Synthesis, structure, and spectroscopy of pseudotetrahedral CoIIN3(SR) complexes. Active site approximations to the cobalt(II)-substituted type 1 copper proteins

Jeffery S. Thompson, Theophilus Sorrell, Tobin J Marks, James A. Ibers

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Abstract

Complexes of the stoichiometry CoIIN3(SR) were prepared by the reaction of CoCl(SR) (SR = O-ethylcysteinate) with potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate, K(HB(3,5-Me2pz)3), or by the reaction of CoBr(HB(3,5-Me2pz)3) with NaSR (SR = p-nitrobenzenethiolate or pentafluorophenylthiolate). These complexes are synthetic approximations to a proposed active site in the cobalt(II)-substituted blue copper proteins. The complexes were characterized by electronic spectral, NMR, and XPS techniques. The complex pentafluorophenylthiolato(hydrotris(3,5-dimethyl-1-pyrazolyl)borato)-cobalt(II) was also characterized by single-crystal X-ray diffraction methods. The complex crystallizes in the monoclinic space group C2h5-P21/n with four molecules in a unit cell of dimensions a = 15.46 (1) Å, b = 7.841 (8) Å, c = 22.20 (2) Å, and β = 91.89 (2)° (-162°C). Least-squares refinement of the 106 variables has led to a value of the conventional R index (on F) of 0.106 for 827 independent reflections having Fo2 > 3σ(Fo2). The geometry about the cobalt(II) ion, which is coordinated to three nitrogen atoms and one sulfur atom, is distorted tetrahedral, with N-Co-N angles ranging from 89.3 (7) to 94.1 (7)° and with N-Co-S angles ranging from 107.7 (6) to 138.3 (6)°. The Co-N distances range from 1.97 (2) to 2.01 (2) Å, and the Co-S distance is 2.26 (1)Å.

Original languageEnglish
Pages (from-to)4193-4200
Number of pages8
JournalJournal of the American Chemical Society
Volume101
Issue number15
Publication statusPublished - 1979

Fingerprint

Cobalt
Stoichiometry
Copper
Catalytic Domain
Spectrum Analysis
Spectroscopy
Proteins
Borates
Least-Squares Analysis
Sulfur
X-Ray Diffraction
Atoms
Potassium
Nitrogen
Ions
X ray photoelectron spectroscopy
Nuclear magnetic resonance
Single crystals
X ray diffraction
Molecules

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis, structure, and spectroscopy of pseudotetrahedral CoIIN3(SR) complexes. Active site approximations to the cobalt(II)-substituted type 1 copper proteins. / Thompson, Jeffery S.; Sorrell, Theophilus; Marks, Tobin J; Ibers, James A.

In: Journal of the American Chemical Society, Vol. 101, No. 15, 1979, p. 4193-4200.

Research output: Contribution to journalArticle

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title = "Synthesis, structure, and spectroscopy of pseudotetrahedral CoIIN3(SR) complexes. Active site approximations to the cobalt(II)-substituted type 1 copper proteins",
abstract = "Complexes of the stoichiometry CoIIN3(SR) were prepared by the reaction of CoCl(SR) (SR = O-ethylcysteinate) with potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate, K(HB(3,5-Me2pz)3), or by the reaction of CoBr(HB(3,5-Me2pz)3) with NaSR (SR = p-nitrobenzenethiolate or pentafluorophenylthiolate). These complexes are synthetic approximations to a proposed active site in the cobalt(II)-substituted blue copper proteins. The complexes were characterized by electronic spectral, NMR, and XPS techniques. The complex pentafluorophenylthiolato(hydrotris(3,5-dimethyl-1-pyrazolyl)borato)-cobalt(II) was also characterized by single-crystal X-ray diffraction methods. The complex crystallizes in the monoclinic space group C2h5-P21/n with four molecules in a unit cell of dimensions a = 15.46 (1) {\AA}, b = 7.841 (8) {\AA}, c = 22.20 (2) {\AA}, and β = 91.89 (2)° (-162°C). Least-squares refinement of the 106 variables has led to a value of the conventional R index (on F) of 0.106 for 827 independent reflections having Fo2 > 3σ(Fo2). The geometry about the cobalt(II) ion, which is coordinated to three nitrogen atoms and one sulfur atom, is distorted tetrahedral, with N-Co-N angles ranging from 89.3 (7) to 94.1 (7)° and with N-Co-S angles ranging from 107.7 (6) to 138.3 (6)°. The Co-N distances range from 1.97 (2) to 2.01 (2) {\AA}, and the Co-S distance is 2.26 (1){\AA}.",
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AU - Sorrell, Theophilus

