysis, EPR, UV/Vis and IR‐spectroscopic investigations confirm the formation of [Ni(cod)(C6Me6)][Al(ORF)4] (2) as well as [Ni(cod)(mes)][Al(ORF)4] (3, mes = mesitylene) with η6‐coordinated arenes and bidentate cod ligands. The reaction with benzene is plausible but remains less characterized. The energetics of these reactions were used to evaluate diverse DFT methods. 16 functionals with and without D3(BJ) dispersion correction failed to describe the reaction energetics correctly. However, correcting the basic reaction energies with a CCSD(T)/TZ→QZ approach and using further isodesmic reactions with inclusion of COSMO‐RS solvation gave reaction energetics in best agreement with all experimental observations. [ABSTRACT FROM AUTHOR]