ABSTRACT
Unambiguous assignment of redox sites on ferrocene coupled N-heterocyclic carbene gold(I) complexes [(Fc-NHC)2Au(I)]+ is critical to gain a greater mechanistic understanding of their activity in a cellular environment. Such information can be garnered with isolation and detailed characterization of the oxidized version of [(Fc-NHC)2Au(I)]+. Herein we disclose a study that unambiguously illustrates redox events pertaining to [(Fc-NHC)2Au(I)]+ that stem exclusively from ferrocene sites. This work also describes novel synthetic methodologies for isolating ferrocenium coupled N-heterocyclic carbene gold(I) complexes.
ABSTRACT
Zn(OTf)2 (OTf- = trifluoromethanesulfonate) catalyzes the silylation of pyridine, 3-picoline, and quinoline to afford the silylated products, where the silyl groups are meta to the nitrogen. The isolated yields of the products range from 41 to 26%. The 2- and 4-picolines yielded the silylmethylpyridines, where the CH3 groups were silylated instead of the ring. The pyridine silylation can occur via two separate pathways, involving either a 1,4- or a 1,2-hydrosilylation of pyridine as the first step. A byproduct of the pyridine silylation is a head-to-tail dimerization of N-silyl-1,4-dihydropyridine to form a diazaditwistane molecule.
