Synthesis of N,C bound sulfur, selenium, and tellurium heterocycles via the reaction of chalcogen halides with -CH3 substituted diazabutadiene ligands.
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.
Dutton
Jason L
JL
Department of Chemistry, The University of Western Ontario, 1151 Richmond St., London, Ontario, N6A 5B7, Canada.
Martin
Caleb D
CD
Sgro
Michael J
MJ
Jones
Nathan D
ND
Ragogna
Paul J
PJ