Halo- and alkyl(pentamethylcyclopentadienyl)[1,2-bis(diphenylphosphino)ethane]iron(III) 17-electron complexes: synthesis, NMR and magnetic properties and EHMO calculations

Roger, Christophe; Toupet, Loı̈c; Rabaâ, Hassan; Saillard, Jean Yves; Hamon, Jean‐René; Lapinte, Claude

doi:10.1021/om00050a041

Cited by 151 publications

(201 citation statements)

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“…[26] Experimental Section All manipulations were carried out under an argon atmosphere by standard Schlenk techniques. The [Cp*Fe(dppe)H] hydride was synthesized according to reference [27].…”

Section: (Dppe)]mentioning

confidence: 99%

Experimental and Computational Studies of Hydrogen Bonding and Proton Transfer to [Cp*Fe(dppe)H]

Belkova

Collange

Dub

et al. 2005

Chemistry A European J

133

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The present contribution reports experimental and computational investigations of the interaction between [Cp*Fe(dppe)H] and different proton donors (HA). The focus is on the structure of the proton transfer intermediates and on the potential energy surface of the proton transfer leading to the dihydrogen complex [Cp*Fe(dppe)(H2)]+. With p-nitrophenol (PNP) a UV/Visible study provides evidence of the formation of the ion-pair stabilized by a hydrogen bond between the nonclassical cation [Cp*Fe(dppe)(H2)]+ and the homoconjugated anion ([AHA]-). With trifluoroacetic acid (TFA), the hydrogen-bonded ion pair containing the simple conjugate base (A-) in equilibrium with the free ions is observed by IR spectroscopy when using a deficit of the proton donor. An excess leads to the formation of the homoconjugated anion. The interaction with hexafluoroisopropanol (HFIP) was investigated quantitatively by IR spectroscopy and by 1H and 31P NMR spectroscopy at low temperatures (200-260 K) and by stopped-flow kinetics at about room temperature (288-308 K). The hydrogen bond formation to give [Cp*Fe(dppe)H]HA is characterized by DeltaH degrees =-6.5+/-0.4 kcal mol(-1) and DeltaS degrees = -18.6+/-1.7 cal mol(-1) K(-1). The activation barrier for the proton transfer step, which occurs only upon intervention of a second HFIP molecule, is DeltaH(not equal) = 2.6+/-0.3 kcal mol(-1) and DeltaS(not equal) = -44.5+/-1.1 cal mol(-1) K(-1). The computational investigation (at the DFT/B3 LYP level with inclusion of solvent effects by the polarizable continuum model) reproduces all the qualitative findings, provided the correct number of proton donor molecules are used in the model. The proton transfer process is, however, computed to be less exothermic than observed in the experiment.

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Section: (Dppe)]mentioning

confidence: 99%

Experimental and Computational Studies of Hydrogen Bonding and Proton Transfer to [Cp*Fe(dppe)H]

Belkova

Collange

Dub

et al. 2005

Chemistry A European J

133

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“…The detailed synthesis and the properties of these compounds have already been presented elsewhere [43][44][45][46][47][48][49][50][51][52][53][54]. The oneelectron oxidized complexes present a mixed-valence character and as monoradicals they are paramagnetic.…”

Section: Introductionmentioning

confidence: 99%

Magnetic perturbation of the redox potentials of localized and delocalized mixed-valence complexes

Lapinte

2008

Journal of Organometallic Chemistry

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“…This new complex 4[BPh 4 ] was formed overnight by reaction of 1 equiv 2,2 0 -bipyridine (3) with the known Fe(II) chloride precursor 2 in presence of NaBPh 4 (Scheme 2) [11]. Dark red crystals of this compound, which constitutes the unique product of the reaction according to mass spectrometry (MS-ESI), were obtained by slow diffusion of npentane into a saturated CH 2 Cl 2 solution of the above complex.…”

Section: Resultsmentioning

confidence: 99%

Unexpected isolation and structural characterization of a redox-active Fe(II) piano-stool complex with an η1-dppe ligand

Ghazala¹,

Paul²,

Toupet³

et al. 2007

Journal of Organometallic Chemistry

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Halo- and alkyl(pentamethylcyclopentadienyl)[1,2-bis(diphenylphosphino)ethane]iron(III) 17-electron complexes: synthesis, NMR and magnetic properties and EHMO calculations

Cited by 151 publications

References 0 publications

Experimental and Computational Studies of Hydrogen Bonding and Proton Transfer to [Cp*Fe(dppe)H]

Experimental and Computational Studies of Hydrogen Bonding and Proton Transfer to [Cp*Fe(dppe)H]

Magnetic perturbation of the redox potentials of localized and delocalized mixed-valence complexes

Unexpected isolation and structural characterization of a redox-active Fe(II) piano-stool complex with an η1-dppe ligand

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