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Volumn 125, Issue 19, 2003, Pages 5897-5914

Spectroscopic and computational studies of Co3+-corrinoids: Spectral and electronic properties of the B12 cofactors and biologically relevant precursors

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXATION; COMPUTATIONAL METHODS; ELECTRONIC PROPERTIES; MOLECULES; RAMAN SPECTROSCOPY; WATER;

EID: 0038295926     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja029328d     Document Type: Article
Times cited : (124)

References (109)
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    • 12; Wiley: New York, 1982.
    • (1982) 12
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    • Banerjee, R., Ed.; Wiley: New York
    • 12; Banerjee, R., Ed.; Wiley: New York, 1999; pp 113-164.
    • (1999) 12 , pp. 113-164
    • Pratt, J.M.1
  • 23
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    • Lever, A. B. P., Gray, H. B., Eds.; Addison-Wesley: Reading, MA
    • Makinen. M. W.; Churg, A. K. In Iron Porphyrins; Lever, A. B. P., Gray, H. B., Eds.; Addison-Wesley: Reading, MA, 1983; Vol. 1, pp 141-235.
    • (1983) Iron Porphyrins , vol.1 , pp. 141-235
    • Makinen, M.W.1    Churg, A.K.2
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    • 12; Dolphin, D., Ed.; Wiley: New York, 1982; Vol. 1, pp 23-106.
    • (1982) 12 , vol.1 , pp. 23-106
    • Glusker, J.P.1
  • 29
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    • Banerjee, R., Ed.; Wiley: New York
    • 12; Banerjee, R., Ed.; Wiley: New York, 1999; pp 73-112.
    • (1999) 12 , pp. 73-112
    • Pratt, I.M.1
  • 57
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    • note
    • + model.
  • 58
    • 0038418719 scopus 로고    scopus 로고
    • note
    • TD-DFT calculations on a similar MeCbl model using more typical C-H bond lengths of 1.08 Å were performed, and results showed no significant differences in MO composition or transition state energies as compared to the results from the model with shorter C-H bond lengths.
  • 67
    • 0038756785 scopus 로고    scopus 로고
    • unpublished results
    • Ahlrichs, R., unpublished results.
    • Ahlrichs, R.1
  • 68
    • 0031285839 scopus 로고    scopus 로고
    • The Ahlrichs auxiliary basis sets were obtained from the TurboMole basis set library under ftp.chemie.uni-karlsruhe.de/pub/cbasen. Weigend, F.; Haeser, M. Theor. Chem. Acc. 1997, 97, 331-340.
    • (1997) Theor. Chem. Acc. , vol.97 , pp. 331-340
    • Weigend, F.1    Haeser, M.2
  • 85
    • 0004247468 scopus 로고    scopus 로고
    • Banerjee, R., Ed.; Wiley: New York
    • 12; Banerjee, R., Ed.; Wiley: New York, 1999), but analysis of the corresponding transitions is beyond the scope of this study.
    • (1999) 12
    • Pratt, J.M.1
  • 86
    • 0038080155 scopus 로고    scopus 로고
    • note
    • The fold angle φ is described by the angle between the planes formed by N21-C4-C5-C6-N22-C9-C10 and C10-C11-N23-C14-C15-C16-N24. For AdoCbl, φ is 13.3° (see ref 55), and for MeCbl, φ is 14,7° (see ref 54).
  • 93
    • 0038080154 scopus 로고    scopus 로고
    • note
    • The replacement of the DMB by an imidazole in the Cbl models requires no change in the conformation of the corrin ring, as the coordinates for all corrin atoms are taken directly from the X-ray data. As such, the frozen macrocycle maintains all steric effects imposed by outer ring substituents including the nucleotide loop and DMB, which are not explicitly included in our models.
  • 95
    • 0038418716 scopus 로고    scopus 로고
    • note
    • + are presented in Figures S5 and S7, respectively.
  • 96
    • 0037742633 scopus 로고    scopus 로고
    • note
    • Note that the x and y axes are rotated by 45° about z from their usual orientations along the metal-ligand bonds. The designation of Co 3d orbitals contributing to Cbl MOs reflects this rotation.
  • 97
    • 0038080152 scopus 로고    scopus 로고
    • note
    • The percentages listed give the contributions of individual one-electron excitations required to model the charge distribution in the corresponding excited state. It is expected that those excitations with donor and acceptor MOs composed of similar atomic orbitals are the dominant intensity contributors to the overall transition.
  • 98
    • 0038418717 scopus 로고    scopus 로고
    • note
    • + (see Figure S5 and Table S 13).
  • 99
    • 0037742634 scopus 로고    scopus 로고
    • note
    • The relatively high intensity of this transition derives from the fact that the corrin C and N 2p orbitals contributing to the donor MO (#114) are also the main contributors to the acceptor MO (#117).
  • 106
    • 0038756784 scopus 로고    scopus 로고
    • note
    • + as compared to that for AdoCbl are not inconsistent with our computations that suggest a similar Co-C bond strength in the two species, in nice agreement with published RR and IR data.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.