Copper(I)–Anilide Complex [Na(phen) 3 ][Cu(NPh 2 ) 2 ]: An Intermediate in the Copper‐Catalyzed N‐Arylation of N ‐Phenylaniline

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 CN cross‐coupling reaction with the CuI/phen/ t BuONa (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 CN 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.