| 1. |
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| 2. |
- Ivanov, M.A., et al.
(författare)
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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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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 58:2, s. 197-205
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Tidskriftsartikel (refereegranskat)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. |
- Bredyuk, O. A., et al.
(författare)
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Structural organization of cadmium(II) and copper(II) dithiocarbamate complexes with dialkyl-substituted and cyclic ligands: Synthesis, single-crystal X-ray diffraction, EPR, and CP/MAS13C, 15N, and 113Cd NMR
- 2005
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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 50:11, s. 1710-1726
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Tidskriftsartikel (refereegranskat)abstract
- A comparative study of polynuclear thallium complexes with dialkyldithiocarbamates [Tl2{S2CNR2} 2]n (R = CH3, i-C3H7, C4H9, and i-C4H9; R2 = (CH2)6) was performed by solid-state 13C and 15N CP/MAS NMR spectroscopy. The dithiocarbamate groups were found to be structurally equivalent in the complexes studied. An increase in the positive inductive effect of alkyl substituents at the N atom increased 15N chemical shifts as a result of a combination of positive inductive effect of the alkyl substituents and the mesomeric effect of =NC(S)S-groups. The first representative of thallium(I) complexes with a cyclic dithiocarbamate ligand [Tl2{S2CN(CH2) 6}2]n was obtained. Its molecular structure was determined from X-ray diffraction data. The β-form of the isotope-substituted complex [63/65CuTl2{S 2CN(CH2)6}4] was obtained and examined by EPR spectroscopy. The EPR spectra were modeled at the second order of the perturbation theory. The spin density at the thallium atoms was calculated and its distribution over the AOs of thallium was determined.
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| 4. |
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| 5. |
- Ivanov, Alexander V., et al.
(författare)
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Chemisorption Synthesis of the Ion-Polymeric Heteronuclear Gold(III)-Bismuth(III) Complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n Based on [Bi2{S2CN(C3H7)2}6]: 13C MAS NMR, Supramolecular Structure, and Thermal Behavior
- 2018
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Ingår i: Russian journal of coordination chemistry. - : Springer. - 1070-3284 .- 1608-3318. ; 44:8, s. 518-531
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Tidskriftsartikel (refereegranskat)abstract
- Chemisorption synthesis on the basis of the binuclear compound [Bi2{S2CN(C3H7)2}6] (I) and preparative isolation of the ion-polymeric heteronuclear gold(III)-bismuth(III) complex ([Au{S2CN(C3H7)2}2]3[Bi2Cl9])n (II) are carried out. Compounds I and II are characterized in comparison by IR spectroscopy and 13C CP-MAS NMR. According to the X-ray diffraction analysis data (CIF file CCDC no. 1407705), the cationic moiety of compound II exhibits an unusually complicated supramolecular structure including six isomeric noncentrosymmetric complex cations [Au{S2CN(C3H7)2}2]+ (hereinafter A-F) and two binuclear anions [Bi2Cl9]3- as conformers. The isomeric gold(III) cations perform various structural functions. Owing to pair secondary interactions Au···S, cations B, C, E, and F form centrosymmetric ([E···E], [F···F]) and noncentrosymmetric ([B···C]) binuclear aggregates [Au2{S2CN(C3H7)2}4]2+, whereas cations A and D are not involved in dimerization. The strongest secondary Au···S bonds are formed between the binuclear and mononuclear cations, resulting in the formation of supramolecular cation-cationic polymer chains of two types: (⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅A⋅⋅⋅[B⋅⋅⋅C]⋅⋅⋅)n and (D⋅⋅⋅[E⋅⋅⋅E]⋅⋅⋅D⋅⋅⋅[F⋅⋅⋅F]⋅⋅⋅])n. In both chains, the gold atoms of the binuclear cations are characterized by a distorted octahedral coordination [S6], whereas in the mononuclear cations the gold atoms retain the square environment [S4]. The cation-anionic interactions are provided by secondary bonds Cl⋅⋅⋅S involving the terminal chlorine atoms of isomeric [Bi2Cl9]3- and the sulfur atoms of the binuclear cations [Au2{S2CN(C3H7)2}4]2+. The character of the thermal behavior of compounds I and II is studied by simultaneous thermal analysis with the identification of intermediate and final products of the thermal transformations. The thermolysis of compound I at 193-320°C is accompanied by the formation of Bi2S3 with an impurity of reduced metallic bismuth particles. The final products of the thermal transformations of compound II are reduced elemental gold and Bi2O3, and the thermal transformation intermediates are BiCl3 and Bi2S3.
