Ni(I)–XComplexes Bearing a Bulky α‑DiimineLigand: Synthesis, Structure, and Superior Catalytic Performance inthe Hydrogen Isotope Exchange in Pharmaceuticals
2019
The synthesis and spectroscopic characterization of a family of Ni–X (X = Cl, Br, I, H) complexes supported by the bulky α-diimine chelate N,N′-bis(1R,2R,3R,5S)-(−)-isopinocampheyl-2,3-butanediimine (ipcADI) are described. Diimine-supported, three-coordinate nickel(I)–X complexes have been proposed as key intermediates in a host of catalytic transformations such as C–C and C–heteroatom cross-coupling and C–H functionalization but have until now remained synthetically elusive. A combination of structural, spectroscopic, electrochemical, and computational studies were used to establish the electronic structure of each monomeric [(ipcADI)NiX] (X = Cl, Br, I) complex as a nickel(I) derivative supported by a redox-neutral α-diimine chelate. The dimeric nickel hydride, [(ipcADI)Ni(μ2-H)]2, was prepared and characterized by X-ray diffraction; however, magnetic measurements and 1H NMR spectroscopy support monomer formation at ambient temperature in THF solution. This nickel hydride was used as a precatalyst for t...
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