Binding of Gold(III) from Solutions by Tetranuclear Lead(II) Dipropyldithiocarbamate [Pb4{S2CN(C3H7)2}8] and Chemisorption Synthesis of the Double Ionic Polymer Complex ([Au{S2CN(C3H7)2}2][PbCl3] · 0.5CH3–C6H5) n: Heteronuclear (13 C, 15 N) CP-MAS NMR, Structural Organization, and Construction Principles of Cationic and Anionic Polymer Chains

A. V. Ivanov, A. S. Zaeva, A. I. Smolentsev

Research output: Contribution to journalArticlepeer-review

Abstract

Solid-state 13C and 15N CP-MAS NMR data adequately reflected the presence of four nonequivalent PrDtc ligands in the tetranuclear lead(II) N,N-dipropyldithiocarbamate (PrDtc), [Pb4{S2CN(C3H7)2}8] (I); the spin–spin coupling constants 3J(15N–207Pb) for the ligands were estimated. It was shown by 13C MAS NMR that the chemisorption binding of AuCl3 from a solution in 2M HCl using lead(II) dipropyldithiocarbamate is accompanied by complete redistribution of the PrDtc ligands from Pb(II) to Au(III) coordination sphere; this gives the double complex of [Au{S2CN(C3H7)2}2][PbCl3] (II). Upon crystallization from an acetone–toluene mixture (3 : 1), this complex was isolated as the solvated form ([Au{S2CN(C3H7)2}2][PbCl3] ⋅ 1/2CH3C6H5)n (IIa), which was characterized by X-ray diffraction (CIF file CCDC no. 1978947). The cationic part of the complex is represented by non-centrosymmetric gold(III) complex ions, [Au{S2CN(C3H7)2}2]+, which are combined by pairs of nonequivalent Au···S secondary bonds, thus forming supramolecular pseudo-polymer chain ([Au{S2CN(C3H7)2}2]+)n. The 1D polymeric trichloroplumbate(II) anion, {[Pb(μ2-Cl)3]}n, acts as the counter-ion. The C–H···Cl hydrogen bonds between the anionic and cationic chains lead to formation of channels in the crystal lattice, which are occupied by solvating toluene molecules.

Original languageEnglish
Pages (from-to)828-837
Number of pages10
JournalRussian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya
Volume46
Issue number12
DOIs
Publication statusPublished - Dec 2020

Keywords

  • Au⋅⋅⋅S secondary bonds
  • chemisorption synthesis
  • gold(III)–lead(II) double complexes
  • lead(II) dialkyldithiocarbamates
  • supramolecular self-organization
  • &#8901
  • CRYSTAL-STRUCTURE
  • N-15
  • SUPRAMOLECULAR SELF-ORGANIZATION
  • lead(II) double complexes
  • THERMAL-BEHAVIOR
  • Au&#8901
  • S secondary bonds
  • gold(III)&#8211
  • PRECURSORS

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