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-(Ph P(CH CH O) ) C H , has been synthesized and used to prepare a number of conformationally restrained metallacrown ethers. The reaction of 1,2-(Ph P(CH CH O) ) C H and Mo(CO) (nbd) gives a good yield of cis-Mo-(CO) {1,2-(Ph P(CH CH O) ) C H -P,P′}. This complex has been isomerized to trans-Mo-(CO) {1,2-(Ph P(CH CH O) ) C H -P,P′} using both UV light and HgCl catalysis. The reaction of 1,2-(Ph P(CH CH O) ) C H with fac-RuCl (CO) (THF) initially yields a mixture of monomeric and oligomeric cis,cis,trans-[RuCl (CO) {1,2-(Ph P(CH CH O) ) C H -P,P′}] 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-RuCl (CO) {Ph P(CH CH O) -CH CH PPh -P,P′}] metallacrown ethers. The X-ray crystal structure of cis-Mo(CO) {1,2-(Ph P(CH CH O) ) C H -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 Ph P(CH CH O) CH CH PPh ligands. 2 2 2 2 2 6 4 2 2 2 2 2 6 4 4 4 2 2 2 2 2 6 4 4 2 2 2 2 2 6 4 2 2 2 2 2 2 6 4 2 3 2 2 2 2 2 2 2 6 4 n 2 2 2 2 2 4 2 2 2 n 4 2 2 2 2 2 6 4 2 2 2 4 2 2 2
  • 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