Scorpionate Ligands Based on 2-Mercaptopyridine: A Ligand with a Greater Propensity To Sting?

The synthesis and characterization of the first platinum group metal complexes of the recently reported ligand (H2B(mp)(2)](-) (where mp = 2-mercaptopyridyl) are presented herein. Addition of 2 equiv of Na[H2B(mp)(2)] to [MCl(COD)](2) (where M = Rh, Ir; COD = 1,5-cyclo-octadiene) leads to the hydride migration products [Rh{kappa(3)-SSB-BH(mp)(2)}(eta(3)-C8H13)] and [Ir(H){kappa(3)-SSB-BH(mp)(2)}-(eta(4)-C8H12)], respectively. Structural characterization of the rhodium complex reveals a notably short rhodium-boron distance of 2.054(2) angstrom. The reactivity observed for the rhodium complex is different from that of all known scorpionate ligands, suggesting a higher propensity for hydride migration within the 2-mercaptopyridine-based ligands. The complex [Ir(Cl){kappa(3)-SSB-BH(mp)(2)}(eta(4)-C8H12)}, which is formed via hydride/halide exchange in chloroform, is also structurally characterized. The new complexes provide rare examples of metallaboratrane complexes where one hydrogen substituent remains at the boron center.