1,3-benzothiazole-2-thiolate;iridium(3+);triphenylphosphane;carbonate | 168286-69-9

• 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: 1,3-benzothiazole-2-thiolate;iridium(3+);triphenylphosphane;carbonate
• CAS: 168286-69-9
• 化学式: C₄₄H₃₄IrNO₃P₂S₂
• 分子量: 943.058
• InChiKey: HYRUQXZCOYJSIG-UHFFFAOYSA-K

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：

  盐酸 、 1,3-benzothiazole-2-thiolate;iridium(3+);triphenylphosphane;carbonate 以 二氯甲烷 、 丙酮 为溶剂， 以70%的产率得到1,3-benzothiazole-2-thiolate;dichloroiridium(1+);triphenylphosphane
  参考文献：
  名称：

  铱双氧配合物对底物的氧化：一氧化碳的分子内氧化和杂环氮的攻击激活羰基。

  摘要：

  The square-planar complex [Ir(C7H4NS2)(CO)(PPh(3))(2)] (1) is obtained in high yield from the reaction of lithium benzothiazole-2-thiolate (LiC7H4NS2) with Vaska's complex, [IrCl(CO)(PPh(3))(2)]. Coordination of the new ligand in 1 and in the homologous rhodium complex should occur through the sulfur atom, as shown by their protonation reactions with HBF4, which give the hydridoiridium(III) complex [IrH(C7H4NS2)(CO)(PPh(3))(2)]BF4 and the rhodium(I) compound [Rh(CO)(PPh(3))(2)(C7H5NS2)]BF4, respectively. The neutral ligand C7H5NS2 reacts with 1 to give [IrH(C7H4NS2)(2)(CO)(PPh(3))(2)] (4). Complex 1 adds dihydrogen, methyl iodide, and dioxygen. The dioxygen complex [Ir(C7H4NS2)(O-2)(CO)(PPh(3))(2)] (7) undergoes an intramolecular oxidation of the carbonyl ligand, catalyzed by water, to yield the carbonate complex [Ir(C7H4NS2)(CO3)(PPh(3))(2)] (8). Labeling studies show that the reaction is multistep and oxygen from water is incorporated into the carbonate ligand. Sulfur dioxide is oxidized by complex 7, but in addition, activation of the carbonyl group occurs by attack of the heterocyclic nitrogen of the benzothiazole-2-thiolate ligand to give [Ir{C(O)NC(S)SC6H4}(SO4)(PPh(3))(2)] (11). In 8 both benzothiazole-2-thiolate and carbonate anions act as N,S- and O,O-chelating ligands. The structure of II shows a C,S-chelating ligand, obtained by an unprecedented incorporation of the carbonyl group of 7 into the benzothiazole-2-thiolate through the heterocyclic nitrogen, in addition to a chelating sulfate ligand.

  DOI：

  10.1021/om00010a044
• 作为产物：
  描述：

  、 氧气 以 四氢呋喃 、 水 为溶剂， 以78%的产率得到1,3-benzothiazole-2-thiolate;iridium(3+);triphenylphosphane;carbonate
  参考文献：
  名称：

  铱双氧配合物对底物的氧化：一氧化碳的分子内氧化和杂环氮的攻击激活羰基。

  摘要：

  The square-planar complex [Ir(C7H4NS2)(CO)(PPh(3))(2)] (1) is obtained in high yield from the reaction of lithium benzothiazole-2-thiolate (LiC7H4NS2) with Vaska's complex, [IrCl(CO)(PPh(3))(2)]. Coordination of the new ligand in 1 and in the homologous rhodium complex should occur through the sulfur atom, as shown by their protonation reactions with HBF4, which give the hydridoiridium(III) complex [IrH(C7H4NS2)(CO)(PPh(3))(2)]BF4 and the rhodium(I) compound [Rh(CO)(PPh(3))(2)(C7H5NS2)]BF4, respectively. The neutral ligand C7H5NS2 reacts with 1 to give [IrH(C7H4NS2)(2)(CO)(PPh(3))(2)] (4). Complex 1 adds dihydrogen, methyl iodide, and dioxygen. The dioxygen complex [Ir(C7H4NS2)(O-2)(CO)(PPh(3))(2)] (7) undergoes an intramolecular oxidation of the carbonyl ligand, catalyzed by water, to yield the carbonate complex [Ir(C7H4NS2)(CO3)(PPh(3))(2)] (8). Labeling studies show that the reaction is multistep and oxygen from water is incorporated into the carbonate ligand. Sulfur dioxide is oxidized by complex 7, but in addition, activation of the carbonyl group occurs by attack of the heterocyclic nitrogen of the benzothiazole-2-thiolate ligand to give [Ir{C(O)NC(S)SC6H4}(SO4)(PPh(3))(2)] (11). In 8 both benzothiazole-2-thiolate and carbonate anions act as N,S- and O,O-chelating ligands. The structure of II shows a C,S-chelating ligand, obtained by an unprecedented incorporation of the carbonyl group of 7 into the benzothiazole-2-thiolate through the heterocyclic nitrogen, in addition to a chelating sulfate ligand.

  DOI：

  10.1021/om00010a044