C-H Activation of Benzene by a Photoactivated Ni^II(azide): Formation of a Transient Nickel Nitrido Complex

Abstract Photochemical activation of nickel-azido complex 2 [Ni(N<inf>3</inf>)(PNP)] (PN^HP=2,2'-di(isopropylphosphino)-4,4'-ditolylamine) in neat benzene produces diamagnetic complex 3 [Ni(Ph)(PN^PN^H)], which is crystallographically characterized. DFT calculations support photoinitiated N<inf>2</inf>-loss of the azido complex to generate a rare, transient Ni^IV nitrido species, which bears significant nitridyl radical character. Subsequent trapping of this nitrido through insertion into the Ni-P bond generates a coordinatively unsaturated Ni^II imidophosphorane P=N donor. This species shows unprecedented reactivity toward 1,2-addition of a C-H bond of benzene to form 3. The structurally characterized chlorido complex 4 [Ni(Cl)(PN^PN^H)] is generated by reaction of 3 with HCl or by direct photolysis of 2 in chlorobenzene. This is the first report of aromatic C-H bond activation by a trapped transient nitrido species of a late transition metal.