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.

中文翻译：

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四环式铅（II）二丙基二硫代氨基甲酸酯[Pb 4 {S 2 CN（C 3 H 7）2} 8]结合溶液中的金（III）和双离子聚合物配合物（[Au {S 2 CN（C 3 H 7）2} 2] [PbCl 3]·0.5CH 3 -C 6 H 5）n：异核（13 C，15 N）CP-MAS NMR，结构组织以及阳离子和阴离子聚合物链的结构原理

摘要

固态¹³ C和¹⁵ N CP-MAS NMR数据充分反映了四核铅（II）N中的四个非等价PrDtc配体N，N-二丙基二硫代氨基甲酸酯（PrDtc），[Pb ₄ {S ₂ CN（C ₃ H ₇）₂ } ₈ ]（I）；估计了配体的自旋-自旋偶合常数³ J（¹⁵ N– ²⁰⁷ Pb）。它是由显示¹³ ÇMAS NMR，该化学吸附AUCL结合₃使用二丙基二硫代氨基甲酸铅（II）从2M HCl溶液中萃取，伴随着PrDtc配体从Pb（II）完全重新分布到Au（III）配位球；得到[Au {S ₂ CN（C ₃ H ₇）₂ } ₂ ] [PbCl ₃ ]（II）的双络合物。在丙酮-甲苯混合物（3：1）中结晶后，该复合物以溶剂化形式分离[[Au {S ₂ CN（C ₃ H ₇）₂ } ₂ ] [PbCl ₃ ]⋅1 / 2CH ₃ C ₆高₅）_n（IIa），其特征在于X射线衍射（CIF文件CCDC号1978947）。络合物的阳离子部分由非中心对称的金（III）络合物离子[Au {S ₂ CN（C ₃ H ₇）₂ } ₂ ] ^+表示，它们由成对的非等价的Au···S次要离子对组合键，从而形成超分子假聚合物链（[Au {S ₂ CN（C ₃ H ₇）₂ } ₂ ] ⁺）_n。一维聚合trichloroplumbate（II）的阴离子，{[铅（μ ₂ -Cl）₃ ] ^- } _Ñ，作为抗衡离子。阴离子和阳离子链之间的C–H···Cl氢键导致晶格中形成通道，这些通道被溶剂化的甲苯分子占据。