Synthesis of 1,1′-ferrocene bis(carboxypyrazole) compounds and displacement of the pyrazole ligands

The reaction of 1,1′-ferrocenedicarbonyl chloride with pyrazole or 3,5-dimethyl pyrazole generates novel 1,1′-ferrocene bis(amide) compounds 1 and 2, respectively. The crystal structure of 1 shows that the pyrazole rings are essentially co-planar with each other and with the cyclopentadienyl rings. Attempts to use the complexes as a chelating ligand were unsuccessful. Instead, treatment of 1 or 2 with Mo(CO)4(pip)2, pip = piperidine, led to displacement of the pyrazole ligands and formation of the known amide compound, 1,1′-ferrocene bis carbonyl piperidine. Replacement of the pyrazole is ascribed to the weakness of the amide bond caused by the aromaticity of the pyrazole ring. Crystal data for C18H14FeN4O2 (1): monoclinic P2(1)/c, a = 13.3907(18) Å, b = 10.2112(14) Å, c = 11.3082(16) Å, β = 105.209(2)°, V = 1492.1(4) Å3, Z = 4.