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2016-02-08

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Please use this identifier to cite or link to this item: https://hdl.handle.net/2445/128170

Pyridinethiolate titanocene metalloligands and their self-assembly reactions to yield early-late metallamacrocycles

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https://doi.org/10.1021/acs.organomet.5b00876

Abstract

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.

Subject

Lligands, Metalls, Espectroscòpia de ressonància magnètica nuclear, Espectrometria de masses amb ionització per electroesprai, Química supramolecular

Subject (English)

Ligands, Metals, Nuclear magnetic resonance spectroscopy, Electrospray ionization mass spectrometry, Supramolecular chemistry

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Articles publicats en revistes (Química Inorgànica i Orgànica)
Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB))

Citation

FERRER GARCÍA, Montserrat, et al. Pyridinethiolate titanocene metalloligands and their self-assembly reactions to yield early-late metallamacrocycles. Organometallics. 2016. Vol. 35, num. 3, pags. 336-345. ISSN 0276-7333. [consulted: 13 of August of 2026]. Available at: https://hdl.handle.net/2445/128170

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