Novel organometallic building blocks for molecular crystal engineering. Part 4. Synthesis and characterization of mono- and bis-amido derivatives of [CoIII(h5-C5H4COOH)2]+ and their utilization as ligands.

The synthesis and structural characterization of the hexafluorophosphate salts of the substituted bis-amido mol. complexes [CoIII(h5-C5H4CONHC4H3N2)2]+ (1), [CoIII(h5-C5H4CONHCH2C5H4N)2]+ (2), [CoIII(h5-C5H4CON(C5H4N)2)2]+ (3), and of the amido-carboxyl complexes [CoIII(h5-C5H4CON(C5H4N)2)(h5-C5H4COOH)]+ (4), and [CoIII(h5-C5H4CONHC2N3(C5H4N)2)(h5-C5H4COOH)]+ (5) are reported. The pyridyl and pyrazine substituted amido ligands on the sandwich cores have been chosen because they allow both coordination to metal centers and participation in hydrogen bonding. The hydrogen bonding interactions established by the family of complexes in the solid state has been investigated. The utilization of complex 5 for the prepn. of the complex of complexes [Cd(NO3)2{CoIII(h5-C5H4CONHC2N3(C5H4N)(C5H4NH))(h5-C5H4COOH)}2]6+ (6) is reported as a first example of the potential of the substituted mono-and bis-amides as ligands. The isolation and structural characterization of the carbonyl chloride cation [CoIII(h5-C5H4COCl)2]+ (7) as its tetrachloro cobaltate anion salt is also described.