Synthesis, characterization, and spectroscopy of model molybdopterin complexes

J Inorg Biochem. 2007 Nov;101(11-12):1601-16. doi: 10.1016/j.jinorgbio.2007.07.012. Epub 2007 Jul 21.

Abstract

The preparation and characterization of new model complexes for the molybdenum cofactor are reported. The new models are distinctive for the inclusion of pterin-substituted dithiolene chelates and have the formulation Tp(*)MoX(pterin-R-dithiolene) (Tp(*)=tris(3,5,-dimethylpyrazolyl)borate), X=O, S, R=aryl. Syntheses of Mo(4+) and (5+) complexes of two pterin-dithiolene derivatives as both oxo and sulfido compounds, and improved syntheses for pterinyl alkynes and [Et(4)N][Tp(*)Mo(IV)(S)S(4)] reagents are described. Characterization methods include electrospray ionization mass spectrometry, electrochemistry, infrared spectroscopy, electron paramagnetic resonance and magnetic circular dichroism. Cyclic voltammetry reveals that the Mo(5+/4+) reduction potential is intermediate between that for dithiolenes with electron-withdrawing substituents and simple dithiolates chelates. Electron paramagnetic resonance and magnetic circular dichroism of Mo(5+) complexes where X=O, R=aryl indicates that the molybdenum environment in the new models is electronically similar to that in Tp(*)MoO(benzenedithiolate).

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Circular Dichroism
  • Coenzymes / chemistry*
  • Electron Spin Resonance Spectroscopy
  • Magnetic Resonance Spectroscopy
  • Metalloproteins / chemistry*
  • Models, Chemical
  • Molecular Structure
  • Molybdenum Cofactors
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry*
  • Pteridines / chemistry*
  • Pterins / chemistry
  • Spectrometry, Mass, Electrospray Ionization

Substances

  • Coenzymes
  • Metalloproteins
  • Molybdenum Cofactors
  • Organometallic Compounds
  • Pteridines
  • Pterins
  • pyranopterin
  • molybdenum cofactor