Reactivity of [K3(phen)8][Cu(NPh2)2]3—a possible intermediate in the copper(i)-catalyzed N-arylation of N-phenylaniline?

Dalton Transactions Pub Date: 2014-02-24 DOI: 10.1039/C4DT00051J

Abstract

Complex [K3(phen)8][Cu(NPh2)2]3 (1, phen = phenanthroline) was isolated from the catalytic C–N cross coupling reaction based on the CuI-phen-tBuOK catalytic system. Complex 1 can react with 4-iodotoluene to give 4-methyl-N,N-diphenylaniline (3a) in 50% yield (based on all available NPh2? ligands of complex 1). In addition, 1 can also work as an effective catalyst for the C–N coupling reactions under the same reaction conditions, indicating that 1 may be an effective intermediate of the catalytic system. In the presence of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO), a radical scavenger, the stoichiometric reaction between complex 1 and 4-iodotoluene was significantly quenched to give a low yield of 12%. The results suggest that the radical path dominates in the reaction, with (phen)KNPh2 as the possible radical source. The structures of 1 and (phen)KNPh2 were both determined by single crystal X-ray diffraction studies.

Graphical abstract: Reactivity of [K3(phen)8][Cu(NPh2)2]3—a possible intermediate in the copper(i)-catalyzed N-arylation of N-phenylaniline
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