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Title: Pyridinethiolate titanocene metalloligands and their self-assembly reactions to yield early-late metallamacrocycles
Author: Ferrer García, Montserrat
Gomez-Bautista, Daniel
Gutiérrez i Currius
Orduña-Marco, Guillermo
Oro, Luis A.
Pérez-Torrente, Jesús J.
Rossell, Oriol
Ruiz Sabín, Eliseo
Keywords: Lligands
Espectroscòpia de ressonància magnètica nuclear
Espectrometria de masses amb ionització per electroesprai
Química supramolecular
Nuclear magnetic resonance spectroscopy
Electrospray ionization mass spectrometry
Supramolecular chemistry
Issue Date: 8-Feb-2016
Publisher: American Chemical Society
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.
Note: Versió postprint del document publicat a:
It is part of: Organometallics, 2016, vol. 35, num. 3, p. 336-345
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ISSN: 0276-7333
Appears in Collections:Articles publicats en revistes (Química Inorgànica i Orgànica)
Articles publicats en revistes (Institut de Química Teòrica i Computacional (IQTCUB))

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