NiCl2(dtbbpy)

Technical Specifications

Product Description & Scientific Applications

NiCl2(dtbbpy) [(4,4'-dtbbpy)NiCl2] is the preformed nickel(II) dichloride complex of 4,4'-di-tert-butyl-2,2'-bipyridine (C18H24Cl2N2Ni, 398.0 g/mol). Preformed is not merely convenient: in α-arylation of N-alkyl N-heterocycles the well-defined complex showed significantly higher activity than NiCl2 alone or NiCl2 combined with the dtbbpy ligand in the flask.

Ni(I)(dtbbpy)+ is the species that performs oxidative addition to an aryl bromide. The solid is air-stable, but stability is not inertness: in Ir/Ni coupling in DMF under CFL irradiation molecular oxygen was essential for activation, where Ni(COD)2 required none.

Applications and Reactions

• α-Arylation of N-heterocycles: 7 mol% with 2 mol% [Ir(dF(CF3)ppy)2(dtbbpy)][PF6], 2,6-lutidine, DMF, 440 nm blue LED — 81% isolated yield.
• Aldehyde synthesis: with an iridium photocatalyst under blue LED, aryl chlorides functionalise 1,3-dioxolane at C2, giving aryl and heteroaryl aldehydes after mild acidic workup.
• C–N amidation: irradiated with an organic amine base, aryl chlorides couple with amides in 80% isolated yield.
• Decarboxylative coupling: oxamates with aryl bromides, 4CzIPN photocatalyst, DMA, 456 nm, 40–45 °C — 71%.
• C(sp3)–H arylation: with TBADT as HAT co-catalyst at 390 nm, gives 1,2-diaryl-syn-diols in 83% yield and greater than 20:1 diastereoselectivity.
• Alkene dicarbofunctionalisation: three-component coupling of electron-deficient alkenes, alcohols and aryl bromides under acridinium/PCET catalysis at 450 nm — 82%.
• Electrochemical cross-electrophile coupling: 2 mol% with a cobalt phthalocyanine mediator sustains 12 mA/cm2 at 95% yield; unmediated, C(sp2)–C(sp3) coupling runs at 73%.
• Aryl esterification: with an energy-transfer photocatalyst in 1:1 DMSO/toluene, benzoic acid couples to 5-bromophthalide in 81% yield.
• Limitations: performance is ligand-sensitive, not universal. In an electrochemical Ni-catalysed C–N coupling of an aryl halide with pyrrolidine, dtbbpy gave 22% where other sp2-N ligands did better — worth screening alternatives when electrochemical amination is the target.

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