(4-methylpiperazinecarbodithioato)(thiocyanato-N)(triphenylphosphine)nickel(II) | 935742-13-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪烷类
• 英文名称: (4-methylpiperazinecarbodithioato)(thiocyanato-N)(triphenylphosphine)nickel(II)
• 英文别名: [Ni(4-mpzdtc)(PPh3)(NCS)]
• CAS: 935742-13-5
• 化学式: C₂₅H₂₆N₃NiPS₃
• 分子量: 554.363
• InChiKey: IJVFEPRVMBHOEO-UHFFFAOYSA-M

反应信息

• 作为产物：
  描述：

  N-甲基哌嗪 以 甲醇 、 乙醇 、 水 、 乙腈 为溶剂， 生成 (4-methylpiperazinecarbodithioato)(thiocyanato-N)(triphenylphosphine)nickel(II)
  参考文献：
  名称：

  Synthesis, NMR spectral and single crystal X-ray structural studies on Ni(II) dithiocarbamates with NiS2PN, NiS2PC, NiS2P2 chromophores: Crystal structures of (4-methylpiperazinecarbodithioato)(thiocyanato-N) (triphenylphosphine)nickel(II) and bis(triphenylphosphine) (4-methylpiperazinecarbodithioato)nickel(II) perchlorate monohydrate

  摘要：

  Four Ni(II) dithiocarbamates with NiS2PX (X = NCS or CN or P) chromophores have been synthesized [[Ni(4-mpzdtc)(PPh3)(NCS)] (1), [Ni(4-mpzdtc)(PPh3)(CN)] (2), [Ni(4-mpzdtc)(PPh3)(2)]ClO4 center dot H2O (3) and [Ni(4-mpzdtc)(dppe)]ClO4 (4) (where 4-mpzdtc = 4-methylpiperazinecarbodithioato anion, PPh3 = triphenylphosphine and dppe = 1,2-bis((diphenylphosphino)ethane))] from [Ni(4-mpzdtc)(2)]. Electronic spectra of the complexes show bands corresponding to d(z2)/d(xy) -> d(x2-y2) transitions. IR spectra of all the compounds showed characteristic bands due to the dithiocarbamate ligand around 1500 cm(-1) and 990 cm(-1). CV studies showed a higher reduction potential for the parent complex indicating the reluctance to add more electron density to the already electron rich metal centre. H-1 NMR spectra of the complexes showed the deshielding of alpha-CH2 protons on complexation. The C-13 signals show interesting variations for the S-2-C-13 N carbon signals between the neutral [1 and 2] and ionic complexes [3 and 4]. The S-2- C-13 N chemical shifts of the three complexes with PPh3 follow the order: 3 < 1 < 2 indicating the influence of PPh3, NCS, CN respectively on the mesomeric drift of electron density towards nickel. The PPh3 complexes show the following order of increasing P-31 chemical shifts: 3 (30.9 ppm) > 2 (22.1 ppm) > 1 (20.5 ppm). The observed order clearly establishes the ease with which the back bonding interaction takes place. The back bonding is best observed in the case of the NiS2P2 chromophore. Single crystal X-ray structures of [Ni(4-mpzdtc)(PPh3)(NCS)] and [Ni(4-mpzdtc)(PPh3)(2)]ClO4 indicate that the central metal atom is in a planar environment for both complexes. The planarity of the molecules is supported by the observed diamagnetism of the complexes. The short S-2-C N bonds indicate the partial double bond character in both cases. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.poly.2006.10.006