Please use this identifier to cite or link to this item: http://hdl.handle.net/2445/128138
Title: Dinuclear Pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture
Author: Ferrer García, Montserrat
Gómez Bautista, Daniel
Gutiérrez i Currius, Albert
Miranda, José R.
Orduña Marco, Guillermo
Oro, Luis A.
Pérez Torrente, Jesús J.
Rossell, Oriol
García Orduña, Pilar
Lahoz, Fernando J.
Keywords: Lligands
Complexos metàl·lics
Rodi
Iridi
Química supramolecular
Ligands
Metal complexes
Rhodium
Iridium
Supramolecular chemistry
Issue Date: 17-Jan-2014
Publisher: American Chemical Society
Abstract: A series of dinuclear pyridine-4-thiolate rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 (diolef = 1,5-cyclooctadiene, cod; M = Rh (1), Ir (2); 2,5-norbornadiene, nbd; M = Rh (3)) have been prepared by reaction of Li(4-Spy) with the appropriate compound [M(μ-Cl)(diolef)]2 (M = Rh, Ir). The dinuclear compound [Rh(μ-4-Spy)(CO)(PPh3)]2 (4) has been obtained by reaction of [Rh(acac)(CO)(PPh3] with 4-pySH. Compounds 1-4 have been assessed as metalloligands in self-assembly reactions with the cis-blocked [M(cod)(NCCH3)2](BF4) (M = Rh (a) and M = Ir (b)) and [M(H2O)2(dppp)](OTf)2 (M = Pd (c), Pt (d)) (dppp = 1,3-bis(diphenylphosphino)propane) acceptors. Homo [{M2(μ-4-Spy)2(cod)2}2{M(cod)}2](BF4)2 (M = Rh (1a)2, and M = Ir (2b)2), and hetero [{Rh2(μ-4-Spy)2(cod)2}2{Ir(cod)}2](BF4)2 (1b)2, [{Rh2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 ( M' = Pd (1c)2 and M'= Pt (1d)2) and [{Ir2(μ-4-Spy)2(cod)2}2{M'(dppp)}2](OTf)4 ( M' = Pd (2c)2 and M'= Pt (2d)2) hexanuclear metallomacrocycles have been obtained. NMR spectroscopy, in combination with ESI mass spectrometry has been used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of synthesized species have shown to be non-rigid in solution and their fluxional behavior has been studied by VT 1H NMR spectroscopy. An X-ray diffraction study on the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 x 6.6 Å) hexanuclear metallomacrocycles with alternating dinuclear (Rh2) and mononuclear (Rh or Pt) corners. The hexanuclear core is supported by four pyridine-4-thiolate linkers, which are bonded through the thiolate moiety to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners.
Note: Versió postprint del document publicat a: https://doi.org/10.1021/ic402838y
It is part of: Inorganic Chemistry, 2014, vol. 53, num. 3, p. 1699-1711
Related resource: https://doi.org/10.1021/ic402838y
URI: http://hdl.handle.net/2445/128138
ISSN: 0020-1669
Appears in Collections:Articles publicats en revistes (Química Inorgànica i Orgànica)

Files in This Item:
File Description SizeFormat 
631654.pdf9.78 MBAdobe PDFView/Open


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.