| 154071-36-0

• CAS: 154071-36-0
• 化学式: C₁₉H₂₇O₂OsP
• 分子量: 508.596
• InChiKey: DTBGZYKMIYIRIT-UHFFFAOYSA-L

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

• 作为产物：
  描述：

  (η6-p-cymene)(catecholato)osmium 、 三甲基膦 以 氘代苯 为溶剂， 以99%的产率得到
  参考文献：
  名称：

  亚碘os（II）系统中的杂原子交换反应：Os-N多键的裂解和Os-X键的形成（X = O，S，C）

  摘要：

  The monomeric imido complex CymOsN-t-Bu (2) (Cym = eta6-p-cymene) was used as a convenient precursor in exchange reactions with a variety of H-X bonds (X = O, S, C). Complex 2 reacts with alkoxides HOCMe(CF3)2, pinacol, catechol, and 1,2-(H2N) (HO)C6H4 to give CymOs(NH-t-Bu)[OCMe(CF3)2] (4), CymOs[OC(CH3)cE(CH3)20] (5), CymOs[1,2-O2C6H4] (6), and CymOs[1,2-0(HN)C6H4](7), respectively. CymOs(O-t-Bu)2(3) was not formed by this method but was generated by treatment of [CymOsCl2]2 (1) with KO-t-Bu. Addition of H2N-t-Bu to 3 gave 2, and reaction of 5 with catechol gave 6. Complex 6 adds PMe3 to give CymOs[1,2-O2C6H4] (PMe3) (8). Catechol, 1,2-(H2N)2CrH4, or H2N-p-tol hydrogen bond or coordinate to the metal in 6 or CymOs[1,2-(NH)2C6H4] (10). Reactivity patterns generally correlate with the pK. of the substrate, but other factors are also involved. Several analogous thiolate complexes were also prepared. For example, imido complex 2 or bis(tert-butoxide) 3 reacted readily with t-BU-SH to give CymOs(S-t-BU)2 (13). The analogous osmium complexes with 2,6-Me2C6H3 and 2,4,6-Me3C6H2 groups attached to the sulfur atoms (14 and 15, respectively) were obtained by treatment of imido complex 2 with the appropriate thiols. However, reaction of 2 with p-tol-SH gave the dimeric thiolate complex [CymOs(S-p-Me-C6H4)2]2 (16). Complex 2 also reacts with carbon acids. The more acidic C-H bond of H2C(COMe)2 (acacH) caused the addition of 2 mol of diketone with tert-butylamine loss to give CymOs[CH(COMe)2][(OC(Me))2CH-O,O] (18) whereas the weaker acid (H2C(CO2Me)2) added only once across the Os-N bond to give CymOs(NH-t-Bu)[CH(CO2Me)2] (17). Treatment of dichloro dimer [CymOsCl2]2 with K2CO3 and acacH quantitatively provided yellow CymOs(acac-0,O)Cl(19). Monoacetylacetonato complex 19 was treated with AgOAc (Ac = COMe) to give CymOs(acac)(OAc) (21). Dimethyl malonate complex 17 was independently treated with acacH and H2C(CO(Ph))2 to give CymOs[CH(CO2Me)2][(OC(Me))2CH] (22) and bright red CymOs[CH(CO2Me)2][(OC(Ph))2CH] (23). Carbon-proton NMR coupling data provided evidence for the presence of carbon-metal bound diketonate ligands in 17, 18, 22, and 23.

  DOI：

  10.1021/om00015a021