| 168097-71-0

• 分子结构分类: 有机化合物 - 苯类化合物
• CAS: 168097-71-0
• 化学式: C₁₂H₂₂P₂Pt
• 分子量: 423.334
• InChiKey: GNJRRFNQKSVRFG-UHFFFAOYSA-N

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：

  以 四氢呋喃 、 二氯甲烷 、 水 、 苯 为溶剂， 生成
  参考文献：
  名称：

  cis-Hydroxyplatination of Dimethyl Maleate: Modeling the Intermediates in a Catalytic Alkene-Hydration Cycle with Organoplatinum(II)-Hydroxo Complexes

  摘要：

  Dimethyl maleate adds to the Pt-OH bonds of cis-Pt(OH)(Me)(PPh(3))(2) (2), Pt(OH)(Me)(dppe) (3), and Pr(OH)(Me)(pdmp) (5) [dppe = 1,2-bis(diphenylphosphino)ethane, Ph(2)PCH(2)CH(2)PPh(2); pdmp = o-phenylenebis-(dimethylphosphine), o-C6H4(PMe(2))(2)] to give cis-PtMe{CH(CO(2)Me)CH(OH)(CO(2)Me)}L(2) [L(2) = 2PPh(3) (6), dppe (7), pdmp (8)]. Crystals of 6 are monoclinic, space group P2(1)/n, with a = 12.858(2) Angstrom, b = 21.688(4) Angstrom, c = 14.340(2) Angstrom, beta = 97.25(1)degrees, and Z = 4. The structure was solved by the heavy atom method and refined by least-squares analysis to R = 0.027 and R(w) = 0.032 based on 4508 unique observed reflections. The platinum atom is planar-coordinated by two cis-PPh(3) ligands, a methyl group [r(Pt-C) = 2.111(6) Angstrom], and a CH(CO(2)Me)CH(OH)(CO(2)Me) group [r(Pt-C) = 2.152(7) Angstrom]. The threo-(R*,R*)-configuration of the PtCH(CO(2)Me)CH(OH)(CO(2)Me) moiety indicates that dimethyl maleate undergoes syn addition to the Pt-OH bond of 2, probably by cis-migratory insertion into the Pt-OH bond of a five-coordinate intermediate Pt(OH)(Me)(PPh(3))(2)(eta(2)-(Z)-MeO(2)CCH=CHCO(2)Me). Dimethyl maleate does not insert into the Pt-OH bonds of trans-Pt(OH)(Ph)(PEt(3))(2) (1) or Pt(OH)(CF3)(dppe) (4), and dimethyl fumarate is inert toward 1, 2, and 4, but it reacts with 5 to give the monomethyl fumarato complex PtMe{(E)-OC(O)CH=CHCO(2)Me}(pdmp) (9). Treatment of 6 or 7 with aqueous acids cleaves their Pt-CH(CO(2)Me)CH(OH)(CO(2)Me) bonds forming [PtMe(H2O)L(2)](+) and dimethyl malate, MeO(2)CCH(2)CH(OH)CO(2)Me, thus demonstrating two steps necessary for catalysis of addition of water to dimethyl maleate.

  DOI：

  10.1021/ja00137a006
• 作为产物：
  描述：

  bis[dimethyl(μ-dimethylsulfide)platinum(II)] 、 1,2-bis(dimethylphosphino)benzene 以 甲苯 为溶剂， 以84%的产率得到
  参考文献：
  名称：

  cis-Hydroxyplatination of Dimethyl Maleate: Modeling the Intermediates in a Catalytic Alkene-Hydration Cycle with Organoplatinum(II)-Hydroxo Complexes

  摘要：

  Dimethyl maleate adds to the Pt-OH bonds of cis-Pt(OH)(Me)(PPh(3))(2) (2), Pt(OH)(Me)(dppe) (3), and Pr(OH)(Me)(pdmp) (5) [dppe = 1,2-bis(diphenylphosphino)ethane, Ph(2)PCH(2)CH(2)PPh(2); pdmp = o-phenylenebis-(dimethylphosphine), o-C6H4(PMe(2))(2)] to give cis-PtMe{CH(CO(2)Me)CH(OH)(CO(2)Me)}L(2) [L(2) = 2PPh(3) (6), dppe (7), pdmp (8)]. Crystals of 6 are monoclinic, space group P2(1)/n, with a = 12.858(2) Angstrom, b = 21.688(4) Angstrom, c = 14.340(2) Angstrom, beta = 97.25(1)degrees, and Z = 4. The structure was solved by the heavy atom method and refined by least-squares analysis to R = 0.027 and R(w) = 0.032 based on 4508 unique observed reflections. The platinum atom is planar-coordinated by two cis-PPh(3) ligands, a methyl group [r(Pt-C) = 2.111(6) Angstrom], and a CH(CO(2)Me)CH(OH)(CO(2)Me) group [r(Pt-C) = 2.152(7) Angstrom]. The threo-(R*,R*)-configuration of the PtCH(CO(2)Me)CH(OH)(CO(2)Me) moiety indicates that dimethyl maleate undergoes syn addition to the Pt-OH bond of 2, probably by cis-migratory insertion into the Pt-OH bond of a five-coordinate intermediate Pt(OH)(Me)(PPh(3))(2)(eta(2)-(Z)-MeO(2)CCH=CHCO(2)Me). Dimethyl maleate does not insert into the Pt-OH bonds of trans-Pt(OH)(Ph)(PEt(3))(2) (1) or Pt(OH)(CF3)(dppe) (4), and dimethyl fumarate is inert toward 1, 2, and 4, but it reacts with 5 to give the monomethyl fumarato complex PtMe{(E)-OC(O)CH=CHCO(2)Me}(pdmp) (9). Treatment of 6 or 7 with aqueous acids cleaves their Pt-CH(CO(2)Me)CH(OH)(CO(2)Me) bonds forming [PtMe(H2O)L(2)](+) and dimethyl malate, MeO(2)CCH(2)CH(OH)CO(2)Me, thus demonstrating two steps necessary for catalysis of addition of water to dimethyl maleate.

  DOI：

  10.1021/ja00137a006