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AU - Ibers, James A.

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N2 - Complexes of the stoichiometry CoIIN3(SR) were prepared by the reaction of CoCl(SR) (SR = O-ethylcysteinate) with potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate, K(HB(3,5-Me2pz)3), or by the reaction of CoBr(HB(3,5-Me2pz)3) with NaSR (SR = p-nitrobenzenethiolate or pentafluorophenylthiolate). These complexes are synthetic approximations to a proposed active site in the cobalt(II)-substituted blue copper proteins. The complexes were characterized by electronic spectral, NMR, and XPS techniques. The complex pentafluorophenylthiolato(hydrotris(3,5-dimethyl-1-pyrazolyl)borato)-cobalt(II) was also characterized by single-crystal X-ray diffraction methods. The complex crystallizes in the monoclinic space group C2h5-P21/n with four molecules in a unit cell of dimensions a = 15.46 (1) Å, b = 7.841 (8) Å, c = 22.20 (2) Å, and β = 91.89 (2)° (-162°C). Least-squares refinement of the 106 variables has led to a value of the conventional R index (on F) of 0.106 for 827 independent reflections having Fo2 > 3σ(Fo2). The geometry about the cobalt(II) ion, which is coordinated to three nitrogen atoms and one sulfur atom, is distorted tetrahedral, with N-Co-N angles ranging from 89.3 (7) to 94.1 (7)° and with N-Co-S angles ranging from 107.7 (6) to 138.3 (6)°. The Co-N distances range from 1.97 (2) to 2.01 (2) Å, and the Co-S distance is 2.26 (1)Å.

AB - Complexes of the stoichiometry CoIIN3(SR) were prepared by the reaction of CoCl(SR) (SR = O-ethylcysteinate) with potassium hydrotris(3,5-dimethyl-1-pyrazolyl)borate, K(HB(3,5-Me2pz)3), or by the reaction of CoBr(HB(3,5-Me2pz)3) with NaSR (SR = p-nitrobenzenethiolate or pentafluorophenylthiolate). These complexes are synthetic approximations to a proposed active site in the cobalt(II)-substituted blue copper proteins. The complexes were characterized by electronic spectral, NMR, and XPS techniques. The complex pentafluorophenylthiolato(hydrotris(3,5-dimethyl-1-pyrazolyl)borato)-cobalt(II) was also characterized by single-crystal X-ray diffraction methods. The complex crystallizes in the monoclinic space group C2h5-P21/n with four molecules in a unit cell of dimensions a = 15.46 (1) Å, b = 7.841 (8) Å, c = 22.20 (2) Å, and β = 91.89 (2)° (-162°C). Least-squares refinement of the 106 variables has led to a value of the conventional R index (on F) of 0.106 for 827 independent reflections having Fo2 > 3σ(Fo2). The geometry about the cobalt(II) ion, which is coordinated to three nitrogen atoms and one sulfur atom, is distorted tetrahedral, with N-Co-N angles ranging from 89.3 (7) to 94.1 (7)° and with N-Co-S angles ranging from 107.7 (6) to 138.3 (6)°. The Co-N distances range from 1.97 (2) to 2.01 (2) Å, and the Co-S distance is 2.26 (1)Å.

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