2026-04-27T13:52:22Zhttps://uvadoc.uva.es/oai/request

oai:uvadoc.uva.es:10324/287172021-07-06T08:34:36Zcom_10324_28542com_10324_952com_10324_894col_10324_28543

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 SI