Blue Copper Proteins. Synthesis, Chemistry, and Spectroscopy of Cu1N3(SR) and Cu11N3(SR) Active Site Approximations. Crystal Structure of Potassium p-Nitrobenzenethiolato(hydrotris(3,5-dimethyl-l-pyrazolyl)-borato)cuprate(I) Diacetone, K[Cu(HB(3,5-Me2pz)3)-(SC6H4NO2)].2C3H6O

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

Research output: Contribution to journalArticlepeer-review

124 Scopus citations

Abstract

The cuprous complexes K[Cu(HB(3,5-Me2pz)3)(SR)] (SR = p-nitrobenzenethiolate or O-ethylcysteinate; HB(3,5-Me2pz)3= hydrotris(3,5-dimethyI-l-pyrazolyl)borate) can be prepared by the reaction of Cu(SR) or [Cu(SR)]-(CIO4) with KHB(3.5-Me2pz)3at room temperature. The structure of the complex with SR = p-nitrobenzenethiolate has been determined by X-ray diffraction methods. The complex crystallizes in the triclinic space group C1-P1 with two molecules in a unit cell of dimensions a = 10.60(2) Å, b = 18.17 (4) Å, c = 10.33 (4) Å, a = 93.57 (5)°,β = 116.20 (7)°, and γ = 71.89 (5)°. Least-squares refinement of the 117 variables has led to a value of the conventional R index (on F) of 0.092 for 678 independent reflections having F02>3σ(F02). The geometry about the Cu1 atom, which is coordinated to three nitrogen atoms and one sulfur atom, is trigonally distorted tetrahedral. The cupric complexes Cu(HB(3,5-Me2pz)3)(SR) (SR = p-nitrobenzene-thiolate or O-ethylcysteinate) have been prepared by the reaction of KHB(3,5-Me2pz)3with the corresponding [Cu(SR)]-(CIO4) derivatives at -78°C. UV-visible, laser Raman, and EPR data are used to show that the Cu1complexes have a very similar structure to that of the Cu1 complex characterized by X-ray diffraction methods. The Cu1complex Cu(HB(3,5-Me2pz)3(OR) (OR = p-nitrobenzenephenolate, OC6H4NO2) was prepared by the reaction of NaOC6H4NO2-2H2O with CuBr(HB(3,5-Me2pz)3in tetrahydrofuran at room temperature. The UV-visible, laser Raman, and EPR data for this complex are used in the interpretation of the spectra of the Cu11N3(SR) and Cu11N3(SR) complexes. The spectral properties of the Cu11N3(SR) complexes are similar to those of the blue (type 1) copper proteins and allow certain definite conclusions to be drawn concerning the origin of the distinctive UV-visible, resonance Raman, and EPR spectral features of the proteins.

Original languageEnglish (US)
Pages (from-to)4180-4192
Number of pages13
JournalJournal of the American Chemical Society
Volume101
Issue number15
DOIs
StatePublished - Jul 1 1979

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Fingerprint Dive into the research topics of 'Blue Copper Proteins. Synthesis, Chemistry, and Spectroscopy of Cu<sup>1</sup>N<sub>3</sub>(SR) and Cu<sup>11</sup>N<sub>3</sub>(SR) Active Site Approximations. Crystal Structure of Potassium p-Nitrobenzenethiolato(hydrotris(3,5-dimethyl-l-pyrazolyl)-borato)cuprate(I) Diacetone, K[Cu(HB(3,5-Me<sub>2</sub>pz)<sub>3</sub>)-(SC<sub>6</sub>H<sub>4</sub>NO<sub>2</sub>)].2C<sub>3</sub>H<sub>6</sub>O'. Together they form a unique fingerprint.

Cite this