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| 6. |
- Ivanov, Alexander V., et al.
(författare)
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Crystalline cadmium dialkyl phosphorodithioate complexes : synthesis and structural organization as probed by multinuclear C-13, P-31, and Cd-113 CP/MAS NMR and single-crystal X-ray diffraction
- 2007
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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 52:10, s. 1595-1602
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Tidskriftsartikel (refereegranskat)abstract
- The cadmium O,O'-dethyl (I) and O,O'-di-sec-butyl phosphorodithioate (II) complexes have been synthesized and characterized in detail by(13)C, P-31, and Cd-113 CP/MAS NMR. X-ray crystallography shows that complex II has a binuclear molecular structure [Cd-2{S2P(O-s-C4H9)(2)}(4)]. For P-31 and Cd-113 NMR signals, the chemical shift anisotropy delta(aniso) and the asymmetry parameter eta have been calculated. The P-31 NMR signals are assigned to the terminal and bridging ligands in the complexes.
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| 7. |
- Ivanov, Alexander V., et al.
(författare)
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Structures of polynuclear thallium(I) and copper(II)-thallium(I) complexes with dialkyldithiocarbamates: 13C and 15N CP/MAS NMR, EPR, and X-ray diffraction studies
- 2006
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 32:5, s. 339-349
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Tidskriftsartikel (refereegranskat)abstract
- A comparative study of polynuclear thallium complexes with dialkyldithiocarbamates [Tl2{S2CNR2}2]n (R = CH3, i-C3H7, C4H9, and i-C4H9; R2 = (CH2)6) was performed by solid-state 13C and 15N CP/MAS NMR spectroscopy. The dithiocarbamate groups were found to be structurally equivalent in the complexes studied. An increase in the positive inductive effect of alkyl substituents at the N atom increased 15N chemical shifts as a result of a combination of positive inductive effect of the alkyl substituents and the mesomeric effect of=NC(S)S-groups. The first representative of thallium(I) complexes with a cyclic dithiocarbamate ligand [Tl2{S2CN(CH2)6}2]n was obtained. Its molecular structure was determined from X-ray diffraction data. The β-form of the isotope-substituted complex [63/65CuTl2{S2CN(CH2)6}4] was obtained and examined by EPR spectroscopy. The EPR spectra were modeled at the second order of the perturbation theory. The spin density at the thallium atoms was calculated and its distribution over the AOs of thallium was determined.
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| 8. |
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| 9. |
- Ivanov, Alexander V., et al.
(författare)
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Synthesis, structural and multinuclear natural abundance (C-13, P-31, Pt-195) CP/MAS NMR studies of crystalline O,O '-dialkyldithiophosphate platinum(II) complexes
- 2008
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 34:8, s. 584-593
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Tidskriftsartikel (refereegranskat)abstract
- Platinum(II) O,O'-dicyclohexyl dithiophosphate [Pt{S2P(O-cyclo-C6H11)(2)}(2)] (I) and platinum(II) O,O'-diisopropyl dithiophosphate [Pt{S2P(O-iso-C3H7)(2)}(2)] (II) complexes were obtained and studied by solidstate C-13, P-31, and Pt-195 CP/MAS NMR spectroscopy. The dithiophosphate (Dtph) ligands in molecular structure I were found to be coordinated by platinum in S,S'-bidentate fashion to form the planar chromophore [PtS4] (single-crystal X-ray diffraction data). For complex II, a new alpha-form (alpha-II) was obtained and identified by P-31 MAS NMR spectroscopy. The P-31 chemical shift anisotropy delta(aniso) and the asymmetry parameter eta of the P-31 chemical shift tensor were calculated from the whole MAS spectra.
