147043-22-9Relevant academic research and scientific papers
Dialkyl Ether Formation at High-Valent Nickel
Le Vaillant, Franck,Reijerse, Edward J.,Leutzsch, Markus,Cornella, Josep
, p. 19540 - 19550 (2020)
In this article, we investigated the I2-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(sp3)-OC(sp3) using I2 might not be operative. We isolated a paramagnetic bimetallic NiIII intermediate featuring a unique Ni2(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(sp3)-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(sp3)-I bond. The results of this article indicate that the use of F+ oxidants permits the challenging C(sp3)-OC(sp3) 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 NiIII 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.
Oxygen-atom transfer from nitrous oxide (N=N=O) to nickel alkyls. Syntheses and reactions of nickel(II) alkoxides
Matsunaga, Phillip T.,Mavropoulos, John C.,Hillhouse, Gregory L.
, p. 175 - 186 (1995)
The dialkyl nickel complexes (bipy)Ni(R)2 (1, R=Et; 2, R=iso-Bu; bipy .ident. 2,2'-bipyridine) react with nitrous oxide (1 atm) to generate nickel(II) alkoxy alkyl complexes (bipy)Ni(OR)(R) (3, R=Et; 4, R=iso-Bu), which in turn undergo CO-insertion follow
