trans-(PPh3)2Pd(C6H4-4-SC(O)Me)(I) | 886970-58-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯硫酚酯
• 英文名称: trans-(PPh3)2Pd(C6H4-4-SC(O)Me)(I)
• CAS: 886970-58-7
• 化学式: C₄₄H₃₇IOP₂PdS
• 分子量: 909.115
• InChiKey: RAHATWANYFKQJX-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  4-氰基吡啶 、 trans-(PPh3)2Pd(C6H4-4-SC(O)Me)(I) 、 silver trifluoromethanesulfonate 以 二氯甲烷 、 甲苯 为溶剂， 以75%的产率得到trans-(PPh3)2Pd(C6H4-4-SC(O)Me)(iso-nicotinonitrile)OTf
  参考文献：
  名称：

  Rigid-rod structured palladium complexes

  摘要：

  Mononuclear and homobimetallic palladium complexes of structural type [trans-(Me(O)CS-4-C6H4)(Ph3P)(2)Pd((NN)-N-boolean AND)]OTf (8a, (NN)-N-boolean AND=C4H4N2; 8b, (NN)-N-boolean AND=C5H4N-4-C N) and {[trans-(Me(O)CS-4-C6H4)(Ph3P)(2)Pd](2)(NN)-N-boolean AND}(OTf)(2) (9a, (NN)-N-boolean AND=4,4'-bipyridine (=bipy); 9b, (NN)-N-boolean AND = C6H4-1,4-(C N)(2); 9C, (NN)-N-boolean AND = (C6H4-4-C N)(2)) are accessible by the reaction of trans-(Ph3P)(2)Pd(C6H4-4-SC(O)Me)(OTf) (6) with I or 0.5 equivalents of the Lewis-bases (NN)-N-boolean AND (7a, (NN)-N-boolean AND = C4H4N2; 7b, (NN)-N-boolean AND = C5H4N-4-C N; 7c, (NN)-N-boolean AND = bipy; 7d, (NN)-N-boolean AND = C6H4-1,4-(C N)(2); 7e, (NN)-N-boolean AND = (C6H4-4-C N)(2)) in high yield. Complex 6 can be prepared in a two-step synthesis procedure. Oxidative addition Of 1-1-C6H4-4-SC(O)Me (2) to Pd(PPh3)(4) (3) gives trans-(Ph3P)(2)Pd(C6H4-4-SC(O)Me)(1) (4), which further reacts with [AgOTf] (5) to afford 6.The formation of 8 and 9 strongly depends on the size of the Lewis-bases (NN)-N-boolean AND. It is obvious that the co-ordination of the second N-ligated site of 8a or 8b to a further bulky [(PPh3)(2)Pd(C6H4-4-SC(O)Me)](+) unit is not possible. In contrast, more extended (NN)-N-boolean AND species such as 7c-7e will result in the formation of linear structured homobimetallic 9a-9c.The solid-state structures of 4 and 4 center dot CH2Cl2 are reported. Complex 4 is packed in the orthorhombic space group Pbca. The assembly of dichloromethane into the crystal lattice breaks the symmetry, whereby 4 center dot CH2Cl2 crystallises in the triclinic space group P (1) over bar. In both modifications a square-planar palladium(II) ion is present, with the iodo atom and the Me(O)CS-C6H4 unit trans-positioned. The different crystal packing has no significant influence onto the geometry around the d(8)-configurated palladium atoms. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2005.08.033
• 作为产物：
  描述：

  四(三苯基膦)钯 、 1-乙酰巯基-4-碘苯 以 甲苯 为溶剂， 以70%的产率得到trans-(PPh3)2Pd(C6H4-4-SC(O)Me)(I)
  参考文献：
  名称：

  Rigid-rod structured palladium complexes

  摘要：

  Mononuclear and homobimetallic palladium complexes of structural type [trans-(Me(O)CS-4-C6H4)(Ph3P)(2)Pd((NN)-N-boolean AND)]OTf (8a, (NN)-N-boolean AND=C4H4N2; 8b, (NN)-N-boolean AND=C5H4N-4-C N) and {[trans-(Me(O)CS-4-C6H4)(Ph3P)(2)Pd](2)(NN)-N-boolean AND}(OTf)(2) (9a, (NN)-N-boolean AND=4,4'-bipyridine (=bipy); 9b, (NN)-N-boolean AND = C6H4-1,4-(C N)(2); 9C, (NN)-N-boolean AND = (C6H4-4-C N)(2)) are accessible by the reaction of trans-(Ph3P)(2)Pd(C6H4-4-SC(O)Me)(OTf) (6) with I or 0.5 equivalents of the Lewis-bases (NN)-N-boolean AND (7a, (NN)-N-boolean AND = C4H4N2; 7b, (NN)-N-boolean AND = C5H4N-4-C N; 7c, (NN)-N-boolean AND = bipy; 7d, (NN)-N-boolean AND = C6H4-1,4-(C N)(2); 7e, (NN)-N-boolean AND = (C6H4-4-C N)(2)) in high yield. Complex 6 can be prepared in a two-step synthesis procedure. Oxidative addition Of 1-1-C6H4-4-SC(O)Me (2) to Pd(PPh3)(4) (3) gives trans-(Ph3P)(2)Pd(C6H4-4-SC(O)Me)(1) (4), which further reacts with [AgOTf] (5) to afford 6.The formation of 8 and 9 strongly depends on the size of the Lewis-bases (NN)-N-boolean AND. It is obvious that the co-ordination of the second N-ligated site of 8a or 8b to a further bulky [(PPh3)(2)Pd(C6H4-4-SC(O)Me)](+) unit is not possible. In contrast, more extended (NN)-N-boolean AND species such as 7c-7e will result in the formation of linear structured homobimetallic 9a-9c.The solid-state structures of 4 and 4 center dot CH2Cl2 are reported. Complex 4 is packed in the orthorhombic space group Pbca. The assembly of dichloromethane into the crystal lattice breaks the symmetry, whereby 4 center dot CH2Cl2 crystallises in the triclinic space group P (1) over bar. In both modifications a square-planar palladium(II) ion is present, with the iodo atom and the Me(O)CS-C6H4 unit trans-positioned. The different crystal packing has no significant influence onto the geometry around the d(8)-configurated palladium atoms. (c) 2005 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.ica.2005.08.033