[nickel(II)(1,4-diisopropylpiperazine-2,3-dithione)(2-thioxo-1,3-dithiole-4,5-dithiolato)] | 391634-70-1

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: [nickel(II)(1,4-diisopropylpiperazine-2,3-dithione)(2-thioxo-1,3-dithiole-4,5-dithiolato)]
• 英文别名: [Ni(iPr2pipdt)(dmit)]；Ni(Prⁱ₂pipdt)(dmit)；Ni(1,4-diisopropylpiperazine-2,3-dithione)(2-thioxo-1,3-dithiole-4,5-dithiolato)；[Ni(1,4-diisopropylpiperazine-3,2-dithione)(1,3-dithiole-2-thione-4,5-dithiolate)]
• CAS: 391634-70-1
• 化学式: C₁₃H₁₈N₂NiS₇
• 分子量: 485.451
• InChiKey: KPZISPPXASORLX-UHFFFAOYSA-L

反应信息

• 作为反应物：
  描述：

  [nickel(II)(1,4-diisopropylpiperazine-2,3-dithione)(2-thioxo-1,3-dithiole-4,5-dithiolato)] 以 N,N-二甲基甲酰胺 为溶剂， 生成 [Ni(iPr2pipdt(+e))(dmit)](1-)
  参考文献：
  名称：

  R取代基对[Ni（R2pipdt）（dmit）]配合物的性质和晶体结构的影响，其中R = CH2C6H5。

  摘要：

  [Ni（R2pipdt）（dmit）]，（R2pipdt = 1,4-二取代-哌嗪-3,2-二硫酮，R = CH2C6H5; dmit = 1,3-二硫代-2-硫酮-4,5-二硫代磺酸盐）（已经制备和表征了1b），并与属于相同类别的已知配合物2b的性质进行了比较，其中R ＝ Pr i。进行1b和2b的循环伏安法，并将其与相应的R2pipdt配体前体（1a和2a）的伏安法进行比较。pipdt配体的R-基团的性质对氧化还原电势产生影响，并确认LUMO的位置主要位于络合物的R2pipdt部分。因此，与2b的相应跃迁相比，在较低的频率下发现了1b的低频吸收，该低频吸收被分配给具有配体间电荷转移特性的HOMO-LUMO跃迁。对R2pipdt配体前体（1a，2a）和相应的配合物（1b，2b）的电还原自由基进行原位EPR。这表明1b和2b中R2pipdt配体上未成对的电子有相当大的离域，与N和H的偶合常

  DOI：

  10.1039/b712243h
• 作为产物：
  描述：

  (n-Bu₄N)₂[Ni(2-thioxo-1,3-dithiole-4,5-dithiolato)₂] 、 [Ni(1,4-diisopropyl-piperazine-2,3-dithione)2](BF4)2 以 not given 为溶剂， 生成 [nickel(II)(1,4-diisopropylpiperazine-2,3-dithione)(2-thioxo-1,3-dithiole-4,5-dithiolato)]
  参考文献：
  名称：

  R取代基对[Ni（R2pipdt）（dmit）]配合物的性质和晶体结构的影响，其中R = CH2C6H5。

  摘要：

  [Ni（R2pipdt）（dmit）]，（R2pipdt = 1,4-二取代-哌嗪-3,2-二硫酮，R = CH2C6H5; dmit = 1,3-二硫代-2-硫酮-4,5-二硫代磺酸盐）（已经制备和表征了1b），并与属于相同类别的已知配合物2b的性质进行了比较，其中R ＝ Pr i。进行1b和2b的循环伏安法，并将其与相应的R2pipdt配体前体（1a和2a）的伏安法进行比较。pipdt配体的R-基团的性质对氧化还原电势产生影响，并确认LUMO的位置主要位于络合物的R2pipdt部分。因此，与2b的相应跃迁相比，在较低的频率下发现了1b的低频吸收，该低频吸收被分配给具有配体间电荷转移特性的HOMO-LUMO跃迁。对R2pipdt配体前体（1a，2a）和相应的配合物（1b，2b）的电还原自由基进行原位EPR。这表明1b和2b中R2pipdt配体上未成对的电子有相当大的离域，与N和H的偶合常

  DOI：

  10.1039/b712243h

文献信息

• ——
  作者：Francesco Bigoli、Chin-Ti Chen、Wei-Ching Wu、Paola Deplano、Maria Laura Mercuri、Maria Angela Pellinghelli、Luca Pilia、Gloria Pintus、Angela Serpe、Emanuele F. Trogu

  DOI：10.1039/b106064n

  日期：2001.10.23

  A simple method to obtain in high yields mixed-ligand nickel-dithiolene complexes, which show strong negative solvatochromism and negative first molecular hyperpolarizability, and the use of Raman spectroscopy to establish the extent of electronic delocalisation in these complexes, are reported.
• Electronic Factors Affecting Second-Order NLO Properties:  Case Study of Four Different Push-Pull Bis-Dithiolene Nickel Complexes
  作者：Simona Curreli、Paola Deplano、Christophe Faulmann、Andrea Ienco、Carlo Mealli、Maria Laura Mercuri、Luca Pilia、Gloria Pintus、Angela Serpe、Emanuele F. Trogu

  DOI：10.1021/ic0496469

  日期：2004.8.1

  The paper presents a detailed experimental and theoretical study of the four mixed nickel-bisdithiolene complexes [Ni(Pr(2)(i)pipdt)(dmit)] (1b, Pr(2)(i)pipdt = 1,4-diisopropyl-piperazine-3,2-dithione; dmit = 1,3-dithiolo-2-tione-4,5-dithiolato), [Ni(R(2)pipdt)(mnt)] (2b", R = 2-ethylhexyl; mnt = maleonitriledithiolato), [Ni(Pr(2)(i)timdt)(dmit)] (3b, Pr(2)(i)timdt = 1,3-diisopropyl-imidazoline-2,4,5-trithione), and [Ni(Pr(2)(i)timdt)(mnt)] (4b), and their models. All the complexes, with common (C2S2)Ni(C2S2) core and two different terminal groups, are uncharged and square-planar coordinated. Previous measurements of the first molecular hyperpolarizability indicated that some of the species are potential NLO chromophores due to the pi-delocalized character of two frontier levels (HOMO and LUMO) which is asymmetrically perturbed by the combination of one push (R(2)pipdt, R(2)timdt) with one pull ligand (dmit and mnt). The X-ray structure of complex 1b is presented and its geometry is compared with those available in the literature for the four types of complexes under study. The results of electrochemical and spectroscopic measurements (oxidation and reduction potentials, IR, dipole moment, molecular absorptivities, etc.) indicate rather different responses between the pairs of complexes 1-2 and 3-4. Hence, DFT calculations on the model compounds 1a-4a, where hydrogen atoms replace the alkyl groups of R(2)pipdt and R(2)timdt, have been carried out to correlate geometries and electronic structures. Moreover, the first molecular hyperpolarizabilities have been calculated and their components have been analyzed with the simplest two-level approximation. The derived picture highlights the different roles of the two push and pull ligands, but also the peculiar perturbation of the pi-electron density induced by the terminal CS3 grouping of the ligand dmit.