Synthesis of zinc, copper, nickel, cobalt, and iron complexes using tris(pyrazolyl)methane sulfonate ligands: a structural model for N,N,O binding in metalloenzymes

Inorg Chem. 2006 Mar 6;45(5):2242-50. doi: 10.1021/ic051579a.

Abstract

Ligands of intermediate steric bulk were designed to mimic metalloenzymes with histidine and carboxlyate binding sites. The reaction between tris(3-isopropylpyrazolyl)methane and butyllithium followed by SO3NMe3 in THF yielded the new ligand lithium tris(3-isopropylpyrazolyl)methane sulfonate (LiTpmsiPr). Various metal salts reacted with LiTpmsiPr to give the octahedral complexes M(TpmsiPr)2 (M = Zn, Cu, Ni, Co, Fe) in which each ligand has N,N,O binding to the metal. In the reaction between LiTpmsiPr and ZnCl2, in addition to the major product Zn(TpmsiPr)2, [LiTpmsiPrZnCl2].2THF was also formed as a minor product with a tetrahedral zinc atom coordinated to either N,N,Cl,Cl in the solid phase or N,N,N,Cl in acetonitrile solution. Although TpmsiPr is coordinatively flexible and can act as a bipodal or tripodal ligand, it appears to favor the formation of octahedral L2M complexes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Binding Sites
  • Chemistry, Inorganic / methods*
  • Cobalt
  • Copper
  • Enzymes / chemistry*
  • Enzymes / metabolism*
  • Iron
  • Ligands
  • Magnetic Resonance Spectroscopy
  • Metals / chemistry
  • Metals / metabolism*
  • Models, Chemical*
  • Molecular Structure
  • Nickel
  • Nitrogen / chemistry
  • Nitrogen / metabolism
  • Oxygen / chemistry
  • Oxygen / metabolism
  • Pyrazoles / chemistry
  • Solubility
  • Spectrophotometry, Ultraviolet
  • Sulfonic Acids / chemistry
  • Zinc

Substances

  • Enzymes
  • Ligands
  • Metals
  • Pyrazoles
  • Sulfonic Acids
  • tris(pyrazolyl)methane
  • Cobalt
  • Copper
  • Nickel
  • Iron
  • Zinc
  • Nitrogen
  • Oxygen