Control of the hapticity of pyridine-2-thiolate ligands in rhenium(v) oxo complexes

Treatment of [ReO{kappa(3)-B(pz)(4)}(OMe)(2)] 1 with pyridine-2-thiol ligands led to [ReO{kappa(2)-B(pz)(4)}(kappa(2)-Spy*)(OMe)] (Spy*=2-SC5H4N 2 or 2-SC5H3NSiMe3-3 3) or [ReO{kappa(3)-B(pz)(4)}(kappa(1)-2-SC5H4N)(2)] 4, depending on the reaction conditions. Complexes 2 and 3 reacted with trimethylsilyl chloride yielding [ReO{kappa(3)-B(pz)(4)}(kappa(1)-2-SC5H4N)Cl]. HCl 6 and [ReO{kappa(3)-B(pz)(4)}Cl-2], respectively. The characterization of the new compounds involves IR and H-1 NMR spectroscopies, and X-ray diffraction analysis for 3, 4 and 6.