Synthesis, Characterization and Reactivity of N-Heterocyclic Carbene Gold(III) Complexes

• Published in: Organometallics 2007-03, Vol.26 (6), p.1376-1385
• Main Authors: de Frémont, Pierre, Singh, Rohit, Stevens, Edwin D, Petersen, Jeffrey L, Nolan, Steven P
• Format: Article
• Language: English
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/om060887t

A series of (NHC)AuICl (1, NHC = N,N‘-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr); 2, NHC = N,N‘-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes); 3, NHC = N,N‘-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (SIPr); 4, NHC = N,N‘-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes); 5, NHC = N,N‘-dicyclohexylimidazol-2-ylidene (ICy); 6, NHC = N,N‘-diadamantylimidazol-2-ylidene (IAd); 7, NHC = N,N‘-di-tert-butylimidazol-2-ylidene (I t Bu)) complexes were reacted with LiBr to generate [(IPr)AuBr] (8), [(IMes)AuBr] (9), [(SIPr)AuBr] (10), [(SIMes)AuBr] (11), [(ICy)AuBr] (12), [(IAd)AuBr] (13), and [(I t Bu)AuBr] (14). These (NHC)AuIBr complexes undergo oxidative addition of elemental bromine, leading to the new Au(III) complexes [(IPr)AuBr3] (15), [(IMes)AuBr3] (16), [(SIPr)AuBr3] (17), [(SIMes)AuBr3] (18), [(ICy)AuBr3] (19), [(IAd)AuBr3] (20), and [(I t Bu)AuBr3] (21). Complete characterization by NMR spectroscopy and single-crystal X-ray diffraction were performed in order to discern structural differences between organogold(I/III) congeners. A preliminary study examining the activity of (NHC)AuIII species on the addition of water to alkynes is also presented.