Synthesis of N,C Bound Sulfur, Selenium, and Tellurium Heterocycles via the Reaction of Chalcogen Halides with −CH3Substituted Diazabutadiene Ligands Academic Article uri icon

abstract

  • A series of N,C bound chalcogen heterocycles from the reaction of chalcogen halides (ChX(n); Ch = S, Se Te; X = Cl, Br; n = 2, 4) with N-alkyl or N-aryl 1,4-diazabutadiene (DAB) ligands featuring methyl substituents on the backbone C-C linkage are reported. In contrast to what is observed for other p-block elements with the same ligand systems, which typically bind in an N,N' fashion, the chalcogens react with the ligand in an unusual manner, forming N(1)C(3)Ch(1) five-membered rings by incorporating a "backbone" methyl group. Solid state structures of the feature compounds have been confirmed by X-ray crystallographic studies. The reaction mechanism was probed by deuterium isotope labeling of the DAB ligand and analyzed using stopped-flow kinetics experiments, which supported attack by the olefin in the enamine form of the DAB ligand with concomitant loss of HX.

authors

  • Dutton, Jason L
  • Martin, Caleb D
  • Sgro, Michael J
  • Jones, Nathan D
  • Ragogna, Paul J

publication date

  • April 6, 2009