The possibility of synthesis of (poly-)chalcogenide and chalcogenolate ions to manganese, iron and cobalt was expanded with the introduction of the donor ligand carbon monoxide. The metal atoms get than greater coordination numbers. So it was possible to synthesise new metal frameworks, p. e. „Co11E7“ in the complexes [Ph4P]2[Co11Se7(CO)10] and [Ph4P]2[Co11Te7(CO)10], in which the cobalt atoms built a inner centred pentagonal prism. In the examined reaction systems Mn2(CO)10/Na2Sex/Kat, Fe(CO)5/Na2Ex/Kat and Co2(CO)8/Na2Ex/Kat (E = Se or Te; x = 1 or 2; Kat = Ph4PCl or PPNCl) succeeded the synthesis of [Co6Se8(CO)6]-/2-anions as first anionic clusters of the M6E8L6 class. The difference between the new [Co6Se8(CO)4]- anion and the M6E8L6-complex class is the extraordinary compressed Co6-oktaeder and considerable shorter Co-Co-distances. In addition to the higher mentioned compounds it was possible to synthesise and characterize unambiguous with the aid of single crystal x-ray crystallography the following complexes: [Ph4P]2[Fe3Te(CO)9]; [Ph4P][Fe3EH(CO)9] für E=Se,Te; [Ph4P]2 [Fe4Te2(CO)14]; [Ph4P]2 [Fe6Se6(CO)12]; [Ph4P]2 [Mn3Se2(CO)9]. Worth mentioning is also the unusual square pyramidal coordination of the manganese atom in the [Ph4P][Mn(CO)5] crystal. Until now were only penta carbonyl complexes known with a trigonal bipyramidal coordination.