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Pyridinethiolate titanocene metalloligands and their self-assembly reactions to yield early-late metallamacrocycles Ferrer García, Montserrat Gomez-Bautista, Daniel Gutiérrez i Currius, Albert Orduña Marco, Guillermo Oro, Luis A. Pérez Torrente, Jesús J. Rossell Alfonso, Oriol Ruiz Sabín, Eliseo Lligands Metalls Espectroscòpia de ressonància magnètica nuclear Espectrometria de masses amb ionització per electroesprai Química supramolecular Ligands Metals Nuclear magnetic resonance spectroscopy Electrospray ionization mass spectrometry Supramolecular chemistry New titanocene pyridinethiolate compounds [(RCp)(2)Ti(4-Spy)(2)] (R = H (1), Me (2); Cp = cyclo-pentadienyl; 4-Spy = pyridine-4-thiolate) and [Cp2Ti(2-Spy)(2)] (3; 2-Spy = pyridine-2-thiolate) have been prepared by reaction of the corresponding Li(Spy) salt with the appropriate compound [(RCp)(2)TiCl2]. Compounds 1 and 2 have been used as metalloligands in self-assembly reactions with the acceptor late-transition-metal compounds [M(H2O)(2)(dppp)]-(OTf)(2) (M = Pd (a) Pt (b); dppp = 1,3-bis-(diphenylphosphino)propane), and the series of early-late tetranuclear metallamacrocycles [{(RCp)(2)Ti(4-Spy)(2)}{M-(dppp)}](2)(OTf)(4) (R = H, M = Pd (1(2)a(2)); R = H, M = Pt (1(2)b(2)); R = Me, M = Pd (2(2)a(2)); R = Me, M = Pt (2(2)b(2))) arising from the anti isomer of the titanocene metalloligands have been obtained. Only ligand transfer reactions from Ti to either Pd or Pt atoms have been observed when the pyridine-2-thiolate derivative 3 has been assayed in self-assembly processes. The obtained species have been characterized by NMR spectroscopy and ESI(+) mass spectrometry. The supramolecular assemblies have shown to be nonrigid in solution, and their fluxional behavior has been studied by VT H-1 NMR spectroscopy. A DFT study including ab initio molecular dynamics in order to elucidate the structures and the relative stability of the isomers has been performed. 2019-02-12T13:27:02Z 2019-02-12T13:27:02Z 2016-02-08 2019-02-12T13:27:02Z info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Versió postprint del document publicat a: https://doi.org/10.1021/acs.organomet.5b00876 Organometallics, 2016, vol. 35, num. 3, p. 336-345 https://doi.org/10.1021/acs.organomet.5b00876 (c) American Chemical Society , 2016 info:eu-repo/semantics/openAccess American Chemical Society Articles publicats en revistes (Química Inorgànica i Orgànica)