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Volumn 120, Issue 15, 1998, Pages 3704-3716

Tetranuclear manganese-oxo aggregates relevant to the photosynthetic water oxidation center. Crystal structure, spectroscopic properties and reactivity

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE; ADAMANTANE DERIVATIVE; FERROMAGNETIC MATERIAL; LIGAND; MANGANESE OXIDE; WATER;

EID: 0032557238     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja973668v     Document Type: Article
Times cited : (93)

References (128)
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    • note
    • 3tacn, 1,4,7-trimethyl-1,4,7-triazacyclononane; tmpa, tris(2-methylpyridyl)amine; bispicen, N,N′-bis(2-methylpyridyl)-1,2-ethanediamine; bispictn, N,N′- bis-(2-methylpyridyl)-1,3-propanediamine; Fe(Cp*)2, bis(pentamethylcyclo-pentadienyl)iron.
  • 56
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    • 3 (Pal, S.; Chan, M.; Armstrong, W. H. J. Am. Chem. Soc. 1992, 114, 6398-6406) are the only identifiable high oxidation state products obtained. EPR experiments performed at 77 K do, however, show a six-line signal centered at g = 2.0 indicating the presence of an unidentified Mn(II) contaminant. The manganese contaminants were extracted from the crude reaction product as described.
    • (1992) J. Am. Chem. Soc. , vol.114 , pp. 6398-6406
    • Pal, S.1    Chan, M.2    Armstrong, W.H.3
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    • Symbols: vs, very strong; s, strong; m, medium; w, weak; sh, shoulder
    • Symbols: vs, very strong; s, strong; m, medium; w, weak; sh, shoulder.
  • 60
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    • note
    • 4.
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    • note
    • 4]. The source of the H-atom is unknown at this time.
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    • 3tacn for quantitative conversion of 1 to 2, other tertiary amines, including triethylamine, N,N,N′,N′N′-pentamethyldiethylenetriamine, quinuclidine, proton sponge, and DABCO, were effective reductants at somewhat higher concentrations. Triethylamine has been used previously in the reduction of inorganic complexes (Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877-910). The redox chemistry of tertiary amines has been extensively reviewed (Weinberg, N. L.; Weinberg H. R. Chem. Rev. 1968, 68, 449-522).
    • (1996) Chem. Rev. , vol.96 , pp. 877-910
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    • 3tacn for quantitative conversion of 1 to 2, other tertiary amines, including triethylamine, N,N,N′,N′N′-pentamethyldiethylenetriamine, quinuclidine, proton sponge, and DABCO, were effective reductants at somewhat higher concentrations. Triethylamine has been used previously in the reduction of inorganic complexes (Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877-910). The redox chemistry of tertiary amines has been extensively reviewed (Weinberg, N. L.; Weinberg H. R. Chem. Rev. 1968, 68, 449-522).
    • (1968) Chem. Rev. , vol.68 , pp. 449-522
    • Weinberg, N.L.1    Weinberg, H.R.2
  • 65
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    • note
    • + is found for wavelengths less than 400 nm. The spectrum shown in Figure 2 is in good agreement with that of an authentic spectrum of 2 prepared by bulk electrolysis.
  • 66
    • 7144255160 scopus 로고    scopus 로고
    • note
    • 4+ can exist in many possible isomeric forms, yet remarkably, only one is observed in the solid state or in solution.
  • 67
    • 7144257508 scopus 로고    scopus 로고
    • py, which are trans to μ-O ligands
    • py, which are trans to μ-O ligands.
  • 85
    • 7144256841 scopus 로고    scopus 로고
    • note
    • A reversible electron transfer is characterized by a separation of cathodic and anodic CV peak potentials of 59/n mV, quasi-reversibility is characterized by cathodic and anodic peak potentials separated by more than 59/n mV, and irreversibility by the disappearance of a reverse peak (n = the number of electrons). A reversible electron transfer is also distinguished by a peak cathodic current/peak anodic current ratio of 1.
  • 87
    • 7144255845 scopus 로고    scopus 로고
    • B
    • B.
  • 91
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    • note
    • 4+ cores.
  • 103
    • 7144256843 scopus 로고    scopus 로고
    • Unpublished work
    • 4, was determined by spectrophotometric titration with pyridinium triflate in acetonitrile (Dubé, C. E.; Armstrong, W. H. Unpublished work).
    • Dubé, C.E.1    Armstrong, W.H.2
  • 104
    • 7144262027 scopus 로고    scopus 로고
    • note
    • +.
  • 105
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    • note
    • 2 exhibited degradation in aqueous solution by cyclic voltammetry at slower scan rates. Reproducible voltammograms of the coupled processes were collected at 500 mV/s. Voltammetry of aqueous solutions of 1 above pH about 12 was not possible because of complex degradation.
  • 112
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    • note
    • a in water is 13 (vide supra). The conversion of 2 to 1 with protonation is under investigation.
  • 115
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    • See ref 75
    • See ref 75.
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    • Armstrong, W. H. In Manganese Redox Enzymes; Pecoraro, V. L., Ed.; VCH Publishers: New York, 1992; pp 261-286.
    • (1992) Manganese Redox Enzymes , pp. 261-286
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.