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This content will become publicly available on July 11, 2019

Title: Synthesis, Characterization, and Oxidation Catalysis Studies of a Monofunctionalized Copper Pyridine-Aza Macrocycle

For this study, a copper-containing pyridine-aza macrocycle (PyMACs) with a propionic acid functionality was synthesized and characterized using X-ray crystallography and various spectroscopic techniques. The complex was then screened for peroxidase , olefin epoxidation, and phenol oxidation properties, using an ABTS assay, GC-MS, and UV-Vis spectrophotometry, respectively. The control copper (II) perchlorate salts were superior oxidation catalysts to the pentadentate carboxylic acid complex, CuLCOOH, and the unfunctionalized amine PyMAC, CuCRH. This might indicate that free copper ions facilitate the one-electron oxidations necessary for the reactions better than complexed copper. It also indicates that the copper PyMACs are far less effective than the analogous nickel and iron systems. We did, however, obtain valuable insights on the chemistry governing this family of PyMACs by probing the CuLCOOH’s solution and solid-phase protonation equilibria, which will be useful for isolating and studying the analogous iron complex, FeLCOOH.
Authors:
 [1] ;  [1] ;  [1] ;  [1]
  1. Tufts Univ., Medford, MA (United States)
Publication Date:
Grant/Contract Number:
FG02-06ER15799; CHE 1412909; CHE-MRI 0821508; CHECRIF0639138; CHEM-MRI 0320783
Type:
Accepted Manuscript
Journal Name:
Inorganica Chimica Acta
Additional Journal Information:
Journal Name: Inorganica Chimica Acta; Journal ID: ISSN 0020-1693
Publisher:
Elsevier
Research Org:
Tufts Univ., Medford, MA (United States)
Sponsoring Org:
USDOE; National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; bleomycin; peroxide activation catalysis; ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid); PyMAC (pyridine-aza macrocycle)
OSTI Identifier:
1458826