Cobalt(II) chloride adducts with acetonitrile, propan-2-ol and tetrahydrofuran: considerations on nuclearity, reactivity and synthetic applications

摘要

High-spin cobalt(II) complexes are considered useful building blocks for the synthesis of single-molecule magnets (SMM) because of their intrinsic magnetic anisotropy. In this work, three new cobalt(II) chloride adducts with labile ligands have been synthesized from anhydrous CoCl_2, to be subsequently employed as starting materials for heterobimetallic compounds. The products were characterized by elemental, spectroscopic (EPR and FT-IR) and single-crystal X-ray diffraction analyses. trans-Tetrakis(acetonitrile-κN)bis(tetrahydro-furan-κO)cobalt(II)bis[(acetonitrile-κN)trichloridocobaltate(II)], [Co(C_2H_3N)_4-(C_4H_8O)_2][CoCl_3(C_2H_3N)]_2, (1), comprises mononuclear ions and contains both acetonitrile and tetrahydrofuran (thf) ligands, The coordination polymer catena-poly[[tetrakis(propan-2-ol-κO)cobalt(II)]-/x-chlorido-[dichloridocobalt(II)]-μ-chlorido], [Co_2Cl_4(C_3H_8O)_4], (2'), was prepared by direct reaction between anhydrous CoCl_2 and propan-2-ol in an attempt to rationalize the formation of the CoCl_2-alcohol adduct (2), probably CoCl_2(HO~iPr)_m. The binuclear complex di-μ-chlorido-l:2κ~4Cl:Cl-dichlorido-2κ~2Cl-tetrakis(tetrahydrofuran-1κO)-dicobalt(II), [Co_2Cl_4(C_4H_8O)_4], (3), was obtained from (2) after recrystallization from tetrahydrofuran. All three products present cobalt(II) centres in both octahedral and tetrahedral environments, the former usually less distorted than the latter, regardless of the nature of the neutral ligand. Product (2') is stabilized by an intramolecular hydrogen-bond network that appears to favour a trans arrangement of the chloride ligands in the octahedral moiety; this differs from the cis disposition found in (3). The expected easy displacement of the bound solvent molecules from the metal coordination sphere makes the three compounds good candidates for suitable starting materials in a number of synthetic applications.