Photochemically Induced Reductive Elimination as a Route to a Zirconocene Complex with a Strongly Activated N2 Ligand

摘要

The zirconocene dinitrogen complex [f(rf-C5Me4H)2Zr}2(μ2,η~2,~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 compropor-tion to formally Zr~(III) complexes. When N2 is in excess arene displacement gives rise to strong dinitrogen activation.