1,3-bis(2-mercaptophenylthio)-2,2-dimethylpropane | 177750-05-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚类
• 英文名称: 1,3-bis(2-mercaptophenylthio)-2,2-dimethylpropane
• 英文别名: 2-[2,2-dimethyl-3-(2-sulfanylphenyl)sulfanylpropyl]sulfanylbenzenethiol
• CAS: 177750-05-9
• 化学式: C₁₇H₂₀S₄
• 分子量: 352.61
• InChiKey: IPOGSQYTVXUGCS-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.17
• 重原子数：
  21.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  0.0
• 氢给体数：
  2.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1,3-bis(2-mercaptophenylthio)-2,2-dimethylpropane 在 Na/Hg 作用下， 以 四氢呋喃 为溶剂， 生成 2-(2-methanidyl-2-methylpropyl)sulfanylbenzenethiolate;nickel(2+)
  参考文献：
  名称：

  Transition Metal Complexes with Sulfur Ligands. 117.¹ A Reaction Cycle for Nickel Mediated Thioester Formation from Alkyl, CO, and Thiolate Groups Modeling the Acetyl-Coenzyme A Synthase Function of CO Dehydrogenase

  摘要：

  In quest of nickel complexes with sulfur ligation that model the acetyl-CoA synthase function of CO dehydrogenase (CODH), [Ni('S(4)C(3)Me(2)')] (1, 'S(4)C(3)Me(2)'(2-) = 1,3-bis(2-mercaptophenylthio)-2,2-dimethyl-propane-(2-)) was synthesized by template alkylation of Na-2[Ni('S-2')(2)] ('S-2'(2-) = benzene-1,2-dithiolate(2-)) with CMe(2)(CH2Br)(2). Acidic hydrolysis of 1 yielded the thiol ''S(4)C(3)Me(2)''-H-2 (2). Reduction of 1 with Na/Hg resulted in cleavage of the 'S(4)C(3)Me(2)'(2-)ligand and formation of the thermally stable trinuclear nickel(II) alkyl thiolato complex [Ni('mu-S(2)C(3)Me(2)')](3) (3, 'S(2)C(3)Me(2)'(2-) = 1-(2-mercaptophenylthio)-2,2-dimethylpropyl(2-)). Treatment of 3 with L = Py, THF, or PMe(3) afforded the mononuclear compounds [Ni('S(2)C(3)Me(2)')(L)] (4, L = Py; 5, L = PMe(3)). The stoichiometric reaction of [Ni('S(2)C(3)Me(2)')(L)] with CO led to the cyclic thioester 'S(2)C(3)Me(2)CO' (6, 'S(2)C(3)Me(2)CO' = 2,3-benzo-6,6-dimethyl-8-oxo-1,4-dithia-cyclooctane) and Ni(CO)(4). In the analogous reaction of 5 with CO the intermediate nickel(II) acyl thiolato complex [Ni('S(2)C(3)Me(2)CO')(PMe(3))] (7 'S(2)C(3)Me(2)CO'(2-) = 1-(2-mercaptophenylthio)-2,2-dimethyl-3-oxobutyl(2-)) could be intercepted and fully characterized. The reaction of Ni(CO)(4) with the thiol 2 yielded the starting Ni(II) complex 1 and allowed to close the reaction cycle that comprises the CODH sequence: [Ni] --> [Ni-alkyl] --> [Ni-acyl] --> [Ni] + thioester. The net reaction can be formulated as 'S(4)C(3)Me(2)'-H-2 (2) + CO --> 'S(2)C(3)Me(2)CO' (6) + 'S-2'-H-2 and represents the first example of nickel mediated thioester formation in a complete reaction cycle. X-ray structure determinations of complexes 1, 3, 4, and 7 revealed approximately square planar coordination geometry for al Ni centers.

  DOI：

  10.1021/ja952598u
• 作为产物：
  描述：

  二溴新戊烷 、 1,2-苯二硫醇 在 盐酸 、 sodium methylate 、 nickel diacetate 作用下， 生成 1,3-bis(2-mercaptophenylthio)-2,2-dimethylpropane
  参考文献：
  名称：

  Transition Metal Complexes with Sulfur Ligands. 117.¹ A Reaction Cycle for Nickel Mediated Thioester Formation from Alkyl, CO, and Thiolate Groups Modeling the Acetyl-Coenzyme A Synthase Function of CO Dehydrogenase

