Intramolecular C-C Coupling Reactions of Alkynyl, Vinylidene, and Alkenylphosphane Ligands in Rhodium(III) Complexes

Martínez De Salinas, S. ; Díez, J. ; Falvello, L.R. (Universidad de Zaragoza) ; González, J. ; Gamasa, M.P. ; Lastra, E.

Resumen: Electrophilic attack with methyl trifluoromethanesulfonate or tetrafluoroboric acid, to new alkynyl rhodium complexes containing alkenylphosphanes, leads to butenynyl coupling products or to the unprecedented rhodaphosphacycle complexes Rh(¿5-C5Me5){¿4-(P, C, C, C)-iPr2PCH2C(=CH2)C(CH2R)C=C(R)}]BF4] (R = Ph (11a), p-tol (11b)). These complexes 11a, b can be explained as a result of the coupling of three organic fragments in the molecule, the alkynyl, the vinylidene, generated in situ by reaction with HBF4 (A), and the C-C double bond from the alkenylphosphane. DFT computational studies on the formation of complex 11a suggest the 2 + 2] intramolecular cycloaddition between the double bond of the allylphosphane and the Ca-Cß of the vinylidene A as the most plausible pathway for this reaction.

Idioma: Inglés

DOI: 10.1021/acs.organomet.6b00330

Año: 2016

Publicado en: Organometallics 35, 17 (2016), 2793-2805
ISSN: 0276-7333

Factor impacto JCR: 3.862 (2016)

Categ. JCR: CHEMISTRY, ORGANIC rank: 12 / 59 = 0.203 (2016) - Q1 - T1
Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 8 / 46 = 0.174 (2016) - Q1 - T1

Factor impacto SCIMAGO: 1.723 - Inorganic Chemistry (Q1) - Physical and Theoretical Chemistry (Q1) - Organic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/MICINN/CSD2007-00006
Financiación: info:eu-repo/grantAgreement/ES/MINECO/CTQ2011-28641
Financiación: info:eu-repo/grantAgreement/ES/MINECO/MAT2015-68200-C2-1-P

Tipo y forma: Article (PostPrint)

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