C-H Activation of Inert Arenes using a Photochemically Activated Guanidinato-Magnesium(I) Compound

UV irradiation of solutions of a guanidinate coordinated dimagnesium(I) compound, [{(Priso)Mg}₂ ] 3 (Priso=[(DipN)₂ CNPrⁱ ₂ ]^- , Dip=2,6-diisopropylphenyl), in either benzene, toluene, the three isomers of xylene, or mesitylene, leads to facile activation of an aromatic C-H bond of the solvent in all cases, and formation of aryl/hydride bridged magnesium(II) products, [{(Priso)Mg}₂ (μ-H)(μ-Ar)] 4-9. In contrast to similar reactions reported for β-diketiminate coordinated counterparts of 3, these C-H activations proceed with little regioselectivity, though they are considerably faster. Reaction of 3 with an excess of the pyridine, p-NC₅ H₄ Bu^t (py^But ), gave [(Priso)Mg(py^But H)(py^But )₂ ] 10, presumably via reduction of the pyridine to yield a radical intermediate, [(Priso)Mg(py^But ⋅)(py^But )₂ ] 11, which then abstracts a proton from the reaction solvent or a reactant. DFT calculations suggest two possible pathways to the observed arene C-H activations. One of these involves photochemical cleavage of the Mg-Mg bond of 3, generating magnesium(I) doublet radicals, (Priso)Mg⋅. These then doubly reduce the arene substrate to give "Birch-like" products, which subsequently rearrange via C-H activation of the arene. Circumstantial evidence for the photochemical generation of transient magnesium radical species includes the fact that irradiation of a cyclohexane solution of 3 leads to an intramolecular aliphatic C-H activation process and formation of an alkyl-bridged magnesium(II) species, [{Mg(μ-Priso^-H )}₂ ] 12. Furthermore, irradiation of a 1 : 1 mixture of 3 and the β-diketiminato dimagnesium(I) compound, [{(^Dip Nacnac)Mg}₂ ] (^Dip Nacnac=[HC(MeCNDip)₂ ]^- ), effects a "scrambling" reaction, and the near quantitative formation of an unsymmetrical dimagnesium(I) compound, [(Priso)Mg-Mg(^Dip Nacnac)] 13. Finally, the EPR spectrum (77 K) of a glassed solution of UV irradiated 3 is dominated by a broad featureless signal, indicating the presence of a doublet radical species.