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| 2. |
- Ivanov, M.A., et al.
(author)
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The diethyl dithiophosphate complex of tetraphenylantimony(V) and its solvated form, [Sb(C6H5)(4){S2P(OC2H5)(2)}] center dot 1/2 C6H6: Synthesis, crystal structure, and C-13, P-31 CP/MAS NMR study : an example of monodentate coordination of dithio ligands
- 2013
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In: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 58:2, s. 197-205
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Journal article (peer-reviewed)abstract
- The O,O'-diethyl dithiophosphate complex of tetraphenylantimony(V) [Sb(C6H5)(4){S2P(OC2H5)(2)}] (I) and its benzene-solvated form I center dot 1/2C(6)H(6) (II) were synthesized and studied by high-resolution solid-state C-13 and P-31 NMR (MAS NMR). The diethyl dithiophosphate (Dtph) groups in I and II were quantitatively characterized by the P-31 chemical shift anisotropy (delta(aniso)), the asymmetry parameter (eta), and the principal values of chemical shift tensors (delta (xx) , delta (yy) , delta (zz) ). The calculation of the anisotropy parameters included construction of chi(2) statistic diagrams from full P-31 MAS NMR spectra. In both complexes, the Dtph groups were found to have mainly axially symmetric P-31 chemical shift tensors (for delta (zz) < delta (xx) a parts per thousand delta (yy) ) with similar anisotropy parameters (delta(aniso) and eta), which is due to their identical S-monodentate function. According to X-ray diffraction data, II has a trigonal bipyramidal (TBP) molecular structure with Smonodentate coordination of Dtph in the TBP axial position and outer-sphere position of the benzene molecule. The desorption of the outer-sphere benzene solvent molecules from structure II, which was noted in MAS NMR experiment, passes through the formation of three intermediate solvated forms with benzene content n < 1/2.
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| 3. |
- Korneeva, E.V., et al.
(author)
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Binding of gold(iii) with silver(i) dipropyldithiocarbamate : supramolecular self-assembly (role of secondary Au…S and Ag…S bonds) and thermal behavior of the ionic-polymer complex ([Au(S2CNPr2)2][AgCl2])n
- 2019
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In: Russian chemical bulletin. - : Springer. - 1066-5285 .- 1573-9171. ; 68:1, s. 40-47
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Journal article (peer-reviewed)abstract
- The double ionic-polymer complex ([Au(S2CNPr2)2][AgCl2])n (1) was prepared as an individual fixation form of gold(III) from NaCl solutions with silver(I) dipropyldithiocarbamate and was characterized by single-crystal X-ray diffraction and 13C magic-angle spinning (MAS) NMR spectroscopy. The structure of 1 comprises two nonequivalent centrosymmetric complex cations [Au(S2CNPr2)2]+ (A and B) and the discrete linear anion [AgCl2]–. Gold(III) cations are linked by pairs of unsymmetrical secondary Au…S bonds to form linear supramolecular chains (…A…B…)n. Neighboring cations are additionally linked by [AgCl2]– anions via secondary Ag…S and Cl…S bonds, the anions being involved in the overall stabilization of the supramolecular structure. The cation–anion interactions lead to a distortion of the linear configuration of the [AgCl2]– anion. The character of thermolysis of 1 accompanied by quantitative regeneration of bound Au and Ag was established by simultaneous thermal analysis.
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| 4. |
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| 5. |
- Loseva, O.V., et al.
