Conformationally restrained octahedral metallacrown ethers with 1,2-(Ph2P(CH2CH2O)2) 2C6H4 ligands. X-ray crystal structure of cis-Mo(CO)4{1,2-(Ph2P(CH2CH2O) 2)2C6H4-P,P′}

Academic Article

Abstract

  • A new α,ω-bis(phosphine)-polyether ligand, 1,2-(Ph2P(CH2CH2O)2) 2C6H4, has been synthesized and used to prepare a number of conformationally restrained metallacrown ethers. The reaction of 1,2-(Ph2P(CH2CH2O)2) 2C6H4 and Mo(CO)4(nbd) gives a good yield of cis-Mo-(CO)4{1,2-(Ph2P(CH2CH2O) 2)2C6H4-P,P′}. This complex has been isomerized to trans-Mo-(CO)4{1,2-(Ph2P(CH2CH 2O)2)2C6H4-P,P′} using both UV light and HgCl2 catalysis. The reaction of 1,2-(Ph2P(CH2CH2O)2) 2C6H4 with fac-RuCl2(CO)3(THF) initially yields a mixture of monomeric and oligomeric cis,cis,trans-[RuCl2(CO)2{1,2-(Ph2P(CH 2CH2O)2)2C6H 4-P,P′}]n metallacrown ethers. Surprisingly, the oligomeric metallacrown ethers slowly convert into the monomeric metallacrown ether at ambient temperature in a chloroform-d solution. This does not occur with the conformationally mobile [cis,cis,trans-RuCl2(CO)2{Ph2P(CH 2CH2O)4-CH2CH2PPh 2-P,P′}]n metallacrown ethers. The X-ray crystal structure of cis-Mo(CO)4{1,2-(Ph2P(CH2CH2O) 2)2C6H4-P,P′} has also been determined. The four ether oxygens lie in a plane, and the average cross-ring oxygen-oxygen distance is slightly larger than those in metallacrown ethers containing Ph2P(CH2CH2O)4CH2CH 2PPh2 ligands.
  • Authors

    Published In

  • Organometallics  Journal
  • Digital Object Identifier (doi)

    Pubmed Id

  • 16937962
  • Author List

  • Duffey CH; Lake CH; Gray GM
  • Start Page

  • 3550
  • End Page

  • 3556
  • Volume

  • 17
  • Issue

  • 16