C(sp(3))-Cl Bond Activation Promoted by a POP-Pincer Rhodium(I) Complex

Curto, Sheila G. ; Heras, Laura A. de las ; Esteruelas, Miguel A. ; Olivan, Montserrat ; Oñate, Enrique

Resumen: The complex [RhCl(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (1; xant (PiPr(2))(2) = 9, 9-dimethyl-4, 5-bis-(diisopropylphosphino)xanthene) activates C(sp(3))-Cl bonds of mono- and dichloroalkanes and catalyzes the dehalogenation of chloroalkanes and the homocoupling of benzyl chloride. Complex 1 reacts with chlorocyclohexane to give [RhHCl2(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (2) and cyclohexene and promotes the dehalogenation of the chlorocycloalkane to cyclohexane using 2-propanol solutions of sodium formate as the reducing agent. The oxidative addition of benzyl chloride to 1 leads to [Rh(CH2Ph)Cl-2(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (4). The dehalogenation of this chloroalkane with 2-propanol solutions of sodium formate, in the presence of 1, gives toluene and 1, 2-diphenylethane. The latter is selectively formed with KOH instead of sodium formate. Complex 1 also reacts with trans-1, 2-dichlorocyclohexane and dichloromethane. The reaction with the former gives [RhCl3(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (5) and cyclohexene, whereas complex 1 undergoes oxidative addition of dichloromethane to afford cis-dichloride-[Rh(CH2Cl)-Cl-2(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (6a), which evolves into its trans-dichloride isomer 6b. The kinetic study of the overall process suggests that the oxidative addition is cis-concerted and the isomerization an intramolecular reaction which takes place through a sigma-C-Cl intermediate with two conformations.

Idioma: Inglés

DOI: 10.1021/acs.organomet.9b00409

Año: 2019

Publicado en: Organometallics 38, 15 (2019), 3074-3083
ISSN: 0276-7333

Factor impacto JCR: 3.804 (2019)

Categ. JCR: CHEMISTRY, ORGANIC rank: 12 / 57 = 0.211 (2019) - Q1 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 6 / 45 = 0.133 (2019) - Q1 - T1

Factor impacto SCIMAGO: 1.345 - Inorganic Chemistry (Q1) - Physical and Theoretical Chemistry (Q1) - Organic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA/E06-17R
Financiación: info:eu-repo/grantAgreement/ES/DGA/LMP148-18
Financiación: info:eu-repo/grantAgreement/ES/MECD/FPU17-04813
Financiación: info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/CTQ2017-82935-P

Tipo y forma: Article (PostPrint)