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Dinuclear pyridine-4-thiolate-bridged rhodium and iridium complexes as ditopic building blocks in molecular architecture

AutorFerrer, Montserrat; Gómez-Bautista, Daniel ; Gutiérrez, Albert; Miranda, J. R.; Orduña-Marco, Guillermo; Oro, Luis A. ; Pérez-Torrente, Jesús J. ; Rossell, Oriol; García-Orduña, P. ; Lahoz, Fernando J.
Fecha de publicación2014
EditorAmerican Chemical Society
CitaciónInorganic Chemistry 53(3): 1699-1711 (2014)
ResumenA series of dinuclear pyridine-4-thiolate (4-Spy)-bridged rhodium and iridium compounds [M(μ-4-Spy)(diolef)]2 [diolef = 1,5-cyclooctadiene (cod), M = Rh (1), Ir (2); diolef = 2,5-norbornadiene (nbd), M = Rh (3)] were prepared by the 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) was obtained by the reaction of [Rh(acac)(CO)(PPh3)] (acac = acetylacetonate) with 4-pySH. Compounds 1-4 were assessed as metalloligands in self-assembly reactions with the cis-blocked acceptors [M(cod)(NCCH3)2](BF 4) [M = Rh (a), Ir (b)] and [M(H2O)2(dppp)] (OTf)2 [M = Pd (c), Pt (d); dppp = 1,3-bis(diphenylphosphino)propane] . The homometallic hexanuclear metallomacrocycles [{M2(μ-4-Spy) 2(cod)2}2{M(cod)}2](BF 4)2 (M = Rh [(1a)2], Ir [(2b)2]) and the heterometallic hexanuclear metallomacrocycles [{Rh2(μ-4-Spy) 2(cod)2}2{Ir(cod)}2](BF 4)2 [(1b)2], [{Rh2(μ-4-Spy) 2(cod)2}2{M′(dppp)}2](OTf) 4 (M′ = Pd [(1c)2], Pt [(1d)2]), and [{Ir2(μ-4-Spy)2(cod)2}2{M′ (dppp)}2](OTf)4 (M′ = Pd [(2c)2], Pt [(2d)2]) were obtained. NMR spectroscopy in combination with electrospray ionization mass spectrometry was used to elucidate the nature of the metalloligands and their respective supramolecular assemblies. Most of the synthesized species were found to be nonrigid in solution, and their fluxional behavior was studied by variable-temperature 1H NMR spectroscopy. An X-ray diffraction study of the assemblies (1a)2 and (1d)2 revealed the formation of rectangular (9.6 Å × 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 moieties to the dinuclear rhodium units, exhibiting a bent-anti arrangement, and through the peripheral pyridinic nitrogen atoms to the mononuclear corners.
Versión del editorhttp://dx.doi.org/10.1021/ic402838y
URIhttp://hdl.handle.net/10261/111797
DOI10.1021/ic402838y
Identificadoresdoi: 10.1021/ic402838y
issn: 0020-1669
e-issn: 1520-510X
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