Collect. Czech. Chem. Commun. 1994, 59, 2611-2620

Nitrosodicyanomethanide Complexes of Cu(II) and Co(II) with Methylpyrazoles; Nucleophilic Additions and Coligand Isomers

Mária Hvastijováa, Jiří Kohouta, Darina Kováčováa and Renate Skirlb

a Department of Inorganic Chemistry, Slovak Technical University, 812 37 Bratislava, Slovak Republic
b Department of Chemistry, Martin Luther University, Halle-Wittenberg, 06120 Halle (Saale), Germany


From the M(II) ONC(CN)2--L systems, where M = Cu or Co and L = pyrazole (pz), 3(5)-methylpyrazole (mpz), 3,4,5-trimethylpyrazole (tmpz), or indazole (inz), the following new compounds were prepared: [M{ONC(CN)2}2L4] with M = Cu, L = pz; M = Co, L = pz, mpz, inz; [M{ONC(CN)2}2L2] with M = Cu, L = tmpz, inz; M = Co, L = tmpz; [M{L.ONC(CN)2}2] with M = Cu, L = mpz; M = Co, L = tmpz. All compounds were studied by thermal decomposition and by infrared and electronic spectroscopy, the Cu(II) complexes also by ESR spectroscopy. Six-coordinate octahedral or pseudooctahedral structures were assigned to complexes of all the types. Nitrosodicyanomethanide is nitroso-N-bonded and in the [M{OCN(CN)2}2L2] complexes is involved in the bidentate bridging. The [M{L.ONC(CN)2}2] complexes contain anionic chelate ligands formed by nucleophilic addition of the N(imine)-C(cyano) type in the M(II) coordination sphere. The first coligand isomer pair with Co(II) central atom is presented.