Abstract
The current interest in metal complexes possessing coordinated sulfur ligands derives from their potential relevance to active sites in metalloenzymes in biochemistry and also from their essential role in heterogeneous catalysis in inorganic chemistry. The oxidation reactions of metal thiolates by hydrogen peroxide, molecular oxygen, dioxiranes, and peracids have been reviewed. The compounds resulting from oxidation and oxygenation of nickel thiolate complexes have been isolated, separated, and characterized. Molecular oxygen or hydrogen peroxide reacted with (N,N'-bis(mercaptoethyl)-1,5-diazacyclooctane-nickel(II), (BME-DACO)2Ni3 +2, to produce a trimetallic, (N,N'-bismercaptoethyl-1,5-diazacyclooctane-nickel(II))-nickelate, (BME-DACO)2Ni3 2+, resulting from electron-transfer and ligand oxidation, as well as two oxygenates, N,N'-mercaptoethylsulfinylethyldiazacyclooctanenickel(II), (MESE-DACO)Ni, and N,N'-bissulfinylethyldiazacyclooctane nickel(II), (BSE-DACO)Ni. A mechanism involving the formation of thiadioxirane intermediates is proposed for the reaction with molecular oxygen in aprotic solvent.
Soma, Takako (1996). Oxygen addition to sulfur of metal thiolates. Master's thesis, Texas A&M University. Available electronically from
https : / /hdl .handle .net /1969 .1 /ETD -TAMU -1996 -THESIS -S659.