trans-Mo(CO)4(Ph2P(CH2CH2O)4CH2CH2PPh2-P,P') | 156475-51-3

• 英文名称: trans-Mo(CO)4(Ph2P(CH2CH2O)4CH2CH2PPh2-P,P')
• CAS: 156475-51-3
• 化学式: C₃₈H₄₀MoO₈P₂
• 分子量: 782.618
• InChiKey: DJWPXOAVYYDHSY-UHFFFAOYSA-N

反应信息

• 作为产物：
  描述：

  cis-Mo(CO)4[Ph₂P(CH₂CH₂O)4CH₂CH₂PPh₂-P,P'] 以 氘代氯仿 为溶剂， 以15%的产率得到trans-Mo(CO)4(Ph2P(CH2CH2O)4CH2CH2PPh2-P,P')
  参考文献：
  名称：

  由双（膦）配体在八面体金属络合物中反式配位形成的分子陀螺仪-反式Mo（CO）4 {Ph2P（CH2CH2O）4CH2CH2PPh2-P，P'}的合成和X射线晶体结构

  摘要：

  Photolysis of cis-Mo(CO)4{Ph2P(CH2CH2O)4CH2CH2PPh2-P,P'} (1) in THF under nitrogen gives trans-Mo(CO)4{Ph2P(CH2CH2O)4CH2CH2PPh2-P,P'} (2). Complex 2 is the first example of a metalla crown ether in which the alpha,omega-bis(phosphorus donor)polyether ligand is trans coordinated. It is also a rare example of an octahedral complex with a trans-spanning bis(phosphine) ligand.

  DOI：

  10.1021/om00017a002

文献信息

• Metallacrown ethers with trans-tetracarbonylmolybdenum(0) centers. X-ray crystal structures of trans-Mo(CO)4{Ph2P(CH2CH2O)nCH2CH2PPh2-P,P′} (n=3, 5) and trans-Mo(CO)4{Ph2P(CH2CH2O)2-1-C6H4-2-(OCH2CH2)2PPh2-P,P′}
  作者：Christina H Duffey、Charles H Lake、Gary M Gray

  DOI：10.1016/s0020-1693(01)00350-4

  日期：2001.5

  Photolysis of the cis-Mo(CO)(4)Ph2P(CH2CH2O)(n)CH2CH2PPh2-P,P'}, (1, n = 3; 2, b = 4; 3, n = 5) metallacrown ethers in tetrahydrofuran under nitrogen gives moderate yields of the corresponding trans-Mo(CO)(4)Ph2P(CH2CH2O)(n)CH2CH2PPh2-P,P'} (4, n = 3; 5, n = 4; 6, n = 5) metallacrown ethers. The trans-metallacrown ethers are also obtained when catalytic amounts of HgCl2 are added to chloroform solutions of the cis-metallacrown ethers. The 1 reversible arrow 4 and 2 reversible arrow 5 equilibria are established within 3 min at ambient temperature and approximately equal amounts of the cis- and trans-metallacrown ethers are present in the equilibrium mixtures. The 3 reversible arrow 6 equilibrium is more complicated because HgCl2 complexation by 3 also occurs in these solutions. Addition of excess HgCl2 to the equilibrium mixture of 3 and 6 results in the formation of the previously reported cis-Mo(CO)(4)mu -Ph2P(CH2CH2O)(5)CH2CH2PPh2-,P',O,O',O " ,O''',O''''}HgCl2. Comparison of the X-ray crystal structures of the trans-metallacrown ethers 4-6 and trans-Mo(CO)(4)Ph2P(CH2CH2O)(2)-1-C6H4-2-(OCH2CH2)(2)PPh2-P,P'} (7) indicates that both ring size and flexibility affect the conformations of the metallacrown ether rings. The larger oxygen-oxygen distances in the trans-metallacrown ethers, compared with those in the corresponding cis-metallacrown ethers 1, 3 and cis-Mo(CO)(4)Ph2P(CH2CH2O)(2)-1-C6H4-2-(OCH2CH2)(2)PPh2-P,P'} (8), may explain why the trans-metallacrown ethers have not been observed to bind strongly the hard metal cations. (C) 2001 Elsevier Science B.V. All rights reserved.
• Gray, Gary M.; Duffey, Christina H., Organometallics, <hi>1995</hi>, vol. 14, # 1, p. 245 - 250
  作者：Gray, Gary M.、Duffey, Christina H.

  DOI：——

  日期：——