Heteronukleare Komplexverbindungen mit Metall—Metall-Bindungen. IX [1]. Amin-kupfer(I)-carbonylmetallate mit Cobalt,Eisen oder Mangan

Heteronuclear Coordination Compounds with Metal—Metal Bonds. IX. Amine Copper(I) Carbonyl Metalates with Cobalt, Iron, or Manganese Colourless crystals of the carbonyl copper complex [(NH₃)₃(CO)Cu][Co(CO)₄] ( 1 a ) are formed in the reaction of [Cu(NH₃)₄]Cl and Na[Co(CO)₄] (T < ? 8°C, p_CO = 1 bar); above ?5°C and under N₂-atmosphere 1 a converts to [(NH₃)₂CuCo(CO)₄] ( C ), which serves as a starting material for the synthesis of new copper cobaltates: the amines N-amino piperidine, N,N-dimethyl ethylenediamine (dmed) and N-benzyl N,N′-dimethyl ethylenediamine (bn-dmed) replace NH₃ to form [(C₅H₁₀N? NH₂)₃CuCo(CO)₄] ( 1 b ), [(dmed)CuCo(CO)₄] ( 1 c ), [(bn-dmed)CuCo(CO)₄] ( 1 d ) the Cu? Co-bond remaining intact. [(NH₃)₂CuFe(CO)₃NO] ( 2 a ) is isosteric with C ; it is synthesized from [Cu(NH₃)₄]Cl and Na[Fe(CO)₃NO] in aqueous solution; 2 a reacts with N,N,N′,N′-tetramethyl ethylenediamine (tmed) to form [(tmed)(NH₃)CuFe(CO)₃NO] ( 2b ). The [Mn(CO)₅]^? ion reacts with ammine copper ions to form the tetranuclear cluster [{(NH₃)CuMn(CO)₅}₂] ( 3 ). All new compounds have been investigated by X-ray structure analysis.