78309 20200811091507.0 doi 10.1039/c7dt04829g sideral 104653 ART-2018-104653 eng Passera, A. Mechanistic insights into the tropo-inversion of the biphenyl moiety in chiral bis-amido phosphites and in their palladium(II) complexes 2018 Access copy available to the general public Unrestricted 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. info:eu-repo/grantAgreement/ES/DGA-FSE/E07 info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-P info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.052 2018 CHEMISTRY, INORGANIC & NUCLEAR 7 / 45 = 0.156 2018 Q1 T1 1.12 2018 Inorganic Chemistry 2018 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Iuliano, A. (orcid)0000-0002-3327-0918 Pérez-Torrente, J.J. Universidad de Zaragoza (orcid)0000-0002-1735-6439 Passarelli, V. 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 47, 7 (2018), 2292-2305 Dalton Trans. DALTON TRANSACTIONS 1477-9226 872177 http://zaguan.unizar.es/record/78309/files/texto_completo.pdf Postprint 98865 http://zaguan.unizar.es/record/78309/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:78309 articulos driver 2020-08-11-09:03:10 ARTICLE