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| 10. |
- 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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| 11. |
- 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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| 12. |
- Rodina, Tatyana A., et al.
(författare)
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Crystalline O,O’-di-sec-butyl and O,O’-diethyl dithiophosphate platinum(II) complexes : Synthesis, 13C and 31P CP/MAS NMR, single crystal X-ray diffraction studies and thermal behaviour
- 2011
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Ingår i: Polyhedron. - : Elsevier BV. - 0277-5387 .- 1873-3719. ; 30:13, s. 2210-2217
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Tidskriftsartikel (refereegranskat)abstract
- Crystalline bis(O,O’-di-sec-butyldithiophosphato)platinum(II) was prepared and studied by means of 31P, 13C CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. The unit cell of the platinum(II) compound is comprised of one centrosymmetric mononuclear molecule [Pt{S2P(O-sec-C4H9)2}2], in which the dithiophosphate groups display structural equivalence in both 31P NMR and XRD data. A pair of the dithiophosphate ligands exhibit the same S,S’-bidentate chelating structural function and form two planar four-membered chelate rings, [PtS2P], in this molecule. The planar configuration of the [PtS4] chromophore in structure 1 is governed by the dsp2-hybrid state of platinum(II). The structural states of the dithiophosphate groups in two different samples of complex 1 (one crystallised from ethanol and the other one precipitated from an aqueous solution) are all characterised by almost rhombic 31P chemical shift tensors. The observed essential dispersion of the 31P NMR chemical shift is caused by a coexistence of six optical isomers of molecule 1. The thermal behaviour of this compound was studied by means of simultaneous thermal analysis (a combination of TG and DSC) under an argon atmosphere. The thermal behaviour shows that the mass of 1 is lost in three steps, involving successive thermal decompositions of the organic and inorganic parts of this compound with platinum(II) dithio-meta-phosphate and reduced metallic platinum as the intermediate and the final products, respectively.
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| 13. |
- Rodina, T.A., et al.
(författare)
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Synthesis, structure, and 13C and 31P CP/MAS NMR of crystalline modifications of the polynuclear thallium(I) O,O′-dicyclohexyl phosphorodithioate complex [Tl{S2P(O-cyclo-C6H11)2}]n
- 2009
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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 54:11, s. 1779-1788
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Tidskriftsartikel (refereegranskat)abstract
- Two crystalline modifications (Ia and Ib) of the polynuclear thallium (I) O,O′-dicyclohexyl phosphorodithioate complex [Tl{S2P(O-cyclo-C6H11)2}] n have been synthesized and characterized by CP/MAS NMR (13C, 31P). From full 31P CP/MAS NMR spectra, the χ2 plots were constructed to calculate the 31P chemical shift anisotropy 31P - δaniso = (δzz - δiso) and asymmetry parameters η = (δ yy - δ xx )/(δ zz - δiso). The data obtained for the O,O′-dicyclohexyl phosphorodithioate (Dtph) groups (in both modifications) are evidence that the 31P chemical shift tensors are intermediate between rhombic and axially symmetric. However, whereas the rhombic component dominates for Ia, the tensor for Ib is close to axially symmetric (for δ zz < δ yy ≈ δ xx ). The same pattern of the MAS spectra corresponding to negative δaniso (δ zz < δ yy < δ xx ) points to a bridging or terminal/bridging coordination mode of the Dtph groups. X-ray crystallography shows that complex Ib has a polynuclear structure (of the chain polymer type). The chains are composed of alternating structurally nonequivalent noncentrosymmetric binuclear molecules [Tl2{S2P(O-cyclo-C6H11)2}2]. All Dtph ligands have the terminal/μ3-bridging coordination mode.
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| 14. |
- Sharutin, V. V., et al.
