The First Cyanomethyl Complex of Gold, Synthesized by Reaction of a AuI Complex with Acetonitrile in the Presence of a New Guanidine N-Superbase

• Published in: European Journal of Inorganic Chemistry 2010, Vol.2010 (30), p.4783-4789
• Main Authors: Emeljanenko, Dimitri, Peters, Anastasia, Vitske, Viktoriia, Kaifer, Elisabeth, Himmel, Hans-Jörg
• Format: Review
• Language: English
• Subjects: C-H acidity; C-H activation; Gold; Guanidine; Superbase
• ISSN: 1434-1948; 1099-0682
• DOI: 10.1002/ejic.201000691

Herein we report on the synthesis of the new strong N‐base and electron donor tdmegb [1,2,4,5‐tetrakis(N,N′‐dimethylethyleneguanidino)benzene]. Compared to the previously synthesized ttmgb [1,2,4,5‐tetrakis(tetramethylguanidino)benzene], this compound turned out to be a slightly better electron donor and a slightly weaker base. In experiments in which [AuCl(PPH3)] was dissolved in CH3CN together with tdmegb, we observed the formation of the first cyanomethyl complex of Au, namely [Au(CH2CN)(PPh3)] in good yield. This reaction does not take place for ttmgb. Moreover, in CH2Cl2 solutions containing the three components [AuCl(PPh3)], tdmegb and a nitrile (in large excess), only AuI reduction leading to a [Au11Cl3(PPh3)7] cluster is observed. Possible reaction mechanisms for this unusual reaction are discussed. The first cyanomethyl complex of gold, synthesized by reaction between an AuI complex and acetonitrile in the presence of a new guanidine N‐superbase C–H bond activation of acetonitrile by AuI in combination with a newly designed nitrogen base leads to the first structurally characterized (cyanomethyl)gold complex.