HETERONUCLEAR COMPLEXES WITH METAL-METAL BONDS .7. REACTIONS OF (NH3)XCUCO(CO)4 WITH METHYLENEDIAMINE - STRUCTURES OF [(NH3)(ETA-2, MU-2-ME3TRIAZO)/CU2(MU-CO(CO)4)(CO(CO)4)] (ME3TRIAZO=1,3,5-TRIMETHYL-1,3,5-TRIAZACYCLOHEXANE), [(HN(CH2NME2))CUCO(CO)4], [(NPRN(CH2NME2)2)CUCO(CO)4], [((ME2NH)CUCO(CO)4)2] AND [(MU-N-N'-HMT)(CU2(CO(CO)4)2](N/N).THF(HMT=HEXAMETHYLENETETRAMINE)

The reaction of [(NH3)2CuCo(CO)4] (1a) with 1,3,5-trimethyl-1,3,5-triazacyclohexane (Me3triaz) yields the tetranuclear compound [(NH3) (eta-2,mu-2-Me3triaz)Cu2(mu-Co(CO)4)}{Co(CO)4}] with Me3triaz- and Co(CO)4-bridged Cu2-dumbbells. Similar methylenediamine ligands react in a Mannich-type manner: 1a and N,N,N',N'-tetramethylmethylenediamine (tmmd) react to give [{HN(CH2NMe2)2}-CuCo(CO)4] with the bis(N,N-dimethylaminomethyl)amine ligand formed by a twofold aminomethylation of NH3; substitution of NH3 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 tetranuclear Cu2{Co(CO)4}2 units and bridging N:N'-hexamethylenetetramine ligands. All new coordination compounds are characterized by single crystal X-ray structure analysis.