  摘要：

  In quest of nickel complexes with sulfur ligation that model the acetyl-CoA synthase function of CO dehydrogenase (CODH), [Ni('S(4)C(3)Me(2)')] (1, 'S(4)C(3)Me(2)'(2-) = 1,3-bis(2-mercaptophenylthio)-2,2-dimethyl-propane-(2-)) was synthesized by template alkylation of Na-2[Ni('S-2')(2)] ('S-2'(2-) = benzene-1,2-dithiolate(2-)) with CMe(2)(CH2Br)(2). Acidic hydrolysis of 1 yielded the thiol ''S(4)C(3)Me(2)''-H-2 (2). Reduction of 1 with Na/Hg resulted in cleavage of the 'S(4)C(3)Me(2)'(2-)ligand and formation of the thermally stable trinuclear nickel(II) alkyl thiolato complex [Ni('mu-S(2)C(3)Me(2)')](3) (3, 'S(2)C(3)Me(2)'(2-) = 1-(2-mercaptophenylthio)-2,2-dimethylpropyl(2-)). Treatment of 3 with L = Py, THF, or PMe(3) afforded the mononuclear compounds [Ni('S(2)C(3)Me(2)')(L)] (4, L = Py; 5, L = PMe(3)). The stoichiometric reaction of [Ni('S(2)C(3)Me(2)')(L)] with CO led to the cyclic thioester 'S(2)C(3)Me(2)CO' (6, 'S(2)C(3)Me(2)CO' = 2,3-benzo-6,6-dimethyl-8-oxo-1,4-dithia-cyclooctane) and Ni(CO)(4). In the analogous reaction of 5 with CO the intermediate nickel(II) acyl thiolato complex [Ni('S(2)C(3)Me(2)CO')(PMe(3))] (7 'S(2)C(3)Me(2)CO'(2-) = 1-(2-mercaptophenylthio)-2,2-dimethyl-3-oxobutyl(2-)) could be intercepted and fully characterized. The reaction of Ni(CO)(4) with the thiol 2 yielded the starting Ni(II) complex 1 and allowed to close the reaction cycle that comprises the CODH sequence: [Ni] --> [Ni-alkyl] --> [Ni-acyl] --> [Ni] + thioester. The net reaction can be formulated as 'S(4)C(3)Me(2)'-H-2 (2) + CO --> 'S(2)C(3)Me(2)CO' (6) + 'S-2'-H-2 and represents the first example of nickel mediated thioester formation in a complete reaction cycle. X-ray structure determinations of complexes 1, 3, 4, and 7 revealed approximately square planar coordination geometry for al Ni centers.

  DOI：

  10.1021/ja952598u

文献信息

• Trinuclear [NiFe] Clusters as Structural Models for [NiFe] Hydrogenase Active Sites
  作者：Dieter Sellmann、Frank Lauderbach、Frank W. Heinemann

  DOI：10.1002/ejic.200400587

  日期：2005.1

  [Fe(CH3COCH=CHPh)(CO)3] reacts with [Ni('S 4 ')] x (x = 1, 2) or [Ni('S 4 C 3 Me 2 ')] ['S 4 ' 2 - = 1,2-bis(2-mercaptophenylthio)-ethane(2-),'S 4 C 3 Me 2 ' 2 - = 1,3-bis(2-mercaptophenylthio)-2,2-dimethylpropane(2-)] to afford trinuclear [NiFe] clusters [Ni('S 4 ')Fe(CO) 3 } 2 ] (1) and [Ni('S 4 C 3 Me 2 ')Fe(CO) 3 } 2 ] (2) and the dinuclear Fe I I Fe 0 complex [Fe(CO)('S 4 C 3 Me 2 ')Fe(CO) 3

  [Fe(CH3COCH=CHPh)(CO)3] 与 [Ni('S 4 ')] x (x = 1, 2) 或 [Ni('S 4 C 3 Me 2 ')] ['S 4 ' 2 - = 1,2-双(2-巯基苯硫基)-乙烷(2-),'S 4 C 3 Me 2 ' 2 - = 1,3-双(2-巯基苯硫基)-2,2-二甲基丙烷(2- )] 以提供三核 [NiFe] 簇 [Ni('S 4 ')Fe(CO) 3 } 2 ] (1) 和 [Ni('S 4 C 3 Me 2 ')Fe(CO) 3 } 2 ] (2) 和双核 Fe II Fe 0 配合物 [Fe(CO)('S 4 C 3 Me 2 ')Fe(CO) 3 ] (3)。团簇 1 和团簇 2 的 Ni-Fe 键长与 [NiFe] 氢化酶的活性或还原态相似，是 Ni 和铁结合的 CO 以硫为主的配位球。因此，团簇 1 和 2 可作为结构模型复合物[NiFe]