doi:10.1039/c7dt04829gengPassera, A.Iuliano, A.Pérez-Torrente, J.J.Passarelli, V.Mechanistic insights into the tropo-inversion of the biphenyl moiety in chiral bis-amido phosphites and in their palladium(II) complexesART-2018-104653Chiral 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.2018http://zaguan.unizar.es/record/7830910.1039/c7dt04829ghttp://zaguan.unizar.es/record/78309oai:zaguan.unizar.es:78309info:eu-repo/grantAgreement/ES/DGA-FSE/E07info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2013-42532-Pinfo:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-PDALTON TRANSACTIONS 47, 7 (2018), 2292-2305All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess