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Copper(I)–Anilide Complex [Na(phen) 3 ][Cu(NPh 2 ) 2 ]: An Intermediate in the Copper‐Catalyzed N‐Arylation of N ‐Phenylaniline
Author(s) -
Tseng ChiaKai,
Lee ChiRung,
Han ChienChung,
Shyu ShinGuang
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201002661
Subject(s) - catalysis , chemistry , copper , crystal structure , crystallography , octahedron , yield (engineering) , catalytic cycle , mass spectrometry , medicinal chemistry , ion , organic chemistry , materials science , metallurgy , chromatography
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.