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Structural consequences of nickel versus macrocycle reductions in F430 models: EXAFS studies of a Ni(I) anion and Ni(II). pi. anion radicals

Journal Article · · Journal of the American Chemical Society; (USA)
DOI:https://doi.org/10.1021/ja00160a056· OSTI ID:6710197
; ;  [1];  [2]
  1. Brookhaven National Lab., Upton, NY (USA)
  2. Univ. of California, Davis (USA)

Factor 430 (F430) is a nickel tetrapyrrole (hydrocorphin) found in methyl coenzyme M reductase, the enzyme that catalyzes the final stages of the reduction of carbon dioxide to methane in methanogenic bacteria. Reduction of Ni(II) F430 and isobacteriochlorins unambiguously results in Ni(I) species whereas porphyrins, chlorins, and hexahydro- and octahydroporphyrins yield anions variously ascribed to Ni(I) or Ni(II) {pi} radicals with some metal character. The authors present here EXAFS results for the Ni(II) radical anions of a chlorin and a porphycene and for the Ni(I) anion of an isobacteriochlorin (iBC) that clearly demonstrate the structural consequences of metal versus macrocycle reductions.

OSTI ID:
6710197
Journal Information:
Journal of the American Chemical Society; (USA), Journal Name: Journal of the American Chemical Society; (USA) Vol. 112:4; ISSN 0002-7863; ISSN JACSA
Country of Publication:
United States
Language:
English