bis(triphenylphosphoranylidene)ammonium 2-aminobenzenethiolate | 247222-55-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: bis(triphenylphosphoranylidene)ammonium 2-aminobenzenethiolate
• 英文别名: 2-aminobenzenethiolate;bis(triphenyl-λ5-phosphanylidene)azanium
• CAS: 247222-55-5
• 化学式: C₆H₆NS*C₃₆H₃₀NP₂
• 分子量: 662.775
• InChiKey: GLIWBIIPLQLTPH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  7.58
• 重原子数：
  47
• 可旋转键数：
  6
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  28
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  bis(triphenylphosphoranylidene)ammonium 2-aminobenzenethiolate 、 [bis(triphenylphosphoranylidene)ammonium]2[(nitrosyl)Fe(3,6-dichloro-1,2-dithiosemibenzoquinone(1-) radical)(SC6H2-3,6-Cl2-SO2)] 以 四氢呋喃 为溶剂， 以44%的产率得到[bis(triphenylphosphoranylidene)ammonium]2[(nitrosyl)Fe(3,6-dichloro-1,2-benzenedithiolato)(SC6H2-3,6-Cl2-SO2)]
  参考文献：
  名称：

  具有{Fe（NO）} 6/7电子核的亚硝基化硫醇亚铁盐亚铁络合物：与含铁腈水合酶的有价和无价NO结合形式之间的转化有关。

  摘要：

  五配位的硫醇铁亚硝酰基络合物[（NO）Fe（S，S-C6H3R）2]-（R = H（1），m-CH3（2）），[（NO）Fe（S，S- C6H2-3,6-Cl2）2]-（3），[（NO）Fe（S，S-C6H3R）2] 2-（R = H（10），m-CH3（11））和[[ NO）Fe（S，S-C6H2-3,6-Cl2）2] 2-（12）已被分离并进行结构表征。O2触发含有{Fe（NO）} 6核的硫醇铁亚硝基配合物1-3的硫氧合，生成S键合的单亚磺酸盐铁物种[（NO）Fe（S，SO2-C6H3R）（S，S -C6H3R）]-（R = H（4），m-CH3（5））和[（NO）Fe（S，SO2-C6H2-3,6-Cl2）（S，S-C6H2-3,6- Cl2）] 2（2-）（6）。相反，O2对{Fe（NO）} 7络合物10的攻击导致形成络合物1，并伴随有次要产物[Fe（S，S-C6H4）2] 2（2-）和[NO3]

  DOI：

  10.1021/ic050108l

文献信息

• Monoanionic {Mn(NO)}⁵ and Dianionic {Mn(NO)}⁶ Thiolatonitrosylmanganese Complexes: [(NO)Mn(L)₂]⁻ and [(NO)Mn(L)₂]²⁻ (LH₂ = 1,2-Benzenedithiol and Toluene-3,4-dithiol)
  作者：Chia-Huei Lin、Chien-Ge Chen、Ming-Li Tsai、Gene-Hsiang Lee、Wen-Feng Liaw

  DOI：10.1021/ic801553s

  日期：2008.12.1

  The reaction of MnBr2 and [PPN](2)[S1S-C6H3-R] (1:2 molar ratio) in THF yielded [(THF)Mn(S,S-C6H3-R)(2)](-) [R = H (1a), Me (1b); THF = tetrahydrofuran]. Formation of the dimeric [Mn(S,S-C6H3-R)(2)](2)(2-) [R = H (2a), Me (2b)] was presumed to compensate for the electron-deficient Mn-III core via two thiolate bridges upon dissolution of complexes 1a and 1b in CH2Cl2. Complex 2a displays antiferromagnetic coupling interaction between two Mn-III centers (J = -52 cm(-1)), with the effective magnetic moment (mu eff) increasing from 0.85 mu(B) at 2.0 K to 4.86 mu(B) at 300 K. The dianionic manganese(II) thiolate complexes [Mn(S,S-C6H3-R)(2)](2-) [R = H (3a), Me (3b)] were isolated upon the addition of [BH4](-) into complexes la and 1b or complexes 2a and 2b, respectively. The anionic mononuclear (Mn(NO)}(5) thiolatonitrosylmanganese complexes [(NO)Mn(S,S-C6H3-R)(2)](-) [R = H (4a), Me (4b)] were obtained from the reaction of NO(g) with the anionic complexes la and 1b, respectively, and the subsequent reduction of complexes 4a and 4b yielded the mononuclear Mn(NO)}(6) [(NO)Mn(S,S-C6H3-R)(2)](2-) [R = H (5a), Me (5b)]. X-ray structural data, magnetic susceptibility measurement, and magnetic fitting results imply that the electronic structure of complex 4a is best described as a resonance hybrid of [(L)(QMn(III)(NO center dot)](-) and [(L)(L-center dot)Mn-III(NO-)](-) (L = 1,2-benzenedithiolate) electronic arrangements in a square-pyramidal ligand field. The lower IR nu(NO) stretching frequency of complex 5a, compared to that of complex 4a (shifiing from 1729 cm(-1) in 4a to 1651 cm-1 in 5a), supports that one-electron reduction occurs in the (L)(L-center dot)Mn-III} core upon reduction of complex 4a.