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Reaction Diversity of the S–S Bond Promoted by Metal Coordination: From Discovery to Controllable Reactions
Author(s) -
Zhu HaiBin,
Li Lei,
Xu Gang,
Gou ShaoHua
Publication year - 2010
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200900913
Subject(s) - chemistry , pyrimidine , ligand (biochemistry) , yield (engineering) , medicinal chemistry , bond cleavage , solvent , coordination complex , in situ , metal , stereochemistry , catalysis , organic chemistry , receptor , metallurgy , biochemistry , materials science
Promoted by NiCl 2 coordination in the mixed solvent MeOH/CH 2 Cl 2 , diverse in situ S–S bond reactions, such as S ‐oxidation and S–S and C–S bond scission, occurred in the disulfide ligand of 2‐ppds {bis[4‐(pyridin‐2‐yl)pyrimidin‐2‐yl]disulfane} to yield three new components identified as 2‐mpp [2‐methoxy‐4‐(pyridin‐2‐yl)pyrimidine], 2‐ppst { S ‐[4‐(pyridin‐2‐yl)pyrimidin‐2‐yl] 4‐(pyridin‐2‐yl)pyrimidine‐2‐sulfonothioate} and 2‐pps {bis[4‐(pyridin‐2‐yl)pyrimidin‐2‐yl]sulfane}. More importantly, such in situ reactions could be efficaciously controlled so that they proceed in a highly selective manner. Thus, NiCl 2 ‐mediated in situ reaction of 2‐ppds with the aid of continuous air bubbling through the reaction mixture exclusively led to 2‐pps, whereas replacement of NiCl 2 by Cu(OAc) 2 afforded 2‐mpp alone. A confirmatory experiment proved that 2‐ppst served as a decisive intermediate in these in situ reactions.