(author)
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Structural organization of dithiocarbamate heteropolynuclear gold(III)-cadmium complexes from X-ray crystallography and 113Cd MAS NMR spectroscopy data
- 2013
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In: Journal of Structural Chemistry. - 0022-4766 .- 1573-8779. ; 54:3, s. 598-606
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Journal article (peer-reviewed)abstract
- We study the interaction of dialkyl substituted and cyclic cadmium dithiocarbamates with [AuCl4]− anions in 2M HCl medium. The state of the chemisorbents upon contact with AuCl3 solutions is controlled by 113Cd MAS NMR spectroscopy. The result of the heterogeneous reactions involving chemisorption binding of gold(III) from the solutions and partial ion exchange is the formation of heteropolynuclear gold(III)-cadmium complexes. The crystal and molecular structure of the acetone-solvated form of polymeric bis-(N,N-diethyldithiocarbamato-S,S′) gold(III) hexachlorodicadmate is identified by single-crystal XRD. The main structural moieties of the compound are complex [Au{S2CN(C2H5)2}2]+ cations and [Cd2Cl6]2− anions. The structural self-organization of the complex at the supramolecular level is attributed to the secondary Au…S bonds between neighboring isomeric complex gold(III) cations; the bonding results in the formation of linear polymer ([Au{S2CN(C2H5)2}2]+) n chains, with [Cd2Cl6]2− anions alternating to the right and left of the chains.
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| 6. |
- Loseva, O.V., et al.
(author)
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Tetranuclear heteroleptic mercury(ii) complexes of the composition [Hg4(S2CNPr2)6(NO3)2] and [Hg4(S2CNPr2)4Cl4] : structural organization, principles of construction of supramolecular polymeric chains, and thermal behavior
- 2019
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In: Russian chemical bulletin. - : Springer. - 1066-5285 .- 1573-9171. ; 68:4, s. 782-792
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Journal article (peer-reviewed)abstract
- New heteroleptic mercury(ii) complexes [Hg4(S2CNPr2)6(NO3)2] (1) and [Hg4(S2CNPr2)4Cl4] (2) were synthesized and characterized by single-crystal X-ray dif raction and 13C and 15N MAS NMR spectroscopy. In these complexes, the metal atoms are linked in pairs by bridging dipropyldithiocarbamate ligands (Pr2Dtc) to form tetranuclear cations and molecules. The further structural organization of compound 1 to the polymeric chains [Hg4(S2CNPr2)6(NO3)2]n occurs due to the linking of [Hg4(S2CNPr2)6]2+ cations by pairs of bridging nitrate groups. The formation of the supramolecular polymeric structure of 2 is determined by pairwise secondary Hg⋯Cl bonds between the cyclic [Hg4(S2CNPr2)4Cl4] molecules, in which the central eight-membered metallocycle [Hg4S4] adopts a distorted chair conformation. The thermal behavior of compounds 1 and 2 was studied by simultaneous thermal analysis.
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| 7. |
- Novikova, E. V., et al.
(author)
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Heteroleptic Bismuth(III) Dithiocarbamato-Chlorido Complexes of [Bi(S2CNR2)Cl2] and [Bi(S2CNR2)2Cl] (R = C3H7, iso-C4H9): Preparation, 1D Polymer Structures, Heteronuclear (13C, 15N) CP MAS NMR, and Thermal Behavior
- 2021
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In: Russian journal of coordination chemistry. - : Pleiades Publishing, Ltd. - 1070-3284 .- 1608-3318. ; 47:1, s. 43-51
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Journal article (peer-reviewed)abstract
- Crystalline bismuth(III) dithiocarbamato-chlorido complexes [Bi{S2CN(C3H7)2}Cl2] (I) and [Bi{S2CN(iso-C4H9)2}2Cl] (II) were prepared and comparatively studied by (13C, 15N) CP-MAS NMR spectroscopy, IR spectroscopy, and X-ray diffraction (CIF files CCDC nos. 1971976 and 1971975, respectively). The dithiocarbamate ligands are typically coordinated in the S,S'-iso- (I) or aniso- (II) bidentate-terminal mode. In each of the compounds, neighboring molecules are connected through one or two μ2-Cl– ligands into zigzag-like polymer chains, in which the central atom has sixfold coordination: [BiS2Cl4] (I) or [BiS4Cl2] (II). The binding unit in the polymer chains of I is a four-membered [Bi–(μ-Cl)2–Bi] metallocycle in the butterfly conformation (the dihedral angle is 140.51(3)°). Therefore, stronger binding of heteroleptic molecules in polymer chains leads to a considerably shorter interatomic Bi–Bi distances in I (4.0904(4) Å) than in II (4.8772(4) Å). The thermal behavior of heteroleptic bismuth(III) complexes was studied by simultaneous thermal analysis with recording of TG and DSC curves. Although the major product of thermal transformations of I and II is Bi2S3, the microprobe method also identified the presence of reduced bismuth and BiCl3.
