Oxidative Addition of Aryl Electrophiles to a Prototypical Nickel(0) Complex: Mechanism and Structure/Reactivity Relationships

Bajo, S. (Universidad de Zaragoza) ; Laidlaw, G. ; Kennedy, A.R. ; Sproules, S. ; Nelson, D.J.

Resumen: Detailed kinetic studies of the reaction of a model Ni-0 complex with a range of aryl electrophiles have been conducted. The reactions proceed via a fast ligand exchange pre-equilibrium, followed by oxidative addition to produce either [(NiX)-X-I(dppf)] (and biaryl) or [Ni-II(Ar)X(dppf)]; the ortho substituent of the aryl halide determines selectivity between these possibilities. A reactivity scale is presented in which a range of substrates is quantitatively ranked in order of the rate at which they undergo oxidative addition. The rate of oxidative addition is loosely correlated to conversion in prototypical cross-coupling reactions. Substrates that lead to Ni-I products in kinetic experiments conditions. produce more homocoupling products under catalytic conditions.

Idioma: Inglés

DOI: 10.1021/acs.organomet.7b00208

Año: 2017

Publicado en: Organometallics 36, 8 (2017), 1662-1672
ISSN: 0276-7333

Factor impacto JCR: 4.051 (2017)

Categ. JCR: CHEMISTRY, ORGANIC rank: 11 / 57 = 0.193 (2017) - Q1 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 7 / 45 = 0.156 (2017) - Q1 - T1

Factor impacto SCIMAGO: 1.652 - Inorganic Chemistry (Q1) - Physical and Theoretical Chemistry (Q1) - Organic Chemistry (Q1)

Tipo y forma: Artículo (Versión definitiva)

Área (Departamento): Área Química Inorgánica (Dpto. Química Inorgánica)