The Activation of Sulfur Hexafluoride at Highly Reduced Low‐Coordinate Nickel Dinitrogen Complexes

The greenhouse gas sulfur hexafluoride is the common standard example in the literature of a very inert inorganic small molecule that is even stable against O₂ in an electric discharge. However, a reduced β‐diketiminate nickel species proved to be capable of converting SF₆ into sulfide and fluoride compounds at ambient standard conditions. The fluoride product complex features an unprecedented [NiF]⁺ unit, where the Ni atom is only three‐coordinate, while the sulfide product exhibits a rare almost linear [Ni(μ‐S)Ni]²⁺ moiety. The reaction was monitored applying ¹H NMR, IR and EPR spectroscopic techniques resulting in the identification of an intermediate nickel complex that gave insight into the mechanism of the eight‐electron reduction of SF₆.