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 (3a) 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. © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.