Experimental and theoretical studies on cis-dioxomolybdenum(VI) complexes of ONN-donor thiosemicarbazone

Authors : Berat İLHAN CEYLAN, Ayberk YILMAZ, Olcay BÖLÜKBAŞI YALÇINKAYA, Bahri ÜLKÜSEVEN

Pages : 1285-1298

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Publication Date : 0000-00-00

Article Type : Research Paper

Abstract :Cis-dioxomolybdenuminsert ignore into journalissuearticles values(VI); chelate complexes with 5-chloro-2-hydroxybenzophenone S-methyl-4-phenylthiose- micarbazone insert ignore into journalissuearticles values( L ); were synthesized in the general formula insert ignore into journalissuearticles values(MoO 2 ` role=`presentation`> 2 2 _{2} insert ignore into journalissuearticles values(L);D);, where D is an odd- or even-numbered alcohol insert ignore into journalissuearticles values(methanol insert ignore into journalissuearticles values( 1 );, ethanol insert ignore into journalissuearticles values( 2 );, n-propanol insert ignore into journalissuearticles values( 3 );, n-butanol insert ignore into journalissuearticles values( 4 );, and allyl alcohol insert ignore into journalissuearticles values( 5 ););. The structures of 1-5 were verified by elemental analysis, Fourier transform infrared insert ignore into journalissuearticles values(FT-IR);, and 1 ` role=`presentation`> 1 1 ^{1} H NMR spectra. Complex 5 crystallizes in the monoclinic space group P21/n, and its crystalline data showed a dimeric structure formed by a pair of intermolecular hydrogen bonds with 1.92 Å. These dimers are stacked in a similar crystalline structure as a single molecule. The experimental data were compared with the theoretical results obtained by the quantum chemical calculations of the DFT/B3LYP method with LANL2DZ basis set. A detailed interpretation of the FT-IR spectra of the studied compounds was performed based on the total energy distribution. In order to investigate the electronic structures and the UV-Vis spectrum of complex 5 , time-dependent density functional theory calculation was taken into account. The interaction energies between the odd- and even-numbered alcohols and remaining parts of complexes 1-4 were evaluated with the help of natural bonding orbital analysis. In addition, the basis set superposition error correction energies were calculated. The results were evaluated by considering the coordinated alcohols with an even number of carbon atoms to have much higher interaction energy than the next lower homologous alcohols with an odd number of carbon atoms.
Keywords : Thiosemicarbazone, vibrational spectra, density functional theory, time dependent density functional theory, basis set superposition error, natural bonding orbital