Cationic arene complexes [Cb*Co(naphthalene)] + (2, Cb* = C 4 Me 4 ) and [Cb*Co(phenanthrene)] + were synthesized by the reactions of [Cb*Co(MeCN) 3 ] + with arenes. The [Cb*Co(anthracene)] + complex was synthesized by the abstraction of the iodide ion from [Cb*CoI] 2 by TlВF 4 in the presence of anthracene. Complex 2 exchanges the naphthalene ligand for other arenes at room temperature.

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The mononuclear arene complexes [Cb*Co(arene)] + (3a-g; Cb* = C 4 Me 4 ; arene is biphenyl (a), diphenylmethane (b), 1,2 diphenylethane (c), diphenyl ether (d), p terphenyl (e), 1,2 dimesi tylethane (f), or 1,3 dimesitylpropane (g)) were synthesized by the reactions of arenes either with the benzene complex [Cb*Co(C 6 H 6 )] + (1) under visible light irradiation or with the acetonitrile derivative [Cb*Co(MeCN) 3 ] + (2) in refluxing THF. The reactions of 2 with 1,2 diphenyle thane, 1,3 dimesitylpropane, and p terphenyl in a ratio of 2 : 1 afforded the dinuclear complexes [Cb*Co(μ η:η arene)CoCb*] 2+ (4c,e,g). The stability of the dinuclear arene complexes was estimat ed by DFT calculations. The structures of the complexes [3a]PF 6 and [3e]PF 6 were established by X ray diffraction.

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