Structural Flexibility and Role of Vicinal 2-Thienyl Rings in 2, 3-Dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)2Th2Pyz], Its Palladium(II)Complex [(CN)2Th2Pyz(PdCl2)2], and the Related Pentametallic Pyrazinoporphyrazines [(PdCl2)4Th8TPyzPzM] (M = MgII(H2O), ZnII) (Articolo in rivista)

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  • Structural Flexibility and Role of Vicinal 2-Thienyl Rings in 2, 3-Dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)2Th2Pyz], Its Palladium(II)Complex [(CN)2Th2Pyz(PdCl2)2], and the Related Pentametallic Pyrazinoporphyrazines [(PdCl2)4Th8TPyzPzM] (M = MgII(H2O), ZnII) (Articolo in rivista) (literal)
Anno
  • 2011-01-01T00:00:00+01:00 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#doi
  • 10.1021/ic201678p (literal)
Alternative label
  • M. P. Donzello, G. De Mori, E. Viola, C. Ercolani, E. Bodo, L. Mannina, D. Capitani, C. Rizzoli, L. Gontrani, G. Aquilanti, K. M. Kadish, P. D'Angelo (2011)
    Structural Flexibility and Role of Vicinal 2-Thienyl Rings in 2, 3-Dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)2Th2Pyz], Its Palladium(II)Complex [(CN)2Th2Pyz(PdCl2)2], and the Related Pentametallic Pyrazinoporphyrazines [(PdCl2)4Th8TPyzPzM] (M = MgII(H2O), ZnII)
    in Inorganic chemistry (Online)
    (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#autori
  • M. P. Donzello, G. De Mori, E. Viola, C. Ercolani, E. Bodo, L. Mannina, D. Capitani, C. Rizzoli, L. Gontrani, G. Aquilanti, K. M. Kadish, P. D'Angelo (literal)
Pagina inizio
  • 12116 (literal)
Pagina fine
  • 12125 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#url
  • http://dx.doi.org/10.1021/ic201678p (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroVolume
  • 50 (literal)
Rivista
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#pagineTotali
  • 10 (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#numeroFascicolo
  • 23 (literal)
Note
  • ISI Web of Science (WOS) (literal)
  • Scopu (literal)
Http://www.cnr.it/ontology/cnr/pubblicazioni.owl#affiliazioni
  • Dipartimento di Chimica Sapienza Università di Roma Dipartimento di Chimica e Tecnologie del farmaco Sapienza Università di Roma Istituto di Metodologie Chimiche CNR Dipartimento di Chimica Generale e Inorganica Università di Parma Sincrotrone Trieste Dipartimento di chimica Università di Houston (literal)
Titolo
  • Structural Flexibility and Role of Vicinal 2-Thienyl Rings in 2, 3-Dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)2Th2Pyz], Its Palladium(II)Complex [(CN)2Th2Pyz(PdCl2)2], and the Related Pentametallic Pyrazinoporphyrazines [(PdCl2)4Th8TPyzPzM] (M = MgII(H2O), ZnII) (literal)
Abstract
  • The solid state and solution structure of 2,3-dicyano-5,6-di(2-thienyl)-1, 4-pyrazines [(CN)(2)Th(2)Pyz], and its pd(II) derivative, [(CN)(2)Th(2)Pyz(PdCl2)2]center dot H2O, formed by reaction of [(CN)(2)Th(2)Pyz] with [(C6H5CN)(2)Pdcl(2)] were characterized by X-ray, UV-visible, H-1 and C-13 NMR, and extended X-ray absorption fine structure (EXAFS) spectral measurements. The X-ray crystal structure of [(CN)(2)Th(2)Pyz] shows the presence of one thienyl ring positioned orthogonal to the rest of the molecule, with the two vicinal thienyl rings lying orthogonal to each other in a rare arrangement. NMR studies of [(CN)(2)Th(2)Pyz] in the solid state and in solutions of dimethylformamide or dimethyl sulfoxide confirm a nonequivalence of the thienyl rings in the solid state and also in solution. EXAFS results indicate that two distinct Pd-II coordination sites are formed at the di(2-thienyl)pyrazino moiety of [(CN)(2)Th(2)Pyz(PdCl2)(2)]center dot H2O, with identical Pd-N-pyz (2.03(3) angstrom) and Pd-Cl (2.36(3) angstrom) bond lengths but with different Pd-Sl (2.25(4) angstrom) and Pd-S2 (3.21(5) angstrom) bond distances in an overall asymmetric molecular framework. Density functional theory (DFT) and time-dependent DFT (TDDFT) theoretical studies also provide information about the structure and spectral behavior of the precursor and its metalated Pd-II derivative. H-1/C-13 NMR and UV-visible spectral measurements were also carried out on two heteropentametallic porphyrazine macrocycles which were prepared by a reaction of PdCl2 with [Th(8)TPyzPzM] where Th(8)TPyzPz = tetrakis-2,345,6-di-(2-thienyl)-pyrazino]porphyrazinato dianion and M = Mg-II(H2O) or Zn-II. Spectroscopic data on the newly synthesized [(PdCl2)(4)Th(8)TPyzPzM] compounds suggest that the binding of PdCl2 involves coordination sites of the type S2(th)PdCl2 with the two thienyl rings of each di(2-thienyl)pyrazino fragment bound to Pd-II in an equivalent manner (\"th-th\" coordination). This is similar to what was found for the corresponding octapyridinated analogues (\"py-py\" coordination). (literal)
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