(författare)
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Tetraphenyl- and tetratolylantimony complexes with N,N-dialkyldithiocarbamate ligands : synthesis, X-ray diffraction analysis, and 13C and 15N CP/MAS NMR studies
- 2006
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 32:3:6, s. 87-396
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Tidskriftsartikel (refereegranskat)abstract
- Crystalline tetraphenylantimony and tetratolylantimony complexes with N,N-dialkyldithiocarbamate ligands [Sb(C6H5)4(S2CNR2)] (R = CH3, C2H5, and C3H7 and R2 = (CH2)6) were synthesized by ligand exchange reactions and studied by 13C and 15N CP/MAS NMR spectroscopy. X-ray diffraction analysis revealed that the complex [Sb(n-CH3-C6H4)4{S2CN(C3H7)2}] exists as the single molecular form, while [Sb(C6H5)4{S2CN(CH2)6}] exists as two molecular conformers. The 13C and 15N signals were assigned to the positions of the atoms in the isomeric structures [Sb(C6H5)4{S2CN(CH2)6}] in terms of different degrees of double bonding in the formally single =N-C(S)S-bond.
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| 15. |
- Ivanov, Alexander V., et al.
(författare)
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Binding of Au3+ from solutions by nickel(II) and cadmium diisopropyl dithiophosphates: MAS P-31 NMR, structure and thermal behavior of the polynuclear complex [Au-2{S2P(O-iso-C3H7)(2)}(2)] (n)
- 2012
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 38:6, s. 430-439
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Tidskriftsartikel (refereegranskat)abstract
- The paper deals with reactions of freshly precipitated diisopropyl dithiophosphate (Dtph) complexes of nickel(II), [Ni{S2P(O-iso-C3H7)(2)}(2)] and cadmium, [Cd-2{S2P(O-iso-C3H7)(2)}(4)], with the [AuCl4](-) in 2M HCl, resulting in gold transition from the solution to the precipitate as polymeric gold(I) diisopropyl dithiophosphate. The reduction of gold(III) to gold(I) noted in both cases is due to oxidation of the relevant part of the Dtph group to bis(O,O'-di-(iso)-propoxythiophosphoryl) disulfide, (iso-C3H7O)(2)P(S)S-S(S)P(O-iso-C3H7)(2). The polynuclear gold(I) complex [Au-2{S2P(O-iso-C3H7)(2)}(2)] (n) (I) was isolated on a preparative scale from the chemisorption system and studied by MAS P-31 NMR and X-ray diffraction. The key structural unit of I is the non-centrosymmetric binuclear molecule [Au-2{S2P(O-iso-C3H7)(2)}(2)] in which the gold atoms are connected by two bridging Dtph groups. The structure contains two types of non-equivalent binuclear molecules related as conformational isomers. Owing to the relatively weak Au-Au contacts, the neighboring binuclear [Au-2{S2P(O-iso-C3H7)(2)}(2)] molecules are involved in an infinite polymeric chain with conformer alternation along the chain. To elucidate the conditions for the recovery of bound gold(I), the precipitates formed in the sorption systems were studied by simultaneous thermal analysis under argon. As the final product, thermolysis gives reduced metallic gold. The ability of dithiophosphate complexes to bind gold from a solution is much lower than that of dithiocarbamate complexes, which is due to oxidation of some Dtph groups to disulfide.
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| 16. |
- Ivanov, Alexander V., et al.
(författare)
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Conformational isomerism of the binuclear N,N-pentamethylenedithiocarbamate cadmium(II) complex, [Cd2{S2CN(CH2)5}4] on multinuclear (15N, 113Cd) CP/MAS NMR and single-crystal X-ray diffraction data
- 2006
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Ingår i: Inorganica Chimica Acta. - : Elsevier BV. - 0020-1693 .- 1873-3255. ; 359:12, s. 3855-3864
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Tidskriftsartikel (refereegranskat)abstract
- Crystalline N,N-cyclo-pentamethylenedithiocarbamate (PmDtc) cadmium(II) complex was prepared and studied by means of 15N, 113Cd CP/MAS NMR spectroscopy and single-crystal X-ray diffraction. The unit cell of the cadmium(II) compound comprises two centrosymmetric isomeric binuclear molecules [Cd2{S2CN(CH2)5}4], which display structural inequivalence in both 15N and 113Cd NMR and XRD data. There are pairs of the dithiocarbamate ligands exhibiting different structural functions in both isomeric molecules. Each of the terminal ligands is bidentately coordinated to the cadmium atom and forms a planar four-membered chelate ring [CdS2C]; whereas pairs of the tridentate bridging ligands combine two neighbouring cadmium atoms forming an extended eight-membered tricyclic moieties [Cd2S4C2], whose geometry can be approximated by a ‘chair' conformation. The structural states of cadmium atoms were characterised by almost axially symmetric 113Cd chemical shift tensors. All experimental 15N resonance lines were assigned to the nitrogen structural sites in both isomeric binuclear molecules.
