Metal coordination and in situ S-C bond cleavage of the bis(2-pyridylthio)methane ligand

The compound [2bpytmH](2)[I-3](2)[I-2], which contains protonated 2bpytm, and four neutral monomeric complexes [CoCl2(2bpytm)] center dot H2O (1), [CoBr2(2bpytm)] (2), [CoI2(2bpytm)]center dot 1/2H(2)O (3) and [NiBr2(2bpytm)]center dot H2O (4) have been obtained during a study into the reactivity of the bis(2-pyridylthio) methane (2bpytm) ligand towards cobalt(II) and nickel(II) halides. Furthermore, a cyclic dimer [CuBr2(2bpytm)](2) (5) and a 1D polymer [CuBr2(2bpytm)](n)center dot CH3CN (6) have been obtained from copper(II)/(I) bromide salts. An unprecedented S-CH2-S activation and cleavage in 2bpytm has been observed on using copper(II) salts with organic and voluminous inorganic anions. The cleavage of 2bpytm enabled the isolation of copper(II) complexes containing the in situ generated ligands 2- pyridinethiolate, 2- pyridinesulfenate or 2- pyridinesulfonate.