Mechanistic insights into the tropo-inversion of the biphenyl moiety in chiral bis-amido phosphites and in their palladium(II) complexes

Passera, A. ; Iuliano, A. ; Pérez-Torrente, J.J. (Universidad de Zaragoza) ; Passarelli, V.

Resumen: Chiral bis-amido phosphites L1 and L2 containing a diaminobiphenyl unit and a chiral alkoxy group derived from either (-)-menthol or 3-acetoxy deoxycholic methyl ester have been synthesised. Both L1 and L2 react with PdCl2(NCPh)2 affording di- or mononuclear derivatives with formula trans-[Pd(µ-Cl)Cl(L)]2 (1a, L = L1; 1b, L = L2) or trans-PdCl2(L)2 (2a, L = L1; 2b, L = L2) depending on the Pd:L molar ratio. The crystal structure of (M, P)-1a confirms the trans arrangement of the ligand L1 and shows an unusual puckering of the Pd2(µ-Cl)2 core (¿ 46°). Both the ligands L1 and L2 and their complexes (1 and 2) are fluxional in solution as a consequence of the tropo-inversion of the diaminobiphenyl unit. For L1, L2, 1a and 2a a combined study including variable temperature 31P{1H} NMR spectroscopy and line shape analysis, Eyring plots and DFT calculations have shed light on the mechanism of the tropo-inversion.

Idioma: Inglés

DOI: 10.1039/c7dt04829g

Año: 2018

Publicado en: DALTON TRANSACTIONS 47, 7 (2018), 2292-2305
ISSN: 1477-9226

Factor impacto JCR: 4.052 (2018)

Categ. JCR: CHEMISTRY, INORGANIC & NUCLEAR rank: 7 / 45 = 0.156 (2018) - Q1 - T1

Factor impacto SCIMAGO: 1.12 - Inorganic Chemistry (Q1)

Financiación: info:eu-repo/grantAgreement/ES/DGA-FSE/E07
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P
Financiación: info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P

Tipo y forma: Article (PostPrint)

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