Carregant...
Fitxers
Tipus de document
ArticleVersió
Versió acceptadaData de publicació
Tots els drets reservats
Si us plau utilitzeu sempre aquest identificador per citar o enllaçar aquest document: https://hdl.handle.net/2445/128170
Pyridinethiolate titanocene metalloligands and their self-assembly reactions to yield early-late metallamacrocycles
Títol de la revista
Director/Tutor
ISSN de la revista
Títol del volum
Recurs relacionat
Resum
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.
Citació
Citació
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. Pyridinethiolate titanocene metalloligands and their self-assembly reactions to yield early-late metallamacrocycles. _Organometallics_. 2016. Vol. 35, núm. 3, pàgs. 336-345. [consulta: 27 de gener de 2026]. ISSN: 0276-7333. [Disponible a: https://hdl.handle.net/2445/128170]