Fragmentation of (η<sup>5</sup>‐cyclopentadienyl)dicarbonyl‐acyliron complexes under electron impact

Baranowska, E.; Danikiewicz, Witold; Pakulski, Zbigniew; Zamojski, Aleksander

doi:10.1002/jms.1190300124

Cited by 4 publications

(4 citation statements)

References 14 publications

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“…S1). These CO stretching frequencies are similar to those from (η 5 ‐cyclopentadienyl)dicarbonylacyliron complexes in organic solvents or in the dried state [24,25]. Apparently, the electronic state of iron in both complexes is related arguing for an acyl‐iron ligation in the FeGP cofactor of [Fe]‐hydrogenase.…”

Section: Discussionsupporting

confidence: 55%

The crystal structure of C176A mutated [Fe]‐hydrogenase suggests an acyl‐iron ligation in the active site iron complex

et al. 2009

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a b s t r a c t[Fe]-hydrogenase is one of three types of enzymes known to activate H 2 . Crystal structure analysis recently revealed that its active site iron is ligated square-pyramidally by Cys176-sulfur, two CO, an ''unknown" ligand and the sp 2 -hybridized nitrogen of a unique iron-guanylylpyridinol-cofactor. We report here on the structure of the C176A mutated enzyme crystallized in the presence of dithiothreitol (DTT). It suggests an iron center octahedrally coordinated by one DTT-sulfur and one DTToxygen, two CO, the 2-pyridinol's nitrogen and the 2-pyridinol's 6-formylmethyl group in an acyliron ligation. This result led to a re-interpretation of the iron ligation in the wild-type.

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Section: Discussionsupporting

confidence: 55%

The crystal structure of C176A mutated [Fe]‐hydrogenase suggests an acyl‐iron ligation in the active site iron complex

et al. 2009

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“…The fragmentation of the organic part preceding the elimination of all CO molecules was not observed in either 1 or 2 , and this observation is in agreement with published results for complexes obtained from butatriene, hexapentaene and azine systems. However, a distinctive fragmentation was reported for (η 5 ‐cyclopentadienyl)dicarbonylacyliron, where in one of the pathways the alkyl radical was split off at first 15, 16…”

Section: Resultsmentioning

confidence: 99%

“…In mass spectral studies of carbonyliron complexes, a number of projects have been related to the cyclopentadienyliron carbonyl derivatives;15–18 however, for complexes of type I and II , no comparative mass spectral study has been published so far. The aim of this work was to investigate the fragmentation pathways obtained by the electron ionization (EI) method for the title compounds 1 and 2 , representing types I and II , respectively.…”

Section: Introductionmentioning

confidence: 99%

Electron ionization‐induced fragmentation of R₂N₂Fe₂(CO)₆ complexes with distinct geometries of the tetrahedral core: investigation of µ‐1,2‐(1,2‐diaza‐3‐methylcyclopentane)diylbis(tricarbonyliron) and bis(µ₂‐acetophenoniminato)bis(tricarbonyliron)

Zimniak

2002

J. Mass Spectrom.

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Two binuclear bis(tricarbonyliron) title complexes with N(2)Fe(2) tetrahedral cores, 1 and 2, respectively, which show different molecular folding resulting from the appearance (in 1), and absence (in 2) of the N-N sigma-bond, were compared in terms of mass spectral fragmentation routes. A multipath fragmentation noted for the molecule 1 revealing internal stress contrasts with the single-route fragmentation of 2. The fragmentation paths resulting from the admixtures were defined and analyzed from the fragment ion B/E and parent ion B(2)/E linked scan spectra.

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“…ATR-IR analysis of the mutated enzyme before and after the crystal structure determination still showed the presence of two CO ligands with a calculated angle of 901 between them. 46,47 In the mutated enzyme, the hydroxyl group on the pyridinol ligand now interacted via a hydrogen bond to the imidazole group of His14. In addition, the oxygen of the acyl group of the pyridinol ligand was linked via a hydrogen bond to the amide group of Ala176.…”

Section: The Crystal Structure Revealedmentioning

confidence: 99%

Evolution in the understanding of [Fe]-hydrogenase

Corr

Murphy

2011

Chem. Soc. Rev.

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Hydrogenases catalyse redox reactions with molecular hydrogen, either as substrate or product. The enzymes harness hydrogen as a reductant using metals that are abundant and economical, namely, nickel and iron, and should provide new pointers for the economic use of hydrogen in manmade devices. The most recently discovered and perhaps the most enigmatic of the hydrogenases is the [Fe]-hydrogenase, used by certain microorganisms in the pathway that reduces carbon dioxide to methane. Since its discovery some twenty years ago, [Fe]-hydrogenase has consistently provided structural and mechanistic surprises, often requiring complete re-evaluation of its mechanism of action. This tutorial review combines recent advances in X-ray crystallography and other analytical techniques, as well as in computational studies and in chemical synthesis to provide a platform for understanding this remarkable enzyme type.

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Fragmentation of (η⁵‐cyclopentadienyl)dicarbonyl‐acyliron complexes under electron impact

Abstract: Fragmentation patterns under electron impact of selected ($-cyclopentadienyl)dicarbonylacyliron complexes were studied. Fragmentation pathways were confirmed using accurate mass measurements and B/E = constant and mass-analysed ion kinetic energy fragment ion spectra.

Cited by 4 publications

References 14 publications

The crystal structure of C176A mutated [Fe]‐hydrogenase suggests an acyl‐iron ligation in the active site iron complex

The crystal structure of C176A mutated [Fe]‐hydrogenase suggests an acyl‐iron ligation in the active site iron complex

Electron ionization‐induced fragmentation of R₂N₂Fe₂(CO)₆ complexes with distinct geometries of the tetrahedral core: investigation of µ‐1,2‐(1,2‐diaza‐3‐methylcyclopentane)diylbis(tricarbonyliron) and bis(µ₂‐acetophenoniminato)bis(tricarbonyliron)

Evolution in the understanding of [Fe]-hydrogenase

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Fragmentation of (η5‐cyclopentadienyl)dicarbonyl‐acyliron complexes under electron impact

Abstract: Fragmentation patterns under electron impact of selected ($-cyclopentadienyl)dicarbonylacyliron complexes were studied. Fragmentation pathways were confirmed using accurate mass measurements and B/E = constant and mass-analysed ion kinetic energy fragment ion spectra.

Cited by 4 publications

References 14 publications

The crystal structure of C176A mutated [Fe]‐hydrogenase suggests an acyl‐iron ligation in the active site iron complex

The crystal structure of C176A mutated [Fe]‐hydrogenase suggests an acyl‐iron ligation in the active site iron complex

Electron ionization‐induced fragmentation of R2N2Fe2(CO)6 complexes with distinct geometries of the tetrahedral core: investigation of µ‐1,2‐(1,2‐diaza‐3‐methylcyclopentane)diylbis(tricarbonyliron) and bis(µ2‐acetophenoniminato)bis(tricarbonyliron)

Evolution in the understanding of [Fe]-hydrogenase

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Fragmentation of (η⁵‐cyclopentadienyl)dicarbonyl‐acyliron complexes under electron impact

Electron ionization‐induced fragmentation of R₂N₂Fe₂(CO)₆ complexes with distinct geometries of the tetrahedral core: investigation of µ‐1,2‐(1,2‐diaza‐3‐methylcyclopentane)diylbis(tricarbonyliron) and bis(µ₂‐acetophenoniminato)bis(tricarbonyliron)