Synthesis, Characterization, Catalytic Activity, and DFT Calculations of Zn(II) Hydrazone Complexes.

Two new Zn(II) complexes with tridentate hydrazone-based ligands (condensation products of 2-acetylthiazole) were synthesized and characterized by infrared (IR) and nuclear magnetic resonance (NMR) spectroscopy and single crystal X-ray diffraction methods. The complexes 1, 2 and recently synthesized [ZnL3(NCS)2] (L3 = (E)-N,N,N-trimethyl-2-oxo-2-(2-(1-(pyridin-2-yl)ethylidene)hydrazinyl)ethan-1-aminium) complex 3 were tested as potential catalysts for the ketone-amine-alkyne (KA2) coupling reaction. The gas-phase geometry optimization of newly synthesized and characterized Zn(II) complexes has been computed at the density functional theory (DFT)/B3LYP/6-31G level of theory, while the highest occupied molecular orbital and lowest unoccupied molecular orbital (HOMO and LUMO) energies were calculated within the time-dependent density functional theory (TD-DFT) at B3LYP/6-31G and B3LYP/6-311G(d,p) levels of theory. From the energies of frontier molecular orbitals (HOMO-LUMO), the reactivity descriptors, such as chemical potential (µ), hardness (η), softness (S), electronegativity (χ) and electrophilicity index (ω) have been calculated. The energetic behavior of the investigated compounds (1 and 2) has been examined in gas phase and solvent media using the polarizable continuum model. For comparison reasons, the same calculations have been performed for recently synthesized [ZnL3(NCS)2] complex 3. DFT results show that compound 1 has the smaller frontier orbital gap so, it is more polarizable and is associated with a higher chemical reactivity, low kinetic stability and is termed as soft molecule.

2,2'-{1,1'-[2,2'-Oxalylbis(hydrazin-2-yl-1-yl-idene)]diethyl-idyne}dipyridinium bis-(perchlorate) dihydrate.

The title salt, C(16)H(18)N(6)O(2) (2+)·2ClO(4) (-)·2H(2)O, was obtained unintentionally as a major product in the reaction of Zn(ClO(4))(2)·6H(2)O with the N',N'(2)-bis-[(1E)-1-(2-pyrid-yl)ethyl-idene]ethanedihydrazide (H(2)L) ligand. The (H(4)L)(2+) cation lies across a centre of inversion. The pyridiniumimine fragments of (H(4)L)(2+) adopt syn orientations. Intra-molecular N-H⋯N and N-H⋯O hydrogen bonds lead to the formation of S(5) motifs. In the crystal, neighbouring cations are connected by π-π inter-actions between pyridinium units with a centroid-centroid distance of 3.600 (1) Å. Moreover, the crystal components are assembled into two-dimensional layers via N-H⋯O and O-H⋯O hydrogen bonds, with no direct hydrogen-bonding inter-actions between cations.

Tetraaquabis(D-camphor-10-sulfonato)calcium(II).

The structure of the title compound, [Ca(C(10)H(15)O(4)S)(2)(H(2)O)(4)], is the first example in which two D-camphor-10-sulfonate anions are coordinated to a metal ion, in this case with direct Ca-O bonding. The molecule has crystallographically imposed twofold symmetry with the Ca atom on the twofold axis. Hydrogen bonds are formed between the coordinated water molecules and the O atoms of the SO(3)(-) groups of adjacent molecules, leading to the formation of a two-dimensional layered network. The compound displays sharp wavelength-selective transparency in the UV-visible spectrum, offering the potential for application as an optical filter.

Hexaaqua-magnesium(II) bis-(d-camphor-10-sulfonate).

The structure of the title complex, [Mg(H(2)O)(6)](C(10)H(15)O(4)S)(2), consists of regular octa-hedral [Mg(H(2)O)(6)](2+) cations and d-camphor-10-sulfonate anions. A three-dimensional supra-molecular architecture is formed via hydrogen-bond inter-actions [O-H⋯O = 2.723 (2)-2.833 (2) Å] to give alternating layers of [Mg(H(2)O)(6)](2+) cations and d-camphor-10-sulfonate anions. The title compound is isomorphous with the zinc, copper, cadmium and nickel analogues.