Dialkyl Ether Formation at High-Valent Nickel.

ABSTRACT: 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 Ni^III 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

SUBMITTER: Le Vaillant F 

PROVIDER: S-EPMC7677934 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature