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Volumn 130, Issue 10, 2008, Pages 3127-3136

Hydrogen bonding effects on the electronic configuration of five-coordinate high-spin iron(II) porphyrinates

Author keywords

[No Author keywords available]

Indexed keywords

CRYSTALLOGRAPHY; ELECTRONIC STRUCTURE; HYDROGEN BONDS; IRON COMPOUNDS; PROTEINS;

EID: 41449102788     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja078222l     Document Type: Article
Times cited : (31)

References (73)
  • 1
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    • 2 in HRP demonstrates a significant difference between HRP and the globins.
    • 2 in HRP demonstrates a significant difference between HRP and the globins.
  • 4
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    • Salemme, F. R.; Freer, S. T.; Ng Huu Xuong Alden, R. A.; Kraut, J. J. Biol. Chem. 1973, 248, 3910.
    • Salemme, F. R.; Freer, S. T.; Ng Huu Xuong Alden, R. A.; Kraut, J. J. Biol. Chem. 1973, 248, 3910.
  • 19
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    • Lever, A. B. P, Gray, H. B, Eds, VCH Publishers Inc, New York, Chapter 2
    • Debrunner, P. In Iron Porphyrins Part 3; Lever, A. B. P., Gray, H. B., Eds.; VCH Publishers Inc.; New York, 1983; Chapter 2.
    • (1983) Iron Porphyrins , Issue.PART 3
    • Debrunner, P.1
  • 24
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    • The increase in imidazole binding constants upon the addition of 1,10-phenanthroline had been noted previously by Abbott and Raison, but the origin of the effect not established. Abbott, E. H.; Raison, P. A. J. Am. Chem. Soc. 1974, 96, 7378.
    • The increase in imidazole binding constants upon the addition of 1,10-phenanthroline had been noted previously by Abbott and Raison, but the origin of the effect not established. Abbott, E. H.; Raison, P. A. J. Am. Chem. Soc. 1974, 96, 7378.
  • 30
    • 41449095145 scopus 로고    scopus 로고
    • The following abbreviations are used in this paper: Por, generalized porphyrin dianion; TPP, dianion of meso-tetraphenylporphyrin; Tp-OCH3-PP, dianion of meso-tetra-p-methoxyphenylporphyrin; TTP, dianion of meso-tetratolylporphyrin; TpivPP, dianion of α,α,α,α-tetrakis(o- pivalamidophenyl)porphyrin; Piv2C8P, dianion of α,α,5,15-[2,2′-(octanediamido)diphenyl]-α,α, 10-20-bis(o-pivalamidophenyl)porphyrin; Im, generalized imidazole; HIm, imidazole; 2-MeHIm, 2-methylimidazole; 1,2-Me2Im, 1,2-dimethylimidazole; Nax, nitrogen of axial ligand; Np, porphyrinato nitrogen; Cb, porphyrin β carbon; Ct, the center of four porphyrinato nitrogen atoms
    • b, porphyrin β carbon; Ct, the center of four porphyrinato nitrogen atoms.
  • 33
    • 0003946851 scopus 로고
    • Smith, K. M, Ed, Elsevier Scientific Publishing: Amsterdam, The Netherlands, Chapter 5
    • (b) Buchler, J. W. In Porphyrins and Metalloporphyrins; Smith, K. M., Ed.; Elsevier Scientific Publishing: Amsterdam, The Netherlands, 1975; Chapter 5.
    • (1975) Porphyrins and Metalloporphyrins
    • Buchler, J.W.1
  • 37
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    • R1, ∑, F0, F c||/∑|F0, wR2, ∑[w(F02, Fc 2)2]/∑ [w(F0 2)2]}1/2 and R(F2, ∑, F0|2, Fc| 2|/∑ |F0|2. The conventional R-factors R1 are based on F, with F set to zero for negative F2. The criterion of F2 > 2σ(F2) was used only for calculating R 1. R-factors based on F2 (wR 2) are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger
    • 2) are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.
  • 38
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    • Universität Göttingen: Göttingen, Germany
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    • Schultz, A. J.; Van, Derveer, D. G.; Parker, D. W.; Baldwin, J. E. Acta Cryst. C 1990, 46, 276.
    • Schultz, A. J.; Van, Derveer, D. G.; Parker, D. W.; Baldwin, J. E. Acta Cryst. C 1990, 46, 276.
  • 43
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    • Sears, V. F. In Methods of Experimental Physics, 23, Neutron Scattering, Part A. ed.; Academic Press: Orlando, FL, 1986; p 521-550.
    • Sears, V. F. In Methods of Experimental Physics, Vol. 23, Neutron Scattering, Part A. ed.; Academic Press: Orlando, FL, 1986; p 521-550.
  • 47
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    • The preservation of a few crystallizing tubes used in the early investigations reported in ref 43 and in single-crystal nuclear resonance vibrational studies (ref 45) and several prepared subsequent to those experiments support the idea that early crystallization experiments provided a single phase whereas later experiments provided two distinct phases. (All of these experiments were carried out by M.K.E., the later experiment by C.H. agree with the last experiments of M.K.E.)
    • The preservation of a few crystallizing tubes used in the early investigations reported in ref 43 and in single-crystal nuclear resonance vibrational studies (ref 45) and several prepared subsequent to those experiments support the idea that early crystallization experiments provided a single phase whereas later experiments provided two distinct phases. (All of these experiments were carried out by M.K.E., the later experiment by C.H. agree with the last experiments of M.K.E.)
  • 50
    • 41449092043 scopus 로고    scopus 로고
    • Unit cell constants for [Fe(TPP)(2-MeHIm)]·1.5C6H 5Cl:43 a, 12.334(3) Å, b, 13.515(6) Å, c, 14.241(7) Å, α, 70.62(3)°, β, 88.29(2)°, γ, 88.24(3)°, V, 2238(2) Å3; for [Fe(TPP)(2-MeHIm)]2·2-MeHIm)]·C6H 5Cl: a, 13.3632(4) Å, b, 17.1128(6) Å, c, 20.2999(7) Å, α, 73.498(2)°, β, 80.289(2)°, γ, 89.301(2)°, V, 4384.1(3) Å3; for and [Fe(TPP)(2-MeHIm)]2·0.5(C6H5Cl, a, 17.904(4) Å, b, 10.151(2) Å, c, 23.061(5) Å, α, 90.00°, β, 108.47(3)°, γ, 90.00°, V, 3975.2(14) Å3
    • 3.
  • 52
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    • N-H distances from an X-ray analysis will be shorter than those found in a neutron diffraction experiment owing to the known foreshortening. Glusker, J. P, Lewis, M, Rossi, M. Crystal Structure Analysis for Chemists and Biologists; VCH Publishers, Inc, New York, 1994; Chapter 9, p 376
    • N-H distances from an X-ray analysis will be shorter than those found in a neutron diffraction experiment owing to the known foreshortening. Glusker, J. P.; Lewis, M.; Rossi, M. Crystal Structure Analysis for Chemists and Biologists; VCH Publishers, Inc.: New York, 1994; Chapter 9, p 376.
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    • The average N-H distances in Cambridge Structural Data Base from neutron diffraction studies is 1.023(57) Å.
    • The average N-H distances in Cambridge Structural Data Base from neutron diffraction studies is 1.023(57) Å.
  • 54
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    • Collman, J. P.; Kim, N.; Hoard, J. L.; Lang, G.; Radonovich, L. J.; Reed, C. A. Abstracts of Papers; 167th National Meeting of the American Chemical Society; Los Angeles, CA, April 1974; American Chemical Society: Washington, D. C., 1974.
    • (a) Collman, J. P.; Kim, N.; Hoard, J. L.; Lang, G.; Radonovich, L. J.; Reed, C. A. Abstracts of Papers; 167th National Meeting of the American Chemical Society; Los Angeles, CA, April 1974; American Chemical Society: Washington, D. C., 1974.
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    • Hoard, J. L. personal communication to W.R.S. In particular, Prof. Hoard provided a set of atomic coordinates for the molecule.
    • (b) Hoard, J. L. personal communication to W.R.S. In particular, Prof. Hoard provided a set of atomic coordinates for the molecule.
  • 64
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    • is available via the internet at
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  • 73
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    • Perturbation expressions for the ZFS parameters D and E make this expectation plausible for a ground dxy state in the t2g multiplet with octahedral symmetry. However, a very low symmetry ligand field at the iron site may well mix the t 2g states in a way that causes E/D to approach its maximal rhombic value and thus make the sign of D ambiguous. We note that our fits to the spectra resulted in relatively small values for E/D, which provides some modest support for the consistency of constraining D to be negative. Admittedly, E/D is a soft parameter, in that it could be constrained to a much large value and variation of other fit parameters could converge to a fit of nearly comparable quality
    • 2g states in a way that causes E/D to approach its maximal rhombic value and thus make the sign of D ambiguous. We note that our fits to the spectra resulted in relatively small values for E/D, which provides some modest support for the consistency of constraining D to be negative. Admittedly, E/D is a soft parameter, in that it could be constrained to a much large value and variation of other fit parameters could converge to a fit of nearly comparable quality.


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