The synthesis, characterization and computional investigation of new metalloporphyrazine containing 15-membered S-4 donor macrocyclic moieties


Yildiz B., Baygu Y., KARA İ., DAL H., GÖK Y.

TETRAHEDRON, vol.72, no.44, pp.6972-6981, 2016 (SCI-Expanded) identifier identifier

  • Publication Type: Article / Article
  • Volume: 72 Issue: 44
  • Publication Date: 2016
  • Doi Number: 10.1016/j.tet.2016.09.028
  • Journal Name: TETRAHEDRON
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Index Chemicus (IC)
  • Page Numbers: pp.6972-6981
  • Keywords: Tetrathia macrocycle, Metalloporphyrazines, Macrocyclization, Green chemistry, Template effect, Computional chemistry, HIGHLY SELECTIVE IODINATION, STAR-PORPHYRAZINES, II COMPLEXES, CROWN-ETHERS, NI-II, DERIVATIVES, ALCOHOLS, REDUCTION, UNITS, CONVENIENT
  • Anadolu University Affiliated: Yes

Abstract

In this study, an improved synthesis of 1,5-bis(2-formylphenyl)-1,5-dithiapentane(3) has been performed according to the literature in a high yield. 1,5-Bis (2-benzyl alcohol)-1,5-dithia pentane (4) was prepared by the reduction reaction of precursor compound in high yield via solvent-free conditions. Treatment of substituted benzylic alcohol with bromotrimethylsilane in dry acetonitrile in the presence of NaI resulted the formation of desired iodine derivative (5) in very high yield. 7,8-dihydro-6H, 14H, 19H-dibenzo[bj] [1,12,5,8]tetradithiacyclopentadecine-16,17-dicarbonitrile (7) was synthesized by the reaction of compound 7 and dithiomaleonitrile disodium salt. Magnesium porphyrazine carrying symmetrically four 15 membered tetrathia macro-cycles has been synthesized by the cyclotetramerization reaction of dicarbodinitrile compound (7) in the presence of magnesium butoxide according to the Linstead procedure. We focused on the prediction of the geometry optimization, normal mode frequencies, UV absorption spectra, chemical shifts and electronic properties of the compound by using B3LYP method with 6-31G(d) basis set. These novel compounds were characterized by a combination of elemental analysis, H-1, C-13 NMR, FTIR, UV vis and MS spectral data. An X-ray crystal structure of dicarbodinitrile compound (7) is also presented. The computed results are very close to the obtained experimental results by spectroscopic techniques. (C) 2016 Elsevier Ltd. All rights reserved.