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Título
Ranking Ligands by Their Ability to Ease (C6F5)2NiIIL → Ni0L + (C6F5)2 Coupling versus Hydrolysis: Outstanding Activity of PEWO Ligands
Autor
Año del Documento
2020
Editorial
American Chemical Society
Descripción
Producción Científica
Documento Fuente
Inorganic Chemistry, 2020, 59, 24, 18287–18294
Abstract
The NiII literature complex cis-[Ni(C6F5)2(THF)2] is a synthon of cis-Ni(C6F5)2 that allows us to establish a protocol to measure and compare the ligand effect on the NiII → Ni0 reductive elimination step (coupling), often critical in catalytic processes. Several ligands of different types were submitted to this Ni-meter comparison: bipyridines, chelating diphosphines, monodentate phosphines, PR2(biaryl) phosphines, and PEWO ligands (phosphines with one potentially chelate electron-withdrawing olefin). Extremely different C6F5–C6F5 coupling rates, ranging from totally inactive (producing stable complexes at room temperature) to those inducing almost instantaneous coupling at 25 °C, were found for the different ligands tested. The PR2(biaryl) ligands, very efficient for coupling in Pd, are slow and inefficient in Ni, and the reason for this difference is examined. In contrast, PEWO type ligands are amazingly efficient and provide the lowest coupling barriers ever observed for NiII complexes; they yield up to 96% C6F5–C6F5 coupling in 5 min at 25 °C (the rest is C6F5H) and 100% coupling with no hydrolysis in 8 h at −22 to −53 °C.
Materias Unesco
23 Química
ISSN
0020-1669
Revisión por pares
SI
Patrocinador
Ministerio de Economía, Industria y Competitividad (Projects CTQ2017-89217-P and CTQ2016-80913-P)
Junta de Castilla y León (projects VA051P17 and VA062G18)
Ministerio de Economía, Industria y Competitividad FPI scholarship (BES-2017-080726)
Junta de Castilla y León (projects VA051P17 and VA062G18)
Ministerio de Economía, Industria y Competitividad FPI scholarship (BES-2017-080726)
Version del Editor
Propietario de los Derechos
© 2020 American Chemical Society
Idioma
eng
Tipo de versión
info:eu-repo/semantics/acceptedVersion
Derechos
openAccess
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