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| 2. |
- Ivanov, Alexander V., et al.
(författare)
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Adducts of zinc and copper(II) dialkyldithiocarbamate complexes with dialkylamines: Synthesis, EPR, and 13C and 15N CP/MAS NMR
- 2007
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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 52:5, s. 691-697
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Tidskriftsartikel (refereegranskat)abstract
- Crystalline adducts of zinc and copper(II) dithiocarbamate (Dtc) complexes with dialkylamines [M(NHR′2)(S2CNR2)2] (M = Zn, 63Cu, 65Cu; R = CH3, C2H5, or R2 = (CH2)4O; R′ = C2H5, C3H7) have been preparatively isolated. The structures and spectral properties of the adducts have been studied by EPR and 13C and 15N MAS NMR. Chemisorption of bases on powders of dinuclear dithiocarbamates leads to their dissociation into monomeric adducts. Computer simulation demonstrates that the experimental EPR spectra of isotope-substituted copper(II) adducts have an individual character. The geometry of the copper polyhedra is intermediate between a trigonal bipyramid (TBP) and a tetragonal pyramid (TP). The TBP and TP contributions have been quantified based on EPR data. 13C and 15N MAS NMR data show that the Dtc ligands incorporated into the zinc adduct molecule are structurally nonequivalent. The dependence of the isotropic 15N chemical shifts of the Dtc groups on the alkyl substituents at the nitrogen atom is interpreted based on the concept of joint manifestation of the (+)inductive effect of the alkyl substituents and the mesomeric effect of the Dtc groups.
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| 3. |
- Ivanov, Alexander V., et al.
(författare)
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Adducts of zinc and copper(II) morpholinedithiocarbamate complexes with morpholine of the composition [M(Mf)(MfDtC)(2)] and [M(Mf)(MfDtC)(2)]center dot Mf: Synthesis, thermal analysis, EPR, and CP/MAS C-13 NMR
- 2003
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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 48:3, s. 415-421
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Tidskriftsartikel (refereegranskat)abstract
- The zinc and copper(II) morpholineditiohcarbamate complexes [M-2(MfDtc)(4)] and their adducts with morpholine [M(Mf)(MfDtc)(2)], including the solvated forms [M(Mf)(MfDtc)(2)] . Mf (M = Zn, Cu-63, Cu-65), have been synthesized and characterized by thermal analysis, EPR, and CP/MAS C-13 NMR data. Upon thermal destruction, the initial complexes, their adducts, and solvated forms lose weight in one, two, and three steps, respectively. The ultimate products of the thermal destruction of these complexes are zinc and copper sulfides. The range of the thermal destruction of the "dithiocarbamate part" is progressively shifted to lower temperatures in going from the initial binuclear complexes to their adducts and solvated forms. EPR shows that the geometry of the [CuS4N] chromophore in the [Cu(Mf)(MfDtc)(2)] adduct is close to square-pyramidal, the unpaired electron being predominantly localized in the metal 3d(x2-y2) AO. The outer-sphere solvation of the adduct is accompanied by structural reorganization at the molecular level. This reorganization involves a distortion of the [CuS4] base of the square-pyramidal polyhedron [CuS4N] toward a trigonal bipyramid. C-13 NMR shows that all of the zinc complexes under consideration are characterized by intramolecular nonequivalence of dithiocarbamate ligands. The N-15 NMR spectra adequately reflect the difference in the structural functions of pairs of dithiocarbamate ligands in [Zn-2(MfDtc)(4)].
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| 4. |
- Ivanov, Alexander V., et al.
(författare)
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Clathrate Formation of Bis(diethyldithiocarbamato)pyridinezinc(II) and Bis(diethyldithiocarbamato)pyridinecopper(II) with Benzene by EPR, High-Resolution Solid-State 13C and 15N NMR, and X-ray Crystallography
- 1998
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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 43:9, s. 1368-1376
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Tidskriftsartikel (refereegranskat)abstract
- The structures of the clathrates of bis(diethyldithiocarbamato)pyridinezinc(H) and-copper(II) with benzene were studied by EPR, high-resolution solid-state 13C and 15N NMR, and X-ray crystallography. The geometry of the coordination polyhedra in the clathrates M(EDtc)2· Py · C6H6is close to trigonal-bipyramidal. Two short M-S bonds and the M-N bond form the equatorial plane, and two long M-S bonds point toward the axial positions. For the magnetically diluted copper(II) clathrate, the hyperfine structure can be observed at low temperatures due to the nitrogen atom of pyridine, which is associated with the contribution of the dz2orbital to the ground-state wave function of the unpaired electron. The 13C and 15N NMR signals were assigned.
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| 7. |
- Korneeva, E V, et al.
(författare)
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Polymeric Gold(I) Diisobutyl Dithiophosphate, [Au2{S2P(O-iso-C4H9)2}2]n: Synthesis, Supramolecular Self-Organisation (a Role of Aurophilic Interaction), 13C and 31P MAS NMR Spectroscopy, and Thermal Behavior
- 2014
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 40:10, s. 748-756
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Tidskriftsartikel (refereegranskat)abstract
- A new polymeric gold(I) diisobutyl dithiophosphate (Dtph), [Au2{S2P(O-iso-C4H9)2}2] n (I), was preparatively obtained and characterized by 13C and 31P MAS NMR spectroscopy and X-ray diffraction (CIF file CCDC no. 977818). Diagrams of the χ2 statistic were constructed from the complete 31P MAS NMR spectra and used to calculate the 31P chemical shift anisotropy (δ aniso = δ zz − δ iso ) and the asymmetry parameter η = (δ yy − δ xx )/(δ zz − δ iso ). The main structural unit of complex I is the noncentrosymmetric dinuclear molecule [Au2{S2P(O-iso-C4H9)2}2], in which the gold atoms are linked by two bridging ligands Dtph. The central cyclic structural fragment of the dimer [Au2S4P2] is additionally stabilized by the intramolecular aurophilic interaction Au⋯Au. Further supramolecular self-organization of the complex involves intermolecular aurophilic bonds Au⋯Au that serve to unite adjacent dinuclear molecules [Au2{S2P(O-iso-C4H9)2}2] with different spatial orientations into the polymer chains ([Au2{S2P(O-iso-C4H9)2}2]) n . The thermal behavior of complex I was examined by synchronous thermal analysis under argon. The character of the thermolysis of the complex to reduced metallic gold as a final product was determined.
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| 9. |
- Loseva, O.V., et al.
(författare)
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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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Ingår i: Journal of Structural Chemistry. - 0022-4766 .- 1573-8779. ; 54:3, s. 598-606
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Tidskriftsartikel (refereegranskat)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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| 10. |
- Loseva, O.V., et al.
(författare)
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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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Ingår i: Russian chemical bulletin. - : Springer. - 1066-5285 .- 1573-9171. ; 68:4, s. 782-792
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Tidskriftsartikel (refereegranskat)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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