2024-03-29T01:13:41Zhttp://uvadoc.uva.es/oai/requestoai:uvadoc.uva.es:10324/287172021-07-06T08:34:36Zcom_10324_28542com_10324_952com_10324_894col_10324_28543
2018-10-10T23:40:32Z
urn:hdl:10324/28717
Speciation of ZnMe2, ZnMeCl, and ZnCl2 in Tetrahydrofuran (THF), and Its Influence on Mechanism Calculations of Catalytic Processes
Pozo, Juan del
Pérez Iglesias, María
Álvarez, Rosana
Lledós, Agustí
Casares González, Juan Ángel
Espinet Rubio, Pablo
Producción Científica
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.
2018-02-27T10:03:19Z
2018-10-10T23:40:32Z
2017
info:eu-repo/semantics/article
ACS Catalysis, 2017, 7 (5), pp 3575–3583
2155-5435
http://uvadoc.uva.es/handle/10324/28717
10.1021/acscatal.6b03636
ACS Catalysis
eng
https://pubs.acs.org/doi/abs/10.1021/acscatal.6b03636
info:eu-repo/semantics/openAccess
© 2017 American Chemical Society
American Chemical Society