Dialkyl Ether Formation at High-Valent Nickel

[Image: see text] In this article, we investigated the I(2)-promoted cyclic dialkyl ether formation from 6-membered oxanickelacycles originally reported by Hillhouse. A detailed mechanistic investigation based on spectroscopic and crystallographic analysis revealed that a putative reductive elimination to forge C(sp(3))–OC(sp(3)) using I(2) might not be operative. We isolated a paramagnetic bimetallic Ni(III) intermediate featuring a unique Ni(2)(OR)(2) (OR = alkoxide) diamond-like core complemented by a μ-iodo bridge between the two Ni centers, which remains stable at low temperatures, thus permitting its characterization by NMR, EPR, X-ray, and HRMS. At higher temperatures (>−10 °C), such bimetallic intermediate thermally decomposes to afford large amounts of elimination products together with iodoalkanols. Observation of the latter suggests that a C(sp(3))–I bond reductive elimination occurs preferentially to any other challenging C–O bond reductive elimination. Formation of cyclized THF rings is then believed to occur through cyclization of an alcohol/alkoxide to the recently forged C(sp(3))–I bond. The results of this article indicate that the use of F(+) oxidants permits the challenging C(sp(3))–OC(sp(3)) bond formation at a high-valent nickel center to proceed in good yields while minimizing deleterious elimination reactions. Preliminary investigations suggest the involvement of a high-valent bimetallic Ni(III) intermediate which rapidly extrudes the C–O bond product at remarkably low temperatures. The new set of conditions permitted the elusive synthesis of diethyl ether through reductive elimination, a remarkable feature currently beyond the scope of Ni.