CH Activation of Benzene by a Photoactivated NiII(azide): Formation of a Transient Nickel Nitrido Complex |
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| Authors: | Vincent Vreeken Dr Maxime A Siegler Prof Dr Bas de Bruin Prof Dr Joost N H Reek Dr Martin Lutz Dr Ir Jarl Ivar van der Vlugt |
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| Affiliation: | 1. Homogeneous, Bioinspired & Supramolecular Catalysis van't Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1098 XH Amsterdam (The Netherlands);2. Department of Chemistry, John Hopkins University, 3400 N Charles Street, Baltimore, MD 21218 (USA);3. Department of Chemistry, Utrecht University, Padualaan 8, 3584 CH Utrecht (The Netherlands) |
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| Abstract: | Photochemical activation of nickel‐azido complex 2 Ni(N3)(PNP)] (PNHP=2,2′‐di(isopropylphosphino)‐4,4′‐ditolylamine) in neat benzene produces diamagnetic complex 3 Ni(Ph)(PNPNH)], which is crystallographically characterized. DFT calculations support photoinitiated N2‐loss of the azido complex to generate a rare, transient NiIV nitrido species, which bears significant nitridyl radical character. Subsequent trapping of this nitrido through insertion into the Ni? P bond generates a coordinatively unsaturated NiII 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)(PNPNH)] 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. |
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| Keywords: | azides C H activation iminophosphoranes nickel nitridyl radical |
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