RT info:eu-repo/semantics/article
T1 Speciation of ZnMe2, ZnMeCl, and ZnCl2 in Tetrahydrofuran (THF), and Its Influence on Mechanism Calculations of Catalytic Processes
A1 Pozo, Juan del
A1 Pérez Iglesias, María
A1 Álvarez, Rosana
A1 Lledós, Agustí
A1 Casares González, Juan Ángel
A1 Espinet Rubio, Pablo
K1 Negishi
K1 Soluciones THF
AB This paper examines the speciation of ZnMe2, ZnMeCl, and ZnCl2 in tetrahydrofuran (THF) solution, and provides experimental (infrared (IR) and calorimetric experiments) and density functional theory (DFT) data to conclude that the species in THF solution are, beyond a doubt, ZnMe2(THF)2, ZnMeCl(THF)2, and ZnCl2(THF)2. Consequently, coordinated THF should be used in DFT mechanistic calculations (e.g., Negishi reactions in THF). Naked or single THF coordinated molecules are virtually nonexistent in THF solutions. A cluster-continuum model for the solvent is recommended to obtain a more-correct representation. The presence or absence of THF produces a marked effect on the thermodynamics of the Negishi catalysis and a lesser effect on the kinetics of the transmetalation.
PB American Chemical Society
SN 2155-5435
YR 2017
FD 2017
LK http://uvadoc.uva.es/handle/10324/28717
UL http://uvadoc.uva.es/handle/10324/28717
LA eng
NO ACS Catalysis, 2017, 7 (5), pp 3575–3583
NO Producción Científica
DS UVaDOC
RD 18-abr-2024