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

Dalton Transactions : an International Journal of Inorganic Chemistry
Leslie D FieldPeter Turner

Abstract

The 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 formal...Continue Reading

Citations

Sep 10, 2014·Chemistry : a European Journal·Dörthe MellmannMatthias Beller
May 18, 2011·Dalton Transactions : an International Journal of Inorganic Chemistry·Ian Dance
Aug 29, 2006·Inorganic Chemistry·Ryan J TrovitchPaul J Chirik
Sep 8, 2010·Inorganic Chemistry·Leslie D FieldPeter Turner

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