title: Photochemically induced reductive elimination as a route to a zirconocene complex with a strongly activated N₂ ligand.
abstract: The zirconocene dinitrogen complex [{(η(5)-C5Me4H)2Zr}2(μ2,η(2),η(2)-N2)] was synthesized by photochemical reductive elimination from the corresponding zirconium bis(aryl) or aryl hydride complexes, providing a high-yielding, alkali metal-free route to strongly activated early-metal N2 complexes. Mechanistic studies support the intermediacy of zirconocene arene complexes that in the absence of sufficient dinitrogen promote C-H activation or undergo comproportion to formally Zr(III) complexes. When N2 is in excess arene displacement gives rise to strong dinitrogen activation.
authors.affiliation: Department of Chemistry, Princeton University, 292 Frick Laboratory, Princeton, NJ 08544 (USA).
authors.forename: Grant W
authors.initials: GW
authors.lastname: Margulieux
authors.forename: Scott P
authors.initials: SP
authors.lastname: Semproni
authors.forename: Paul J
authors.initials: PJ
authors.lastname: Chirik
keywords: nitrogen fixation; photochemistry; reductive elimination; zirconium