POLYNUCLEAR AGGREGATION OF COBALT AND MANGANESE DICHLORIDES - SYNTHESIS, PROPERTIES AND STRUCTURES OF MONOMERIC [COCL2(TMEN)], IONIC [CO3(MU(3)-CL)(2)-(MU-CL)(3)(TMEN)(3)][BPH(4)], POLYMERIC MNCL2-CENTER-DOT-TMEN AND TETRANUCLEAR [MN-4-(MU-CL)(6)CL-2(TMEN)(4)] (TMEN=ME(2)NCH(2)CH(2)NME(2))

The complexes [CoCl2(tmen)] 1, -3(mu(3)-Cl)(2)(mu-Cl)(3)(tmen)(3)][BPh (4)].[CoCl2 (tmen)] 2, MnCl2 . tmen 3 and [Mn-4(mu-Cl)(6)Cl-2(tmen)(4) ] 4 (tmen = Me(2)NCH(2)CH(2)NMe(2)) have been synthesized and structur ally characterized by X-ray diffraction. The crystals of 1 consist of the tetrahedral [CoCl2(tmen)] molecules. The structure of the co-cryst allite 2 is composed of two independent species, ionic [Co-3(mu(3)-Cl) (2)(mu-Cl)(3)(tmen)(3)][BPh(4)] and molecular [CoCl2(tmen)]. In the fi rst compound the trinuclear [Co-3(mu(3)-Cl)(2)(mu-Cl)(3)(tmen)(3)](+) cations consist of triangulo-{Co3Cl3} units defined by three cobalt at oms with three bridging chloride atoms in the same plane. The remainin g two mu(3)-chloride atoms are symmetrically placed above and below th e molecular plane. The polymeric chain of compound 3 is formed by six- co-ordinate manganese(II) centres linked by double chloride bridges. T wo nitrogen atoms from the co-ordinated tmen complete the octahedral c o-ordination of the manganese. The crystals of compound 4 consist of t etranuclear molecules in which two internal six-co-ordinate and two pe ripheral five-co-ordinate Mn atoms are linked by double chloride bridg es. The natures of the ligand and solvent as key factors promoting the particular aggregation of the cobalt and manganese dichlorides is dis cussed.