Oxorhenium(V) complexes with quinoline-2-carboxylate ligand. X-ray structure of [ReOCl2(quin-2-c)(PPh3)] and [ReOBr2(quin-2-c)(AsPh3)] complexes: DFT and TD-DFT calculations for [ReOCl2(quin-2-c)(PPh3)]

Novel [ReOX₂(quin-2-c)(EPh₃)] complexes (X = Cl, Br; E = As, P; quin-2-c = quinoline-2-carboxylate ion) have been prepared by treatment of [ReOX₃(EPh₃)₂] with quinoline-2-carboxylic acid in acetone at room temperature. All the complexes were characterised by IR, UV–Vis spectroscopy and elemental analysis. The crystal and molecular structures have been determined for [ReOCl₂(qiun-2c)(PPh₃)] (1) and [ReOBr₂(qiun-2c)(AsPh₃)] (4). The electronic structure of 1 has been calculated with the density functional theory (DFT) method. The spin-allowed electronic transitions of 1 have been calculated with the time-dependent DFT method.     

The reactivity of [ReBr3(MeCN)(dppe)] towards gaseous nitric oxide. The X-ray structure of [ReBr3(MeCN)(dppe)] and [ReBr3(NO)(dppe)]0.57[ReOBr3(dppe)]0.43 and DFT calculations for [ReBr3(NO)(dppe)] and [ReOBr3(dppe)]

The [ReOBr₃(dppe)] (dppe=bis(diphenylophosphino)ethane) complex reacts with acetonitrile in the presence of excess of triphenylphpsphine to give a new monomeric nitrile rhenium(III) complex—[ReBr₃(MeCN)(dppe)] (1). The reaction of 1 with gaseous nitric oxide leads to the mixed [ReBr₃(NO)(dppe)]_0.57[ReOBr₃(dppe)]_0.43 complex (2) with rhenium atoms on +2 and +5 oxidation states. This paper presents the synthesis, spectroscopic characterisation and X-ray structure of 1 and 2. The geometries of [ReBr₃(NO)(dppe)] and [ReOBr₃(dppe)] have been optimized using the density functional theory (DFT) and the electronic transitions of [ReBr₃(NO)(dppe)] and [ReOBr₃(dppe)] have been calculated with the time-dependent DFT method (TDDFT). The UV–vis spectrum of 2 has been interpreted on the basis of the experimental data for [ReOBr₃(dppe)] and the calculated transitions for [ReOBr₃(dppe)] and [Re(NO)Br₃(dppe)].     

Heterobimetallic Cu(II)–Hg(II) polynuclear complexes containing Hg(SCN)42− unit – Synthesis,spectroscopic investigations,X-ray studies and magnetic properties

Three novel heterobimetallic polymers with Hg(SCN)₄^2? as a linker have been synthesised and characterized by means of IR, EPR, magnetic measurements and single crystal X-ray. All the obtained compounds [Cu(bpzm)Hg(SCN)₄]_n (1), [Cu(bdmpzm)Hg(SCN)₄]_n (2) and [Cu(dpa)Hg(SCN)₄]_n (3) form supramolecular framework structures. The 1 creates a three-dimensional coordination polymer, and 2 and 3 form two-dimensional nets extending along crystallographic (0 1 0) plane. Each octahedrally coordinated Cu(II) atom of 1 connects to four mercury ions through four thiocyanate bridges, and each Hg(II) ion is bridged with four copper ions via four thiocyanate bridges. The Cu(II) ions of 2 and 3 display a pyramidal coordination geometry, and they are connected to three mercury ions through three thiocyanate bridges, one thiocyanate ion is nonbridging group.     

The new arsine ruthenium(III) complex with pyrazole ligand

The [RuCl₃(AsPh₃)(C₃H₄N₂)₂] complex has been prepared and studied by IR, UV–VIS spectroscopy and X-ray crystallography. The complex was prepared in direct reaction of RuCl₃·H₂O with triphenylarsine and pyrazole in methanol. The electronic structure and UV–Vis spectrum of the obtained compound has been calculated using the TDDFT method.     

