| Article ID | Journal | Published Year | Pages | File Type |
|---|---|---|---|---|
| 1304408 | Inorganic Chemistry Communications | 2009 | 4 Pages |
C–S bond cleavage in pyridylmethylthioether systems promoted by oxorhenium(V) ion has been established performing the reaction of 1,2-bis(2-pyridylmethylthio)ethane(BPT1), 1,3-bis(2-pyridyl-methylthio)propane(BPT2) and 3,4-bis(2-pyridylmethylthio)-5-methyltoluene (BPT3) with Bu4N[ReOCl4] in dry alcoholoic medium. In case of BPT1 and BPT2, new 2-(2-pyridylmethylthio)ethane-1-thiol (L1H) and 3-(2-pyridylmethylthio)propane-1-thiol (L2H) ligand, respectively were formed in situ through cleavage of one C–S(thioether) bond, resulting in the neutral oxorhenium(V) complexes of formulation [ReO(L1)Cl2] (1a) and [ReO(L2)Cl2] (1b); where as in case of BPT3, binary oxorhenium(V) complex of 3,4-dimercapto-toluene ligand (L3H2), formulated as Bu4N[ReO(L3)2] (1c) through cleavage of two C–S(thioether) bonds. The presence of picolinic acid, as by-product in the filtrates of the C–S bond cleavage reactions in dry alcohol, was detected by treatment of copper(II) salts and GC–MS techniques. But in hydrated alcoholic medium no C–S bond cleavage induced by ReO(V) ion occurred in any of the BPT systems rather the conversion of ReO(V) into perrhenate salt was observed; this reaction mixture, in turn on reaction with copper(II) nitrate trihydrate salt, produce [Cu(BPT)Cl]ReO4 (2) type complexes. The solid-state structures of complexes 1a and 2a were established by X-ray crystallography.
Graphical abstractC–S bond cleavage in pyridylmethylthioether systems promoted by oxorhenium(V) ion has been established performing the reaction of 1,2-bis(2-pyridyl-methylthio)ethane(BPT1), 1,3-bis(2-pyridylmethylthio)propane(BPT2) and 3,4-bis(2-pyridylmethylthio)-5-methyltoluene (BPT3) with Bu4N[ReOCl4] in alcoholic medium. Two new oxorhenium(V) complexes of in situ formed new thiol ligands (NSS donor sets) formulated as [ReO(L1)Cl2] (1a) and [ReO(L2)Cl2] (1b) were produced through cleavage of one C–S(thioether) bond in BPT1 and BPT2; where as a binary oxorhenium(V) complex of 3,4-dimercapto-toluene ligand (L3H2) as Bu4N[ReO(L3)2] (1c) through cleavage of two C–S(thioether) bonds in BPT3. The resulting complexes were structurally characterized.Figure optionsDownload full-size imageDownload as PowerPoint slide
