3,6-bis(trimethylsilyl)benzene-1,2-dithiol | 1160172-39-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 英文名称: 3,6-bis(trimethylsilyl)benzene-1,2-dithiol
• 英文别名: H2tmsdt；3,6-Bis(trimethylsilyl)benzene-1,2-dithiol
• CAS: 1160172-39-3
• 化学式: C₁₂H₂₂S₂Si₂
• 分子量: 286.61
• InChiKey: LZJYATYUGKMFIN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.35
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  2
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  六氟磷酸钾 、 甲醇 、 [(tris(2-aminoethyl)amine)CrCl2]Cl 、 3,6-bis(trimethylsilyl)benzene-1,2-dithiol 在 (CH₃)3COK 作用下， 以 甲醇 、 水 为溶剂， 以64%的产率得到[Cr(tren)(tmsdt)]Cl0.5(PF6)0.5*methanol
  参考文献：
  名称：

  Octahedral Monodithiolene Complexes of Cobalt(III) and Chromium(III). Spectroscopic and Density Functional Theoretical Characterization of S,S′-Coordinated Benzene-1,2-dithiolate(1-) π Radicals.

  摘要：

  The reaction of [Mtren)Cl-2]Cl(M=Co(III), Cr(III) with benzene-1,2-dithiol, H-2(bdt), and 3,6-bis(trimethylsilyl)benzene-1,2-dithiol, H-2(tmsdt), in a water/methanol mixture in the presence of potassium tert-butodixe produced green crystals of [Mtren)(bdt)](PF6)(1/2)(Cl)(1/2)H2O (1(PF6)(1/2)(Cl)(1/2)center dot H2O, M = Co; 2(PF6)(1/2)(Cl)(1/2)center dot H2O, M = Cr) and [Mtren)(trnsdt)](PF6)(1/2)(Cl)(1/2)center dot H2O (1a(PF6)(1/2)(Cl)(1/2)center dot H2O, M =Co; 2a(PF6)(1/2)(Cl)(1/2)center dot H2O, M =Cr), respectively, upon addition of KPF6. The structures of 1 (PF6)(1/2)(Cl)(1/2), H2O and 2(PF6)(1/2)(Cl)(1/2)center dot H2O have be. en determined by X-ray crystallography. Octahedral 1 and 1a are diamagnetic whereas 2 and 2a possess an S = 3/2 ground state. Cyclic voltammeryof 1a and 2a in CH2Cl2 solution established that both species undergo a reversible one-electron oxidation generating die stable deatioiLs [Co-III(tren)(tmsdt(center dot))(2+) (S=1/2) and (Cr-III(tren(tmsdt(center dot))(2+) (S = 1) where (tmsdt(center dot))(1-) represents the pi radical monoanion of oxidized (tmsdt)(2-). The electrochemical oxidations art ligand centered processes. These dications have been investigated by UV-vis and EPR spectroscopy and density functional calculations using the B3L P functional. The S,g-coordinated benzene-1,2-dithiolate(1-) radical has been identified and unambiguously characterized. Comparison with the corresponding o-benzosemiquinonate(1-) complexes shows that the S,S-coordinated benzene-1,2-dithiolate(1-) radical is a sulfur centered radical whereas its oxygen containing analogue carries similar to 65% of die spin density oil die six-membered ring.

  DOI：

  10.1021/ic900515j

文献信息

• Characterization and Electronic Structures of Five Members of the Electron Transfer Series [Re(benzene-1,2-dithiolato)₃]^<i>z</i> (<i>z</i> = 1+, 0, 1−, 2−, 3−): A Spectroscopic and Density Functional Theoretical Study
  作者：Stephen Sproules、Flávio Luiz Benedito、Eckhard Bill、Thomas Weyhermüller、Serena DeBeer George、Karl Wieghardt

