An experimental and theoretical (DFT) investigation of the coordination mode of 2,4-dithiouracil (2,4-dtucH(2)) in copper(I) complexes with 1,2-bis(diphenylphosphanyl)benzene (dppbz): The crystal structures of [Cu(mu-Br)(dppbz)](2) and [CuBr(dppbz)(2,4-dtucH(2))]

 
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An experimental and theoretical (DFT) investigation of the coordination mode of 2,4-dithiouracil (2,4-dtucH(2)) in copper(I) complexes with 1,2-bis(diphenylphosphanyl)benzene (dppbz): The crystal structures of [Cu(mu-Br)(dppbz)](2) and [CuBr(dppbz)(2,4-dtucH(2))] (EN)

Aslanidis, P. (EN)

Πανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείας (EL)
Aslanidis, P. (EN)

Novel copper(I) mixed-ligand complexes containing 1,2-bis (diphenylphosphanyl) benzene (dppbz) and 2,4-dithiouracil (2,4-dtucH(2)) ligands have been synthesised by addition of the thione ligand to the dinuclear [Cu(mu-X)(dppbz)](2) intermediate in acetonitrile/methanol or acetone solution. The molecular structures of both the precursor [Cu(mu-Br)(dppbz)]2 and the [CuBr(dppbz)(2,4-dtucH(2))] complexes were established by single-crystal X-ray diffraction. Interestingly, the structure of the thione-free dimer involves two diphosphanechelated Cu-I centres bridged by two bromide ligands, thus forming a non-planar Cu2Br2 core. The structure of [CuBr(dppbz)(2,4-dtucH(2))] corresponds to a four-coordinate Cu-I centre in a tetrahedral coordination environment with the heterocyclic dithione ligand being coordinated to the metal centre in a unidentate fashion through its exocyclic sulfur donor atom. The structural, bonding and electronic properties of the model complexes [Cu(mu-X)(dppbz)](2) and [CuX(dppbz)(2,4-dtucH(2))] (X = Cl, Br, or I) are adequately described by DFT/B3LYP computational techniques. All model dinuclear [Cu(mu-X)(dppbz)](2) complexes exhibit pi-type MOs delocalised over the entire four-membered Cu(mu-X)(2)Cu ring, thereby accounting for the near equivalency of the CuX bonds. Moreover, the [Cu(mu-X)(dppbz)](2) dimers possess a sigma-type MO corresponding to weak Cu center dot center dot Cu bonding interactions, which further stabilize the Cu(mu-X)(2)Cu ring. According to our calculations, the interaction energies of the 2,4-dtucH(2) ligand with the Cu-I centre are predicted to be about 13-16 kcal mol(-1). The coordination of the 2,4-dtucH(2) ligand is further stabilized by an X center dot center dot H-N hydrogen bond that is perpendicular to the plane of the dppbz ligand. (EN)

copper (EN)

Πανεπιστήμιο Ιωαννίνων (EL)
University of Ioannina (EN)

European Journal of Inorganic Chemistry (EN)

Αγγλική γλώσσα

2006

<Go to ISI>://000235349100008



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