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6933762 
Journal Article 
Isolated Cationic Organometallic Nickel(I) Arene Complexes 
Schwab, MM; Himmel, D; Kacprzak, S; Yassine, Z; Kratzert, D; Felbek, C; Weber, S; Krossing, I; , 
2019 
Yes 
European Journal of Inorganic Chemistry
ISSN: 1434-1948
EISSN: 1099-0682 
WILEY-V C H VERLAG GMBH 
WEINHEIM 
2019 
28 
3309-3317 
English 
WOS:000476032400001 
The Ni-I salt [Ni(cod)(2)](+)[Al(ORF)(4)](-) {R-F = 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 eta(6)-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.