Phase transitions and antiferromagnetism in copper(II) hexanoates: a new tetranuclear type of copper carboxylate paddle-wheel association

A series of compounds of formula [{Cu₂(OOCC_mH_2m + 1)₄(urea)}₂] (m=5-11) have been characterized. X-ray structure analysis for the hexanoate compound reveals a new type of tetranuclear dicopper(II) tetracarboxylate, where the central coordination sphere in [{Cu₂(OOCC₅H₁₁)₄(urea)}₂] is composed of two dinuclear dicopper tetracarboxylates, connected via two inter-dinuclear Cu-O coordination bonds at a distance 2.222(2) Å through the apical positions of two dimers. Urea molecules (Cu-O 2.114(2) Å) occupy both outside apical positions of the resulting tetranuclear units. A strong antiferromagnetic behaviour has been shown for [{Cu₂(OOCC₅H₁₁)₄(urea)}₂] (−2J=261.4(4) cm⁻¹), and compared with related isolated dinuclear and polymeric hexanoate compounds [Cu₂(OOCC₅H₁₁)₄(urea)₂], [Cu₂(OOCC₅H₁₁)₄]_n, respectively. Only small differences in the magnetic susceptibility have been found, while EPR spectroscopy showed significantly different results for all three hexanoate compounds, also with the dicopper tetracarboxylate central core and square-pyramidal CuO₄O chromophores. A solid-to-solid phase transition for [{Cu₂(OOCC₅H₁₁)₄(urea)}₂] was observed by magnetic measurement and analysed for the whole series [{Cu₂(OOCC_mH_2m + 1)₄(urea)}₂] by TG, DTA, and variable temperature XRD studies.     

Five-coordinate zinc(II) complexes with optically active Schiff bases derived from (1R,2R)-(−)cyclohexanediamine: X-ray structure and CP MAS NMR characterization of [cyclohexylenebis(5-chlorosalicylideneiminato)zinc(II)pyridine] and [cyclohexylenebis(5-bromosalicylideneiminato)zinc(II)pyridine]

Schiff bases obtained from (1R,2R)-(−)-cyclohexanediamine and 5-chloro- (1) or 5-bromosalicylaldehyde (2) are used as ligands for Zn(II) resulting in [(1R,2R)-cyclohexylenebis(5-chlorosalicylideneiminato)]zinc(II) (1a) and (1R,2R)-[cyclohexylenebis-(5-bromosalicylideneiminato)]zinc(II) (2a). In the presence of pyridine, 1a and 2a turned out into (1R,2R)-[cyclohexylenebis(5-chlorosalicylideneiminato)pyridine]zinc(II) (1b) and (1R,2R)-[cyclohexylenebis(5-bromosalicylideneiminato)pyridine]zinc(II) (2b). Coordination sphere of Zn(II) atoms in both pyridine adducts is a slightly distorted square pyramid, with N₂O₂ chromophore units and axially bonded pyridine as it is evident from single crystal X-ray analyzes of 1b and 2b. The asymmetric unit of 1b and 2b contains two molecules of complexes. The observed distances of Zn-O in both molecules indicate the rigidity of the tetradentate ligand as a main factor influencing the geometry of coordination sphere. Obtained complexes were characterized by ¹H NMR in solution and ¹³C CP MAS NMR. NOE differential experiments revealed significant steric interactions between C(6)-H in the phenyl ring, cyclohexyl C(1)-H and imine hydrogen. Significant coordination shifts of carbons in the closest proximity to the coordination center were noted as well.     

Complexes of copper(II) dihalide with 2,2′-dipyridylamine. X-ray diffraction structures of the [dibromo-bis(dipyam)copper(II)]–water (1:2) and di[chloro-bis(dipyam)copper(II)]diiodide–acetonitrile (1:2) complexes

The formation of complexes between copper(II) halides and 2,2′-dipyridylamine (dipyam) has been studied systematically. Only complexes with a 1:1 and 1:2 metal-to-ligand ratio are formed. Some mixed chloro–iodide and halide–PF₆ compounds have also been isolated. The X-ray diffraction structures of the [Cu(dipyam)₂Br₂] · 2H₂O (I) and the [Cu(dipyam)₂Cl]₂I₂ · 2CH₃CN (II) complexes are reported. I is a rare example of an octahedral coordination among the copper(II) halide complexes of dipyam. The two bromo atoms, which occupy the apical positions, are H-bonded to the water molecules of crystallization. II is a dimer, where each copper forms a cationic chloro-complex of approximately trigonal bipyramidal geometry, the dimerization being due to hydrogen bonds formed by the NH group of one of the two dipyams coordinated to each metal atom with the chlorine atom of the centrosymmetric cationic complex. The iodide anions are hydrogen-bonded to the NH groups of the dipyams not involved in the dimerization.     

[Benzilato(2−)-O,O]bis[1,3-diphenylpropane-1,3-dionato(1−)-O,O]silicon(IV): a neutral heteroleptic hexacoordinate silicon(IV) complex with an SiO6 skeleton

Reaction of tetramethoxysilane with 1,3-diphenylpropane-1,3-dione and benzilic acid (molar ratio 1:2:1) in tetrahydrofuran/n-pentane yielded the neutral heteroleptic hexacoordinate silicon(IV) complex [benzilato(2−)-O¹,O²]bis[1,3-diphenylpropane-1,3-dionato(1−)-O,O]silicon(IV) (5). Compound 5 was structurally characterized by single-crystal X-ray diffraction, solid-state VACP/MAS NMR spectroscopy (²⁹Si), and solution NMR spectroscopy (¹H, ¹³C, ²⁹Si). The chiral silicon(IV) complex, with its octahedral SiO₆ coordination polyhedron, is configurationally stable in solution on the NMR time scale (solvent: CDCl₃; maximum temperature studied: 58 °C).