An iron(II) dihydrogen hydrido complex containing the tripodal tetraphosphine ligand P(CH2CH2PMe2)3

Leslie D. Field*, Hsiu L. Li, Barbara A. Messerle, Ronald J. Smernik, Peter Turner

*Corresponding author for this work

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

The dihydrogen hydrido complex [FeH(H2)(PP3)] + 1 (PP3 = P(CH2CH2PMe 2)3 2) was formed by the protonation of the dihydrido complex FeH2(PP3) 3 with methanol or ethanol. The observation of H-D coupling in partially deuterated isotopomers of 1 and measurement of T1 relaxation times for the hydrido and dihydrogen resonances of 1 confirmed the presence of the η2-dihydrogen ligand. Complex 1 shows dynamic NMR behaviour in both the 31P and H NMR spectra with facile exchange between the protons in the η2- dihydrogen ligand and the η1-hydrido ligand. The dihydrogen ligand of 1 is easily displaced by both anionic and neutral ligands to afford the corresponding hydrido complexes [FeHX(PP3)]+ (X = CO 11, X = PPh3 12) or FeHX(PP3) (X = Cl 13, X = Br 14, X = 115, X = N3 116). Small quantities of the alkoxy hydrido complexes FeH(OR)(PP3) (R = Me 4; R = Et 5) are observed in methanol and ethanol solutions containing 1. In methanol solution, FeH(OMe)(PP3) 4 reacts to form the carbonyl hydrido complex [FeH(CO)(PP3)] - 11 and isotopic labelling confirms that the carbonyl ligand of 11 is derived from the methanol solvent. The mechanism of methanol oxidation presumably proceeds through β-hydride elimination from FeH(OMe)(PP 3) to produce formaldehyde as an intermediate which is further dehydrogenated to form the carbonyl ligand. [FeH(H2)(PP 3)]+ 1 and FeHC1(PP3) 13 react rapidly with paraformaldehyde to also form [FeMe(CO)(PP3)]+ 11. Complex 11 also decarbonylates acetaldehyde to afford the methyl carbonyl complex [FeMe(CO)(PP3)]+ 17. The structure of 17 was confirmed by X-ray crystallography.

Original languageEnglish
Pages (from-to)1418-1423
Number of pages6
JournalDalton Transactions
Issue number9
DOIs
Publication statusPublished - 23 Apr 2004
Externally publishedYes

Keywords

  • Hydrides
  • Iron
  • Molecular hydrogen complexes
  • Nmr spectroscopy
  • P-containing ligands

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