0000000000505387
AUTHOR
Teresa Picher
Molybdenum(VI)-dioxo complexes with sterically bulky thiocarboxylate ligands. Reactions with aliphatic thiols and electrochemical properties
Abstract Under acid conditions, the reaction of (Bu n 4 N)2[Mo VI O 2 (O 2 CC(S)Ph 2 ) 2 ] with aliphatic thiols yields the monomeric [Mo V O(O 2 CC(S)Ph 2 ) 2 ] − as unique complex product. The experimental pseudo-first order rate constant with respect to the Mo(VI) complex was found to be K =6.1 × 10 −5 s −1 . At neutral pH, however, an unstable Mo(IV) species was formed which was also electrochemically detected in a reversible Mo(V,IV) couple. [Mo V O(O 2 CC(S)Ph 2 ) 2 ] − appears to be obtained by the reaction of [Mo IV O(O 2 CC(S)Ph 2 ) 2 ] 2− with unreacted [Mo VI O 2 (O 2 CC(S)Ph 2 ) 2 ] 2− . Steric features on the ligand (gemdiphenyl groups) explain that the latter reaction does not…
Preparation of 4-substituted 1,3-oxathiolan-5-onesviathe sulphenium ion intermediate generated by the pummerer rearrangement
4-Substituted 1,3-oxathiolan-5-ones have been synthesized via the Pummerer rearrangement from the S-oxide of the parent molecule. The 4,5-dione is obtained in the presence of pyridine N-oxide.