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| 17. |
- Ivanov, Alexander V., et al.
(författare)
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Polymeric thallium(I) O,O′-diisopropyl dithiophosphate [Tl{S2P(O-iso-C3H7)2}]n : synthesis, structure, and 13C and 31P CP/MAS
- 2009
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 35:11, s. 857-863
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Tidskriftsartikel (refereegranskat)abstract
- The crystalline polymeric thallium(I) O,O′-diisopropyl dithiophosphate [Tl{S2P(O-iso-C3H7)2}] n (I) was obtained and examined by solid-state 13C and 31P CP/MAS NMR spectroscopy. Diagrams of the χ2 statistic were constructed from the complete 31P MAS NMR spectra and used to calculate the 31P chemical shift anisotropy (δaniso = (δ zz - δiso)) and the asymmetry parameter (η = (δ yy - δ xx )/(δ zz - δiso)). The 31P chemical shift tensor has a nearly axial symmetry (η = 0.22, δ zz < δ yy ≈ δ xx ). The MAS NMR spectral patterns correspond to the negative sign of δaniso (δ zz < δ yy < δ xx ), which indicates bridging or chelating-bridging coordination of the dithiophosphate ligands (Dtph). X-ray diffraction analysis revealed a polymeric structure of compound I. The polymer chain consists of alternating mononuclear [Tl{S2P(O-iso-C3H7)2}] molecules with opposite spatial orientations. The Dtph ligands are coordinated in a mixed, chelating-μ3-bridging fashion. The shape of the 31P NMR signal was interpreted in terms of the 31P-203,205Tl coupling pattern proposed from crystallographic data.
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| 18. |
- Ivanov, Alexander V., et al.
(författare)
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Structural organization of nickel(II) and copper(II) O,O'-dialkyl phosphorodithioate complexes as probed by X-ray diffraction, EPR, and CP/MAS 13C and 31P NMR
- 2004
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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 49:3, s. 373-385
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Tidskriftsartikel (refereegranskat)abstract
- The nickel(II) and copper(II) complexes [M{S2P(OR)(2)}(2)] (M = Ni, Cu-63, Cu-65; R = C2H5, C3H7, i-C3H7, C4H9, i-C4H9, s-C4H9, i-C5H11, c-C6H11) with eight symmetric O,O'-dialkyl phosphorodithioates were synthesized, and their structures and spectral properties were studied by EPR and CP/MAS C-13 and P-31 NMR. As determined by EPR, the [CuS4] chromophores in the lattice of nickel(II) complexes have predominantly a square-planar structure. The chromophores in complexes with phosphorodithioate ligands incorporating bulky alkyl substituents have somewhat distorted geometries. NMR shows that the Dtph groups in most nickel(II) complexes are structurally equivalent. An exception is [Ni{S2P(OC3H7)(2)}(2)], which gives rise to two (1 : 1) P-31 NMR signals. For [Ni(S2P(O-i-C4H9)(2))(2)], the alpha and beta modifications were obtained. In the alpha modification, the phosphorodithioate groups are nonequivalent, whereas the P modification has structurally equivalent ligands. The broadening of the P-31 NMR signal of the [Ni{S2P(O-s-C4H9)(2)}(2)] complex is rationalized by the existence of six optical isomers (due to two chiral centers in each of the ligands). For the Dtph groups acting as bidentate terminal ligands in the nickel(II) complexes, the P-31 chemical shift anisotropy delta(aniso) and asymmetry parameter eta were calculated from experimental NMR spectra. Single-crystal X-ray diffraction shows that bis(O,O'-dipropyl phosphorodithioato)nickel(II) exists in the form of two centrosymmetric molecules. In the structure of alpha-bis(O,O'-dipropyl phosphorodithioato)nickel(II), the Dtph ligands in the molecule are nonequivalent. The experimental P-31 NMR signals in the spectra of [Ni{S2P(OC3H7)(2)}(2)] and alpha-[Ni{S2P(O-i-C4H9)(2)}(2)] are assigned to the structural positions of phosphorus atoms in the corresponding molecular structures determined by X-ray diffraction.