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| 8. |
- Novikova, E. V., et al.
(author)
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Principles of the Construction of Polymer Structures, Heteronuclear (13C, 15N) CP-MAS NMR, and Thermal Behavior of Heteroleptic Bismuth(III) Complexes of the General Composition [Bi(S2CNR2)2X] (X = NO3, Cl)
- 2019
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In: Russian journal of coordination chemistry. - : Springer. - 1070-3284 .- 1608-3318. ; 45:10, s. 695-705
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Journal article (peer-reviewed)abstract
- The crystalline heteroleptic bismuth(III) complexes, [Bi{S2CN(iso-C4H9)2}2(NO3)] (I) and [Bi{S2CN(C3H7)2}2Cl] (II), are isolated in preparative yields. Both compounds form 1D polymer structures and are characterized by X-ray diffraction analysis (CIF files CCDC nos. 1877115 (I) and 1876364 (II)) and (13C, 15N) CP-MAS NMR spectroscopy. The coordination mode of each of the dialkyldithiocarbamate ligands is S,S′-anisobidentately terminal. The inorganic anions performing the μ2-bridging function participate in the binding of the adjacent metallic atoms to form zigzag polymer chains. A new mode of bismuth(III) binding involving all oxygen atoms (O,O'-anisobidentate coordination to each adjacent bismuth atom) is found for the bridging nitrate groups in compound I. The bismuth atoms in the studied compounds are characterized by the eightfold [BiS4O4] (I) or sixfold [BiS4Cl2] (II) environment. The thermal behavior of the synthesized complexes is characterized by the data of simultaneous thermal analysis, using parallel recording of thermogravimetry and differential scanning calorimetry curves. In both cases, Bi2S3 is the only final product of the thermal transformations of compounds I and II.
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| 9. |
- Rodinaa, T.A., et al.
(author)
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CP/MAS NMR (13C, 15N, and 113Cd), thermal behavior, and sorption properties of cadmium Di-Iso-Butyldithiocarbamate : The Gold(III)-Binding species sorbed from solutions
- 2012
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In: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 57:11, s. 1490-1495
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Journal article (peer-reviewed)abstract
- The structure and thermal behavior of cadmium di-iso-butyldithiocarbamate (I) have been stud- ied by solid-state 13C and 15N CP/MAS NMR and simultaneous thermal analysis (STA). The cadmium com- plex forms two crystalline polymorphs, a and β. The structure of each of the polymorphs contains two struc- turally nonequivalent binuclear [Cd 2{S 2CN(iso-C 4H 9) 2} 4] molecules. The STA data have shown the possibil- ity of the α-I β-I phase transition. Studying the thermal behavior of the complex has demonstrated that the end product of thermodestruction is a fine yellow-orange powder of CdS. The sorption properties of I have been studied with respect to gold(III) chloride solutions in 2 M HCl. It has been found that gold(III) is efficiently sorbed from strong acid solutions in the Au3+ concentration range 0.032-3.220 mg/mL. On the basis of multinuclear (13C, 15N, and 113Cd) MAS NMR data, it has been demonstrated that the individual gold(III)-binding species in the sorption system is the ionic gold(III) cadmium-complex of composition [Au{S2CN(iso-C 4H 9) 2} 2] 2[CdCl 4
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