M. Fuss, H. Siehl, B. Olenyuk
Jan 27, 1999
Citations
0
Influential Citations
32
Citations
Journal
Organometallics
Abstract
In the reaction between 3-picoline, 2-bromo-5-methylpyridine, 2-methylquinoline, 3-methylisoquinoline, and [M(R-(+)-BINAP)][OTf]2 (M = Pd, Pt; BINAP = 2,2‘-bis(diphenylphosphino)-1,1‘-binaphthyl), the nature and the distribution of the products were investigated by various physical and spectroscopic methods. The α-substituents on the heteroaryl ring, such as the bromine atom in 2-bromo-5-methylpyridine or the methyl group in 2-methylquinoline, tend to promote the simultaneous formation of mono(heteroaryl)- and bis(heteroaryl)-containing products. The reaction of the most sterically demanding 2-methylquinoline favors the formation of mono(heteroaryl) complexes exclusively within the limits of NMR detection. Reaction of 3-picoline with the chiral Pd(II) and Pt(II) bis(triflates) results in the formation of diastereomeric, square-planar, cationic complexes, due to the hindered rotation about the metal−nitrogen heteroaryl bond. 1H NMR variable-temperature studies of [M(R-(+)-BINAP)(3-picoline)2][OTf]2 were pe...