Metal coordination and in situS–C bond cleavage of the bis(2-pyridylthio)methane ligandElectronic supplementary information (ESI) available: Crystallographic and refinement data, details of intermolecular interactions and torsion angles in the chelate ring. CCDC reference numbers 778412–778418. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c0dt00560f

The compound [2bpytmH]2[I3]2[I2], which contains protonated 2bpytm, and four neutral monomeric complexes [CoCl2(2bpytm)]·H2O (1), [CoBr2(2bpytm)] (2), [CoI2(2bpytm)]·1/2H2O (3) and [NiBr2(2bpytm)]·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·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 situgenerated ligands 2-pyridinethiolate, 2-pyridinesulfenate or 2-pyridinesulfonate. [ABSTRACT FROM AUTHOR]