cis-Mo(CO)4[(2,2'-O2C12H8)PO(CH2CH2O)3-2-C12H8-2'-P(2,2'-C12H8O2)] | 503299-88-5

• 英文名称: cis-Mo(CO)4[(2,2'-O2C12H8)PO(CH2CH2O)3-2-C12H8-2'-P(2,2'-C12H8O2)]
• CAS: 503299-88-5
• 化学式: C₄₆H₃₆MoO₁₃P₂
• 分子量: 954.672
• InChiKey: LGVKSOPCQYSPKL-UHFFFAOYSA-N

计算性质

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

• 作为反应物：
  描述：

  二氯甲烷 、 cis-Mo(CO)4[(2,2'-O2C12H8)PO(CH2CH2O)3-2-C12H8-2'-P(2,2'-C12H8O2)] 以 甲醇 、 二氯甲烷 为溶剂， 生成 cis-Mo(CO)4[(2,2'-O2C12H8)PO(CH2CH2O)3-2-C12H8-2'-P(2,2'-C12H8O2)]*dichloromethane
  参考文献：
  名称：

  Synthesis, NMR Characterization, and Cation Binding of Metallacrown Ethers with Asymmetric Bis(phosphinite) and Bis(phosphite) Ligands Derived from 2-Hydroxy-2‘-(1,4,7-trisoxo-9-nonanol)-1,1‘-biphenyl

  摘要：

  Chlorodiphenylphosphine and 2,2'-biphenylylenephosphorochloridite react with 2-hydroxy-2'-(1,4,7-trisoxo-9-nonanol)-1,1'-biphenyl to yield the new alpha,omega-bis(phosphorus-donor)polyether ligands Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2 and (2,2'-O2C12H8)P(CH2CH2O)(3)-2-C12H8-2'P(2,2'-O2C12H8). These ligands react with Mo(CO)(4)(nbd) to form the monomeric cis-metallacrown ethers cis-Mo(CO)(4){Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2} and cis-Mo(CO)(4)-{(2,2'-O2C12H8)P(CH2CH2O)(3)-2-C12H8-2'-P(2,2'-O2C12H8)}. The X-ray crystal structure of cis-Mo(CO)(4){(2,2'-O2C12H8)P(CH2CH2O)(3)-2-C12H8-2'-P(2,2'-O2C12H8)} indicates that in the solid state three of the four metallacrown ether ring oxygens point away from the cavity in the cis-metallacrown ether ring. Both metallacrown ethers undergo cis-trans isomerization in the presence of catalytic amounts of HgCl2 but yield quite different products, cis-Mo(CO)(4)-{Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2}.HgCl2 and trans-Mo(CO)(4){(2,2'-O2C12H8)P(CH2CH2O)(3)-2-C12H8-2'-P(2,2'-O2C12H8)}.HgCl2, when reacted with a stoichiometric amount of HgCl2. NMR titrations of the cis-metallacrown ethers with lithium salts demonstrate that the cis-metallacrown ethers form 2:1 complexes with Li+. The unexpected 2:1 ratio has been confirmed by the isolation of [cis-Mo(CO)(4){Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2](2)LiBPh4. In dichloromethane-d(2) solution, this complex very slowly isomerizes to form a mixture of [trans-Mo(CO)(4){Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2]LiBPh4 and the free cis-metallacrown ether, indicating that the trans-metallacrown ether more strongly binds Li+ than does the cis-metallacrown ether. Neither 2:1 stoichiometries for Li+ complexes of cis-metallacrown ethers nor complex formation by trans-metallacrown ethers have previously been reported.

  DOI：

  10.1021/om020868t
• 作为产物：
  描述：

  cis-Mo(CO)4[(phenyl)2PO(CH2CH2O)3-2-C12H8-2'-OP(phenyl)2] 在 NaB(C₆H₅)4 作用下， 以 二氯甲烷-D2 为溶剂， 生成 cis-Mo(CO)4[(2,2'-O2C12H8)PO(CH2CH2O)3-2-C12H8-2'-P(2,2'-C12H8O2)]
  参考文献：
  名称：

  Synthesis, NMR Characterization, and Cation Binding of Metallacrown Ethers with Asymmetric Bis(phosphinite) and Bis(phosphite) Ligands Derived from 2-Hydroxy-2‘-(1,4,7-trisoxo-9-nonanol)-1,1‘-biphenyl

  摘要：

  Chlorodiphenylphosphine and 2,2'-biphenylylenephosphorochloridite react with 2-hydroxy-2'-(1,4,7-trisoxo-9-nonanol)-1,1'-biphenyl to yield the new alpha,omega-bis(phosphorus-donor)polyether ligands Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2 and (2,2'-O2C12H8)P(CH2CH2O)(3)-2-C12H8-2'P(2,2'-O2C12H8). These ligands react with Mo(CO)(4)(nbd) to form the monomeric cis-metallacrown ethers cis-Mo(CO)(4){Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2} and cis-Mo(CO)(4)-{(2,2'-O2C12H8)P(CH2CH2O)(3)-2-C12H8-2'-P(2,2'-O2C12H8)}. The X-ray crystal structure of cis-Mo(CO)(4){(2,2'-O2C12H8)P(CH2CH2O)(3)-2-C12H8-2'-P(2,2'-O2C12H8)} indicates that in the solid state three of the four metallacrown ether ring oxygens point away from the cavity in the cis-metallacrown ether ring. Both metallacrown ethers undergo cis-trans isomerization in the presence of catalytic amounts of HgCl2 but yield quite different products, cis-Mo(CO)(4)-{Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2}.HgCl2 and trans-Mo(CO)(4){(2,2'-O2C12H8)P(CH2CH2O)(3)-2-C12H8-2'-P(2,2'-O2C12H8)}.HgCl2, when reacted with a stoichiometric amount of HgCl2. NMR titrations of the cis-metallacrown ethers with lithium salts demonstrate that the cis-metallacrown ethers form 2:1 complexes with Li+. The unexpected 2:1 ratio has been confirmed by the isolation of [cis-Mo(CO)(4){Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2](2)LiBPh4. In dichloromethane-d(2) solution, this complex very slowly isomerizes to form a mixture of [trans-Mo(CO)(4){Ph2PO(CH2CH2O)(3)-2-C12H8-2'-OPPh2]LiBPh4 and the free cis-metallacrown ether, indicating that the trans-metallacrown ether more strongly binds Li+ than does the cis-metallacrown ether. Neither 2:1 stoichiometries for Li+ complexes of cis-metallacrown ethers nor complex formation by trans-metallacrown ethers have previously been reported.

  DOI：

  10.1021/om020868t