[OsCl(η6-p-cymene)]2(μ-OMe)2 | 1068005-86-6

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: [OsCl(η6-p-cymene)]2(μ-OMe)2
• 英文别名: methanolate;1-methyl-4-propan-2-ylbenzene;osmium(2+);dichloride
• CAS: 1068005-86-6
• 化学式: C₂₂H₃₄Cl₂O₂Os₂
• 分子量: 781.817
• InChiKey: DVAJSBAHSJXSRR-UHFFFAOYSA-L

计算性质

• 辛醇/水分配系数(LogP)：
  -1.81
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.45
• 拓扑面积：
  46.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [OsCl(η6-p-cymene)]2(μ-OMe)2 、 碳酸,甲基1-苯基-2-丙烯基酯 以 氘代四氢呋喃 为溶剂， 生成 [(Os(η6-p-cymene))2(μ-OMe)3](OCO2Me)
  参考文献：
  名称：

  Osmium-Catalyzed Allylic Alkylation

  摘要：

  Complex [OSCl2(eta(6)-p-cymene)](2) (1) reacts with (5,7-dioxa-6-phosphadibenzo[a,c]cyclohepten-6-yl)-dimethylamine (L-1) and (-)-(R)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine (L-2) to give OsCl2(eta(6)-p-eymene)L (L = L-1 (2), L-2 (3)). Complexes 1-3 and OsCl1(eta(6)-p-cymene) {P(OPh)3} (4) are efficient catalyst precursors for the alkylation of 1-phenylallyl methylcarbonate (5a), 1-phenylallyl acetate (5b), cinnamyl methylcarbonate (6a), and cinnamyl acetate (6b) with sodium dimethylmalonate to afford 1-phenylallyl dimethylmalonate (7) and cinnamyl dimethy1malonate (8) with branched:linear molar ratios between 97:3 and 67:33. In the absence of sodium dimethylmalonate, the reaction of 1 with 5a leads initially to {OsCl(eta(6) -p-cymene)}(2)(mu-OMe)(2) (9) and subsequently to [{Os(eta(6)- p-cymene)}(2)(mu-OMe)(3)][O2COMe] (10). In the absence of 5a, the reaction of 1 with sodium dimethylmalonate gives Os{kappa(1)-C-3-[CH(CO2Me)(2)]) {kappa(2)-O,O-[CH(CO2Me)(2)]}(eta(6)-p-cymene) (11). Complexes 9-11 are also efficient catalyst precursors for the alkylation of 5a with sodium dimethylmalonate. The activity of 9 and 10 is the same as that of 1. However, complex 11 is significantly less efficient than 1. In contrast to the latter, complexes 2 and 3 do not react with 5a in the absence of sodium dimethylmalonate. In the absence of the substrate, the reactions of 2 and 3 with sodium dimethylmalonate lead to Os{kappa(1)-C-3-[CH(CO2Me)(2)]}CI(eta(6)-p-cymene)L (L = L-1 (12), L-2 (13)), which further react with excess sodium dimethylmalonate to give 11. The catalytic behavior of 12 and 13 has been also studied. Their activities are the same as those of 2 and 3 and intermediate between those of 10 and 11. Complexes 3, 9, 11, and 12 have been characterized by X-ray diffraction analysis.

  DOI：

  10.1021/om800460h
• 作为产物：
  描述：

  [osmium(II)dichloride(η6-p-cymene)]2 、 碳酸,甲基1-苯基-2-丙烯基酯 以 四氢呋喃 为溶剂， 以27%的产率得到[OsCl(η6-p-cymene)]2(μ-OMe)2
  参考文献：
  名称：

  Osmium-Catalyzed Allylic Alkylation

  摘要：

  Complex [OSCl2(eta(6)-p-cymene)](2) (1) reacts with (5,7-dioxa-6-phosphadibenzo[a,c]cyclohepten-6-yl)-dimethylamine (L-1) and (-)-(R)-(3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)dimethylamine (L-2) to give OsCl2(eta(6)-p-eymene)L (L = L-1 (2), L-2 (3)). Complexes 1-3 and OsCl1(eta(6)-p-cymene) {P(OPh)3} (4) are efficient catalyst precursors for the alkylation of 1-phenylallyl methylcarbonate (5a), 1-phenylallyl acetate (5b), cinnamyl methylcarbonate (6a), and cinnamyl acetate (6b) with sodium dimethylmalonate to afford 1-phenylallyl dimethylmalonate (7) and cinnamyl dimethy1malonate (8) with branched:linear molar ratios between 97:3 and 67:33. In the absence of sodium dimethylmalonate, the reaction of 1 with 5a leads initially to {OsCl(eta(6) -p-cymene)}(2)(mu-OMe)(2) (9) and subsequently to [{Os(eta(6)- p-cymene)}(2)(mu-OMe)(3)][O2COMe] (10). In the absence of 5a, the reaction of 1 with sodium dimethylmalonate gives Os{kappa(1)-C-3-[CH(CO2Me)(2)]) {kappa(2)-O,O-[CH(CO2Me)(2)]}(eta(6)-p-cymene) (11). Complexes 9-11 are also efficient catalyst precursors for the alkylation of 5a with sodium dimethylmalonate. The activity of 9 and 10 is the same as that of 1. However, complex 11 is significantly less efficient than 1. In contrast to the latter, complexes 2 and 3 do not react with 5a in the absence of sodium dimethylmalonate. In the absence of the substrate, the reactions of 2 and 3 with sodium dimethylmalonate lead to Os{kappa(1)-C-3-[CH(CO2Me)(2)]}CI(eta(6)-p-cymene)L (L = L-1 (12), L-2 (13)), which further react with excess sodium dimethylmalonate to give 11. The catalytic behavior of 12 and 13 has been also studied. Their activities are the same as those of 2 and 3 and intermediate between those of 10 and 11. Complexes 3, 9, 11, and 12 have been characterized by X-ray diffraction analysis.

  DOI：

  10.1021/om800460h