Heteronucleare komplexverbindungen mit metall-metall-bindungen: VII. Umsetzungen von (NH 3) x,CuCo(CO) 4 mit methylendiaminen. Die strukturen von [(NH 3)(η 2, μ 2-Me 3triaz) Cu 2{μ-Co(CO) 4)} (Co(CO) 4}] (Me 3triaz = 1,3,5-Trimethyl-1,3,5-triazacyclohexan), [{HN(CH 2NMe 2) 2} CuCo(CO) 4], [{ nPrN(CH 2NMe 2) 2}CuCo(CO) 4], [{(Me 2NH)CuCo(CO) 4} 2] und [(μ- N : N′-hmt)Cu 2{Co(CO) 4} 2] 2/2 · THF (hmt =

Abstract

The reaction of [(NH 3) 2CuCo(CO) 4] ( 1a) with 1,3,5-trimethyl-1,3,5-triazacyclohexane (Me 3triaz) yields the tetranuclear compound [(NH 3) (η 2, μ 2-Me 3triaz)Cu 2{μ-Co(CO) 4}{Co(CO) 4}] with Me 3triaz- and Co(CO) 4-bridged Cu 2-dumbbells. Similar methylenediamine ligands react in a Mannich-type manner: 1a and N, N, N′, N′-tetramethylmethylenediamin (tmmd) react to give [{HN(CH 2NMe 2) 2}-CuCo(CO) 4] with the bis( N, N-dimethylaminomethyl)amine ligand formed by a twofold amino of NH 3; substitution of NH 3 by n-propylamine in 1a and reaction with tmmd yields the analogous compound with the N, N-bis( N′, N′-dimethylaminomethyl)-n-propylamine ligand. Dimethylamine, the by-product of the aminomethylation, is detected as a coordination compound with CuCo(CO) 4. The reaction of 1a with methylenediamine dihydrochloride yields a linear polymer with tetranucle ar Cu 2{Co(CO) 4} 2 characterized by single crystal X-ray structure analysis.