  DOI：10.1021/ic9010532

  日期：2009.12.7

  [ReIV(L)3]2− (S = 1/2), and a trianion [ReIII(L)3]3− (S = 1(?)). The unique X-band EPR spectrum of the neutral species clearly describes a diamagnetic Re(V) d2 central ion with the unpaired electron located in a purely ligand-centered molecular orbital, whereas it is metal-centered in the dianionic form: a Re(IV) d3 ion with three dithiolate(2−) ligands. S K-edge and Re L-edge X-ray absorption spectroscopy

  RECL的反应5与3当量的CH一个苯-1,2-二硫醇衍生物的3 CN产生的，在加入后[C 8 H ^ 16 N]溴（[C 8 H ^ 16 N] +是5-氮鎓spiro [4,4] nonane），[C 8 H 16 N] [Re（tms）3 ]（1c）和[C 8 H 16 N] [Re（Cl 2 -bdt）3 ]（2c），其中（tms）2-代表3,6-双（三甲基甲硅烷基）苯-1,2-二硫代酸酯和（Cl 2 -bdt）2-是3,6-二氯苯-1,2-二硫代酸酯。化学还原[Re（bdt）3 ]（3b）在PPh 4 Br存在下用正丁基锂制得[PPh 4 ] [Re（bdt）3 ]（3c），其中（bdt）2-为苯1,2-二硫代苯酚。这三个单阴离子络合物具有反磁性基态（Re（V），d 2，S = 0）。通过X射线晶体学测定了1c ·2CH 3 CN和2c ·C 3 H 6 O的晶体结构。电化学确定，络合物是涉及单阳离子[Re
• Octahedral Monodithiolene Complexes of Cobalt(III) and Chromium(III). Spectroscopic and Density Functional Theoretical Characterization of <i>S</i>,<i>S</i>′-Coordinated Benzene-1,2-dithiolate(1-) π Radicals.
  作者：Carsten Milsmann、Eberhard Bothe、Eckhard Bill、Thomas Weyhermüller、Karl Wieghardt

  DOI：10.1021/ic900515j

  日期：2009.7.6

  The reaction of [Mtren)Cl-2]Cl(M=Co(III), Cr(III) with benzene-1,2-dithiol, H-2(bdt), and 3,6-bis(trimethylsilyl)benzene-1,2-dithiol, H-2(tmsdt), in a water/methanol mixture in the presence of potassium tert-butodixe produced green crystals of [Mtren)(bdt)](PF6)(1/2)(Cl)(1/2)H2O (1(PF6)(1/2)(Cl)(1/2)center dot H2O, M = Co; 2(PF6)(1/2)(Cl)(1/2)center dot H2O, M = Cr) and [Mtren)(trnsdt)](PF6)(1/2)(Cl)(1/2)center dot H2O (1a(PF6)(1/2)(Cl)(1/2)center dot H2O, M =Co; 2a(PF6)(1/2)(Cl)(1/2)center dot H2O, M =Cr), respectively, upon addition of KPF6. The structures of 1 (PF6)(1/2)(Cl)(1/2), H2O and 2(PF6)(1/2)(Cl)(1/2)center dot H2O have be. en determined by X-ray crystallography. Octahedral 1 and 1a are diamagnetic whereas 2 and 2a possess an S = 3/2 ground state. Cyclic voltammeryof 1a and 2a in CH2Cl2 solution established that both species undergo a reversible one-electron oxidation generating die stable deatioiLs [Co-III(tren)(tmsdt(center dot))(2+) (S=1/2) and (Cr-III(tren(tmsdt(center dot))(2+) (S = 1) where (tmsdt(center dot))(1-) represents the pi radical monoanion of oxidized (tmsdt)(2-). The electrochemical oxidations art ligand centered processes. These dications have been investigated by UV-vis and EPR spectroscopy and density functional calculations using the B3L P functional. The S,g-coordinated benzene-1,2-dithiolate(1-) radical has been identified and unambiguously characterized. Comparison with the corresponding o-benzosemiquinonate(1-) complexes shows that the S,S-coordinated benzene-1,2-dithiolate(1-) radical is a sulfur centered radical whereas its oxygen containing analogue carries similar to 65% of die spin density oil die six-membered ring.