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| 19. |
- Ivanov, Alexander V., et al.
(författare)
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Structural organization of silver(I) complexes with O,O′-dialkyl dithiophosphates : Solid-state 13C and 31P CP/MAS NMR and single-crystal X-ray diffraction studies
- 2007
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 33:1, s. 20-31
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Tidskriftsartikel (refereegranskat)abstract
- Silver(I) complexes with four symmetrically substituted O,O′-dialkyl derivatives of dithiophosphoric acid of the general formula [Ag{S2P(OR)2}] n (R = C2H5, i-C3H7, C4H9, and s-C4H9) were obtained. Their structures and spectroscopic characteristics were studied by solid-state 13C and 31P CP/MAS NMR spectroscopy and X-ray diffraction analysis. The parameters of the anisotropy of the 31P chemical shift 31P-δ aniso and η (δ aniso is the chemical shift anisotropy and η is the asymmetry parameter) calculated from the diagrams of the x 2-statistic revealed that the (RO)2PS2 groups act as bridging ligands in all the silver(I) complexes obtained. The hexanuclear complex [Ag6{S2P(O-i-C3H7)2}6] was found to form two modifications α and β. According to the X-ray diffraction data, the silver(I) complex with O,O′-di-s-butyl dithiophosphate exists as discrete hexanuclear molecules [Ag6{S2P(O-s-C4H9)2}6]. In the clear molecules β-[Ag6{S2P(O-i-C3H7)2}6], the signals for the phosphorus atoms were assigned to their positions determined from the X-ray diffraction data.
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| 20. |
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| 21. |
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| 22. |
- Ivanov, M.A., et al.
(författare)
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Synthesis, structure, and 13C and 31P CP/MAS NMR of the tetraphenylantimony(V) di-iso-propyl phosphorodithioate complex [Sb(C6H5)4{S2P(O-iso-C3H7)2}] and its solvated form [Sb(C6H5)4{S2P(O-iso-C3H7)2}] · 1/2C6H6 : an example of the monodentate coordination of dithio ligands
- 2009
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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 54:5, s. 708-716
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Tidskriftsartikel (refereegranskat)abstract
- The crystalline tetraphenylantimony(V) O,O′-di-iso-propyl phosphorodithioate complex [Sb(C6H5)4{S2P(O-i-C3H7)2}](I) and its solvated form [Sb(C6H5)4{S2P(O-i-C3H7)2}] · 1/2C6H6(II) were synthesized. Solid compounds I and II were studied by MAS NMR (13C, 31P). The 31P NMR chemical shift anisotropy 31P δaniso = (δ zz - δiso) and asymmetry parameter η = (δ yy - δ xx )/(δ zz - δiso) were calculated using χ 2 plots constructed on the basis of the 31P MAS NMR data. The O,O′-di-iso-propyl phosphorodithioate ligands in both complexes are characterized by predominantly the axially symmetric 31P chemical shift tensor (for the case δ zz < δ xx ≈ δ yy ) with close values of anisotropy parameters (δaniso and η), which reflects their identical S-monodentate structural function. X-ray crystallography showed that II has a trigonal-bipyramidal molecular structure with the uncommon monodentate coordination of the Dtph ligands through an S atom in an axial position of the trigonal bipyramid and the benzene molecule in the outer sphere.
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| 23. |
- Ivanov, M.A., et al.
