title: Copper(I)-anilide complex [Na(phen)3][Cu(NPh2)2]: an intermediate in the copper-catalyzed N-arylation of N-phenylaniline.
abstract: Complex [Na(phen)(3)][Cu(NPh(2) )(2)](2), containing a linear bis(N-phenylanilide)copper(I) anion and a distorted octahedral tris(1,10-phenanthroline)sodium counter cation, has been isolated from the catalytic C-N cross-coupling reaction with the CuI/phen/tBuONa (phen=1,10-phenanthroline) catalytic system. Complex 2 can react with 4-iodotoluene to produce 4-methyl-N,N-diphenylaniline (3 a) with 70.6 % yield. In addition, 2 can work as an effective catalyst for C-N coupling under the same reaction conditions, thus indicating that 2 is the intermediate of the catalytic system. Both [Cu(NPh(2))(2)](-) and [Cu(NPh(2))I](-) have been observed by in situ electron ionization mass spectrometry (ESI-MS) under catalytic reaction conditions, thus confirming that they are intermediates in the reaction. A catalytic cycle has been proposed based on these observations. The molecular structure of 2 has been determined by single-crystal X-ray diffraction analysis.
authors.affiliation: Institute of Chemistry Academia Sinica, Taipei, Taiwan, Republic of China.
authors.forename: Chia-Kai
authors.initials: CK
authors.lastname: Tseng
authors.forename: Chi-Rung
authors.initials: CR
authors.lastname: Lee
authors.forename: Chien-Chung
authors.initials: CC
authors.lastname: Han
authors.forename: Shin-Guang
authors.initials: SG
authors.lastname: Shyu