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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

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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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Notes

  1. Some of the 13C CP-MAS NMR measurements were carried out on a Bruker Avance III 500 spectrometer (Bruker) operating at 125.76 MHz (B0 = 11.74 T) at the Umeå University, Umeå, Sweden.

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ACKNOWLEDGMENTS

X-ray diffraction studies were carried out using research equipment of the Molecular Structure Research Center of the Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences. Electron microscopy studies and recording of energy dispersive spectra were performed at the Analytical Center for Mineralogical and Geochemical Studies of the Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences.

The authors are grateful to the Knut and Alice Wallenberg Foundation (NMR for Life program), SciLifeLab Laboratory, and personally to Dr. Tobias Sparrman for help in conducting some 13C CP-MAS NMR experiments at the Umeå University, Umeå, Sweden.

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Authors and Affiliations

  1. Institute of Geology and Nature Management, Far Eastern Branch, Russian Academy of Sciences, Blagoveshchensk, Russia

    E. V. Novikova & A. V. Ivanov

  2. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia

    K. L. Isakovskaya

  3. Mendeleev University of Chemical Technology of Russia, Moscow, Russia

    K. L. Isakovskaya

  4. Luleå University of Technology, Luleå, Sweden

    O. N. Antzutkin

  5. University of Warwick, Coventry, UK

    O. N. Antzutkin

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  1. E. V. Novikova
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  2. K. L. Isakovskaya
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  3. O. N. Antzutkin
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  4. A. V. Ivanov
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Correspondence to A. V. Ivanov.

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Translated by Z. Svitanko

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Novikova, E.V., Isakovskaya, K.L., Antzutkin, O.N. et al. 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. Russ J Coord Chem 47, 43–51 (2021). https://doi.org/10.1134/S1070328421010036

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