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Issue 9, 2004
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An iron(II) dihydrogen hydrido complex containing the tripodal tetraphosphine ligand P(CH2CH2PMe2)3

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Abstract

The dihydrogen hydrido complex [FeH(H2)(PP3)]+1 (PP3 = P(CH2CH2PMe2)32) 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 1H 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 = PPh312) or FeHX(PP3) (X = Cl 13, X = Br 14, X = I 15, X = N316). 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)(PP3) to produce formaldehyde as an intermediate which is further dehydrogenated to form the carbonyl ligand. [FeH(H2)(PP3)]+1 and FeHCl(PP3) 13 react rapidly with paraformaldehyde to also form [FeH(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.

Graphical abstract: An iron(ii) dihydrogen hydrido complex containing the tripodal tetraphosphine ligand P(CH2CH2PMe2)3

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Publication details

The article was received on 09 Feb 2004, accepted on 03 Mar 2004 and first published on 29 Mar 2004


Article type: Paper
DOI: 10.1039/B401954G
Dalton Trans., 2004, 1418-1423

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

    L. D. Field, H. L. Li, B. A. Messerle, R. J. Smernik and P. Turner, Dalton Trans., 2004, 1418
    DOI: 10.1039/B401954G

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