Novel rhenium oxocomplexes of indazole-3-carboxylic acid – Synthesis,X-ray studies,spectroscopic characterization and DFT calculations

Three novel rhenium oxocomplexes incorporating indazole-3-carboxylate ligand: cis-[ReOCl₂(Ind-3-COO)(PPh₃)]·OPPh₃ (1a), cis-[ReOCl₂(Ind-3-COO)(PPh₃)] (1b) and cis-[ReOBr₂(Ind-3-COO)(PPh₃)]·OPPh₃ (2) have been synthesized and characterised spectroscopically and structurally (by single-crystal X-ray diffraction). The 1a and 2 are isostructural in solid state. The electronic spectrum of 1a was investigated at the TDDFT level employing B3LYP functional in combination with LANL2DZ. Additional information about binding in the complex 1a was obtained by NBO analysis.     

Synthesis,X-ray studies,spectroscopic investigation,and DFT calculations of [ReBr<Subscript>3</Subscript>(dppt)(OPPh<Subscript>3</Subscript>)]

The reaction of [ReOBr₃(PPh₃)₂] with 5,6-diphenyl-3-(2-pyridyl)-1,2,4-trazine (dppt) has been examined and [ReBr₃(dppt)(OPPh₃)] has been obtained. It was characterised by IR, UV–Vis spectroscopy, magnetic measurements, and X-ray crystallography. The electronic structure of [ReBr₃(dppt)(OPPh₃)] has been studied by DFT/B3LYP level calculations, and TDDFT calculations were employed for discussion of its electronic spectrum in more detail. The magnetic behavior is characteristic of mononuclear complexes with d⁴ low-spin octahedral Re(III) complexes (³T_1g ground state) and arise because of the large spin–orbit coupling (ζ = 2500 cm⁻¹), which gives diamagnetic ground state.     

Copper(II) complexes of bis(pyrazol-1-yl)methane - Synthesis, spectroscopic characterization, X-ray structure and DFT calculations

Two novel copper(II) complexes incorporating bis(pyrazol-1-yl)methane ligand (bpzm) have been synthesized. The compounds [CuCl(bpzm)₂(H₂O)]Cl·H₂O (1) and [Cu(N₃)₂(bpzm)]_n (2) have been studied by IR, UV-Vis spectroscopy and X-ray crystallography. The experimental studies on the compounds 1 and 2 have been accompanied computationally by the density functional theory (DFT) calculations.     

Coordination studies of 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine towards Cu cation. X-ray studies,spectroscopic characterization and DFT calculations

The reactions of 5,6-diphenyl-3-(2-pyridyl)-1,2,4-triazine with CuCl₂ · 2H₂O, Cu(NO₃)₂ · 3H₂O and CuSO₄ · 5H₂O have been examined, and four [CuCl₂(dppt)] (1), [CuCl₂(dppt)₂] · 2MeOH (2), [Cu(dppt)₂(H₂O)₂](NO₃)₂ (3) and [Cu(SO₄)(dppt)(H₂O)]_n · nH₂O (4) complexes have been obtained. All the complexes have been structurally and spectroscopically characterized, and compound 4 has been additionally studied by magnetic measurements. The electronic structure of 1 has been calculated with the density functional theory (DFT) method, and the time-dependent DFT calculations have been employed to calculate the electronic spectrum of 1.     

Condensation Reaction of Dimethyltin(IV) Oxide with 2‐(2,3‐Dichloroanilino)benzoic Acid Synthesis and Study of a Novel Dimeric Tetraorganodistannoxane

The novel symmetric dimeric tetraorganodistannoxane [(Me₂Sn)₄(DCPA)₂)O₂(OH)₂] ( 2 ) and [(Me₂Sn)₄(DCPA)₂)O₂(OC₂H₅)₂] ( 3 ) where HDCPA is 2‐(2,3‐dichloroanilino)benzoic acid ( 1 ) have been prepared. The crystal structure of 3 has been determined by X‐ray crystallography. Three distannoxane rings are present to the centrosymmetric dimeric tetraorganodistannoxane by virtue of μ₃‐oxo form the central R₄Sn₂O₂ core with a planar Sn₂O₂ ring, resulting in a ladder type structural motif. Five‐coordinated tin atoms are present in the distannoxane dimer. The ligands act as monodentate agents, thus rendering the tin atom five‐coordinated. Significant π → π stacking interactions and intramolecular hydrogen bonds stabilize the structure 3 . The polar imino hydrogen atom participates in intramolecular hydrogen bonds. The formation of the dimeric distannoxanes 2 and 3 represent a ladder‐type carboxylates in which the insertion of a μ₂‐OH or a μ₂‐OC₂H₅ group occurs. This unusual result can be interpreted in terms of a competition between the strength different donors, in which the –OH or the –OC₂H₅ groups show higher donor capacity than the carboxylato group of DCPA.