Tricarbonylmanganese(I) derivatives of [Di(pyrazolyl)(2-pyridyl)methyl]aryl scorpionates

The cobalt(II) chloride catalyzed Peterson rearrangement reactions between sulfinyldi-(pyrazolyl) and aryl(pyridyl)methanone derivatives yield di(pyrazolyl)(pyridyl)hetero-scorpionate ligands. Reaction of these ligands with Mn(CO)5Br in the presence of a silver salt produces the monometallic complexes {[κ3-PhC(pz)2(2-py)]Mn(CO)3}(O3SCF3) (1a), {[κ3-PhC(pz)2(2-py)]Mn(CO)3}(PF6) (1b), {[κ3-PhC(4-Mepz)2(2-py)]Mn(CO)3}(PF6) (2), {[κ3-p-BrC6H4C(pz)2(2-py)]Mn(CO)3}(PF6) (3), and the bimetallic complexes [(CO)3Mn{m-C6H4[C(pz)2(2-py)]2}Mn(CO)3](BF4)2 (5a) and {m-C6H4[C(pz)2(2-py)Mn(CO)3]2}(PF6)2 (5b) (pz = pyrazolyl ring, py = pyridyl ring). These octahedral manganese complexes show interesting structural diversity, with the complexes being organized in the solid state into complex supramolecular structures by an array of non-covalent forces.