Synthesis and characterization of [Pd2X2 (μ-X)2{Ph2P-(CH2 CH2O)nCH2 CH2PPh2-P,P′}]m (n = 3, 5, X = Cl, I) dimetallacrown ethers and the related dinuclear (see abstract)

Academic Article

Abstract

  • Reactions of the metallacrown ethers, [PdCl {PPh (CH CH O) CH CH PPh -P,P′}] (n = 3, 5), with PdCl or Pd(PhCN) Cl yield the new dimetallacrown ethers, [Pd Cl (μ-Cl) {PPh (CH CH O) CH CH PPh -P,P′}] (n = 3 (3), n = 5 (4)). Similar reactions of [PdCl {PPh (CH ) PPh -P,P′}] and [PdCl {PPh (CH CH O) CH CH -P} ] with PdCl or Pd(PhCN) Cl yield [Pd Cl (μ-Cl ){PPh (CH ) PPh -P,P′}] (5) and [Pd Cl (μ-Cl) {PPh (CH CH O) -CH CH -P} ] (6), respectively. The chloride-bridged dimetallacrown ethers, 3 and 4, are cleanly converted into the iodide-bridged dimetallacrown ethers, [Pd I (μ-I) {PPh (CH CH O) CH CH PPh -P,P′}] (n = 3 (7), n = 5 (8)) by reaction with excess NaI. In solution, 3 and 4 exist as mixtures of syn monomers and cyclic oligomers while 7 and 8 exist as mixtures of both syn and anti monomers and cyclic oligomers. The solid states structures of syn-[Pd I (μ-I) -{PPh (CH CH O) CH CH PPh -P,P′}] (syn-7) and of anti-[Pd I (μ-I) {Ph P(CH CH O) CH CH ) -P} } (anti-9) have been determined. These structures are consistent with the major species present in the solutions. They also suggest that syn-7 experiences ring-strain, which is consistent with the results from the P{ H} NMR studies. 2 2 2 2 n 2 2 2 m 2 2 2 2 2 2 2 2 2 n 2 2 2 m 2 2 2 12 2 m 2 2 2 2 2 2 3 2 2 2 2 2 2 2 2 2 12 2 m 2 2 2 2 2 2 2 2 3 2 2 2 2 2 2 2 n 2 2 2 m 2 2 2 2 2 2 3 2 2 2 2 2 2 2 2 2 2 2 3 2 2 31 1
  • Authors

    Author List

  • Smith DC; Lake CH; Gray GM
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  • 2950
  • End Page

  • 2955
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  • 14