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The reactivity of Co III  amine-thiolate complexes with terminal and bridging thiolate functions towards oxidizing agents has been investigated. The mononuclear Co III  N 3 S 3  complex [Co III (L 1 )] (2) (H 3 L 1  represents the hexadentate ligand N,N′,N″-Tris(2-thio-benzyl)-1,1,1 -tris- (aminomethyl)ethane) featuring three terminal thiolate ligands, and the binuclear N 3 Co III - (μ-S) 3 Co III N 3  complex [Co III  2 (L 2 )] 3+  (4) (H 3 L 2  = N,N′,N″-Tris-[2-thio-3-aminomethyl-5-terrbutyl- benzyl]-1,1,1-tris(aminomethyl)ethane) featuring three bridging thiolates were selected. Hydrogen peroxide was the oxidizing agent. Whereas the thiolato-bridged complex 4 is resistant towards oxidation by hydrogen peroxide, 2 undergoes a ligand-based oxidation reaction to give the amine-sulfinate complex [Co(L 1′ )] 5, where all three terminal thiolates have been oxidized to sulfinates without gross structural changes of the parent complex 2. In contrast to 4, the cyclic voltammogram of 2 reveals an irreversible oxidation wave at E = +0.52 V vs SCE which can be attributed to a ligand-centered oxidation reaction. 4 and 5 have been structurally characterized by X-ray crystallography.

Reactivity of Cobalt(III) Amine-Thiolate Complexes with Terminal and Bridging Thiolate Functions towards Hydrogen Peroxide