title: Nucleophilicities and carbon basicities of pyridines.
abstract: Rate and equilibrium constants for the reactions of pyridines with donor-substituted benzhydrylium ions have been determined spectrophotometrically. The correlation equation log k(20 degrees C)=s(N+E), in which s and N are nucleophile-specific parameters and E is an electrophile-specific parameter, has been used to determine the nucleophilicity parameters of various pyridines in CH(2)Cl(2) and aqueous solution and to compare them with N of other nucleophiles. It is found that the nucleophilic organocatalyst 4-(dimethylamino)pyridine (DMAP) and tertiary phosphanes have comparable nucleophilicities and carbon basicities despite widely differing Brønsted basicities. For that reason, these reactivity parameters are suggested as guidelines for the development of novel organocatalysts. The Marcus equation is employed for the determination of the intrinsic barriers of these reactions.
authors.affiliation: Department Chemie und Biochemie, Ludwig-Maximilians-Universität München, Butenandtstr. 5-13 (Haus F), 81377 München, Germany.
authors.forename: Frank
authors.initials: F
authors.lastname: Brotzel
authors.forename: Bernhard
authors.initials: B
authors.lastname: Kempf
authors.forename: Thomas
authors.initials: T
authors.lastname: Singer
authors.forename: Hendrik
authors.initials: H
authors.lastname: Zipse
authors.forename: Herbert
authors.initials: H
authors.lastname: Mayr