Organoactinides promote the Tishchenko reaction: The myth of inactive actinide-alkoxo complexes

TY - JOUR

T1 - Organoactinides promote the Tishchenko reaction

T2 - The myth of inactive actinide-alkoxo complexes

AU - Andrea, Tamer

AU - Barnea, Eyal

AU - Eisen, Moris S.

PY - 2008/2/27

Y1 - 2008/2/27

N2 - For many decades, compounds containing oxygen atoms were excluded from the actinide-catalysis field because of the high oxophilic nature of these complexes. Pursuing the conceptual question about the potential activity of actinide-oxo bonds we were surprised to find that the coupling of aromatic aldehydes catalyzed by Cp*2ThMe2 and Th(NEtMe)4 via thorium-alkoxide intermediates takes place in high yields to produce the corresponding esters. In this paper we present our breakthrough results including comprehensive mechanistic, deuterium labeling, kinetic, and thermodynamic studies. A plausible mechanism is presented taking into account as well the thermochemistry of the process.

AB - For many decades, compounds containing oxygen atoms were excluded from the actinide-catalysis field because of the high oxophilic nature of these complexes. Pursuing the conceptual question about the potential activity of actinide-oxo bonds we were surprised to find that the coupling of aromatic aldehydes catalyzed by Cp*2ThMe2 and Th(NEtMe)4 via thorium-alkoxide intermediates takes place in high yields to produce the corresponding esters. In this paper we present our breakthrough results including comprehensive mechanistic, deuterium labeling, kinetic, and thermodynamic studies. A plausible mechanism is presented taking into account as well the thermochemistry of the process.

UR - http://www.scopus.com/inward/record.url?scp=39749085755&partnerID=8YFLogxK

U2 - 10.1021/ja710843q

DO - 10.1021/ja710843q

M3 - 文章

C2 - 18232694

AN - SCOPUS:39749085755

SN - 0002-7863

VL - 130

SP - 2454

EP - 2455

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 8

ER -