(författare)
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Tetraphenylantimony(V) O,O″-dialkyl dithiophosphates [Sb(C 6H5)4{S2P(OR)2}] (R = s-C4H9, c-C6H11) : synthesis, structures, and 13C and 31P CP/MAS NMR spectra
- 2008
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Ingår i: Russian journal of coordination chemistry. - 1070-3284 .- 1608-3318. ; 34:7, s. 527-535
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Tidskriftsartikel (refereegranskat)abstract
- Tetraphenylantimony(V) O,O′-di-sec-butyl dithiophosphate (I) and tetraphenylantimony(V) O,O′-dicyclohexyl dithiophosphate (II) [Sb(C 6H5)4{S2P(OR)2}] (R = sec-C4H9 or cyclo-C6H11) were obtained. Their structures and spectroscopic properties were studied by X-ray diffraction analysis and 13C and 31P CP/MAS NMR spectroscopy. The dithiophosphate (Dtph) ligands in complexes I and II were found to be coordinated in S-monodentate and S,S′-bidentate fashions, respectively (MAS NMR data). According to X-ray diffraction data, the coordination polyhedron of antimony in molecular structure I is a trigonal bipyramid with unusual monodentate coordination of the Dtph group in the axial position.
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| 24. |
- Rodina, Tatyana A., et al.
(författare)
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A pyridine adduct of bis(di-iso-butyldithiocarbamato-S,S′)cadmium(II) : multinuclear (13C, 15N, 113Cd) CP/MAS NMR spectroscopy, crystal and molecular structure, and thermal behaviour
- 2011
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Ingår i: Inorganica Chimica Acta. - : Elsevier BV. - 0020-1693 .- 1873-3255. ; 368:1, s. 263-270
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Tidskriftsartikel (refereegranskat)abstract
- Crystalline bis(N,N-di-iso-butyldithiocarbamato-S,S′)(pyridine)cadmium(II) – adduct 1 was prepared and studied by means of multinuclear 13C, 15N, 113Cd CP/MAS NMR spectroscopy, single-crystal X-ray diffraction and simultaneous thermal analysis (STA). In molecular structure 1, the cadmium atom coordinates with four sulphur atoms and one nitrogen atom of pyridine, forming a coordination polyhedron [CdS4N] whose geometry is an almost ideal tetragonal pyramidal (C4v). The coordinated py molecule is in the apical position, while two structurally non-equivalent di-iso-butyldithiocarbamate ligands, playing the same terminal S,S’-chelating function, define the basal plane. To characterise additionally the structural state of the cadmium atom in this five-fold coordination, 113Cd chemical shift anisotropy (CSA) parameters, δaniso and η, were calculated from experimental MAS NMR spectra that revealed an almost axially symmetric 113Cd chemical shift tensor. From a combination of TG and DSC measurements taken under an argon atmosphere, we found that the mass of adduct 1 is lost in two steps involving initial desorption of coordinated py molecules with subsequent thermal destruction of liberated cadmium(II) di-iso-butyldithiocarbamate, with yellow-orange, fine-powdered solid CdS as the final product.
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| 25. |
- Rodina, T. A., et al.
(författare)
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Structural organization of the tetranuclear zinc di-iso-propyl phosphorodithioate complex [Zn4O{S2P(O-iso-C3H7))(2)}(6)] as probed by single-crystal X-ray diffraction and C-13 and P-31 CP/MAS NMR
- 2008
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Ingår i: Russian Journal of Inorganic Chemistry. - 0036-0236 .- 1531-8613. ; 53:7, s. 1098-1109
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Tidskriftsartikel (refereegranskat)abstract
- The zinc O,O'-di-iso-propyl phosphorodithioate complex [Zn4O⨑ub;S2P(O-iso-C3H7)2⫂ub;6] (I) has been synthesized and characterized by multinuclear MAS NMR (13C, 31P). The metal core of the tetranuclear structure of I, determined by single-crystal X-ray diffraction, is a tetrahedron centered by an oxygen atom. All Dtph ligands are structurally nonequivalent and act as μ2 bridges combining pairs of zinc atoms. Bonding of all metal atoms to the μ4 oxygen atom provides additional stabilization of the structure. For 31P NMR signals, the chemical shift anisotropy δaniso and the asymmetry parameter η were calculated, which allowed to assign them to the phosphorus positions in the structure of I.
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