TY - JOUR

T1 - 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

T2 - Heteronuclear (13 C, 15 N) CP-MAS NMR, Structural Organization, and Construction Principles of Cationic and Anionic Polymer Chains

AU - Ivanov, A. V.

AU - Zaeva, A. S.

AU - Smolentsev, A. I.

N1 - Publisher Copyright: © 2020, Pleiades Publishing, Ltd. Copyright: Copyright 2020 Elsevier B.V., All rights reserved.

PY - 2020/12

Y1 - 2020/12

N2 - 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.

AB - 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.

KW - Au⋅⋅⋅S secondary bonds

KW - chemisorption synthesis

KW - gold(III)–lead(II) double complexes

KW - lead(II) dialkyldithiocarbamates

KW - supramolecular self-organization

KW - &#8901

KW - CRYSTAL-STRUCTURE

KW - N-15

KW - SUPRAMOLECULAR SELF-ORGANIZATION

KW - lead(II) double complexes

KW - THERMAL-BEHAVIOR

KW - Au&#8901

KW - S secondary bonds

KW - gold(III)&#8211

KW - PRECURSORS

UR - http://www.scopus.com/inward/record.url?scp=85097511893&partnerID=8YFLogxK

U2 - 10.1134/S1070328420110032

DO - 10.1134/S1070328420110032

M3 - Article

AN - SCOPUS:85097511893

VL - 46

SP - 828

EP - 837

JO - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

JF - Russian Journal of Coordination Chemistry/Koordinatsionnaya Khimiya

SN - 1070-3284

IS - 12

ER -