Synthesis, Structure and Catalytic Properties of Two Complexes: ((Butylthio)(8)porphyrazinato)cobalt(II), Co(PzS(8)) and ((Butyloxyl) (Butylthio)(7)porphyrazinato)cobalt(II), Co (PzOS(7))

摘要

abstract_textpA novel porphyrazine, 2H 2-butyloxy-3,7,8,12,13,17,18-heptakis( butylthio) porphyrazine (H(2)PzOS(7)), was obtained with a yield 13 when preparing 2H 2,3,7,8,12,13,17,18-octakis-(butylthio) porphyrazine (H(2)PzS(8)). The crystal structures of cobalt(II) complexes, CoPzOS(7) and CoPzS(8), were determined by single crystal X-ray diffraction analysis. And the structural characterizations by H-1-NMR, H-1-(HCOSY)-H-1, C-13-NMR, UV-Vis and MALDI-TOF MS were combined for confirmation. Moreover, the cobalt complexes were employed as catalysts in the oxidation of benzyl alcohol with various oxidants including O-2, H2O2 and t-BuOOH. Superior conversion rate was obtained with H2O2 and t-BuOOH at ambient condition. For assessing the capacity of O-2 activation, the reaction was conducted under pressurized condition. Since the beta-pyrrole position was asymmetrically replaced by a butyloxy group, the reaction rate catalyzed by CoPzOS(7) was over twice than by CoPzS(8). The conversion rate of benzyl alcohol reached over 80 within 6 h. Moreover, the aldehyde yield for oxidation of extended substituent benzyl alcohols catalyzed by CoPzOS(7) was also 1-2 times higher than by CoPzS8 in same reaction time. Especially their oxidative selectivities were all 100 ! The cyclic voltammograms indicate that the potentials of CoIII/CoII are closely related to the activity of the catalyst./p/abstract_text