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

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dc.contributor.authorField, L.
dc.contributor.authorLi, H.
dc.contributor.authorMesserle, B.
dc.contributor.authorSmernik, R.
dc.contributor.authorTurner, P.
dc.date.issued2004
dc.description.abstractThe dihydrogen hydrido complex [FeH(H2)(PP3)]+ 1 (PP3 = P(CH2CH2PMe2)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 eta2-dihydrogen ligand. Complex 1 shows dynamic NMR behaviour in both the 31P and 1H NMR spectra with facile exchange between the protons in the eta2-dihydrogen ligand and the eta1-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 = I 15, X = N3 16). 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 beta-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.
dc.description.statementofresponsibilityLeslie D. Field, Hsiu L. Li, Barbara A. Messerle, Ronald J. Smernik and Peter Turner
dc.identifier.citationDalton Transactions, 2004; 2004(9):1418-1423
dc.identifier.doi10.1039/b401954g
dc.identifier.issn1477-9226
dc.identifier.issn1477-9234
dc.identifier.orcidSmernik, R. [0000-0001-6033-5855]
dc.identifier.urihttp://hdl.handle.net/2440/39206
dc.language.isoen
dc.publisherRoyal Soc Chemistry
dc.source.urihttps://doi.org/10.1039/b401954g
dc.titleAn iron(II) dihydrogen hydrido complex containing the tripodal tetraphosphine ligand P(CH2CH2PMe2)3
dc.typeJournal article
pubs.publication-statusPublished

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