[bis(triphenylphosphine)iminium][(THF)Mn(1,2-benzenedithiolate)2] | 1084898-69-0

• 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(triphenylphosphine)iminium][(THF)Mn(1,2-benzenedithiolate)2]
• 英文别名: benzene-1,2-dithiolate;bis(triphenyl-λ5-phosphanylidene)azanium;manganese(3+);oxolane
• CAS: 1084898-69-0
• 化学式: C₁₆H₁₆MnOS₄*C₃₆H₃₀NP₂
• 分子量: 946.093
• InChiKey: QALINNJZEQTMJR-UHFFFAOYSA-J

计算性质

• 辛醇/水分配系数(LogP)：
  10.2
• 重原子数：
  61
• 可旋转键数：
  6
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.08
• 拓扑面积：
  14.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  [bis(triphenylphosphine)iminium][(THF)Mn(1,2-benzenedithiolate)2] 以 二氯甲烷 为溶剂， 以80%的产率得到[bis(triphenylphosphine)iminium]2[Mn(1,2-benzenedithiolate)2]2
  参考文献：
  名称：

  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)

  摘要：

  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.

  DOI：

  10.1021/ic801553s
• 作为产物：
  描述：

  四氢呋喃 、 manganese(II) bromide 、 双(三苯基正膦基)氯化铵 、 1,2-苯二硫醇 在 CH₃ONa 作用下， 以 四氢呋喃 、 甲醇 为溶剂， 以61%的产率得到[bis(triphenylphosphine)iminium][(THF)Mn(1,2-benzenedithiolate)2]
  参考文献：
  名称：

  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)

  摘要：

  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.

  DOI：

  10.1021/ic801553s