Publications related to A Five-Coordinate Iron Center in the Active Site of [Fe]-Hydrogenase: Hints from a Model Study

ONETEP plus TOSCAM: Uniting Dynamical Mean Field Theory and Linear-Scaling Density Functional Theory

We introduce the unification of dynamical mean field theory (DMFT) and linear-scaling density functional theory (DFT), as recently implemented in ONETEP, a linear-scaling DFT package, and TOSCAM, a DMFT toolbox. This code can account for strongly correlate ...

2020

A catalytically active [Mn]-hydrogenase incorporating a non-native metal cofactor

Matthew Wodrich, Xile Hu, Farzaneh Fadaei Tirani, Huijie Pan

Nature carefully selects specific metal ions for incorporation into the enzymes that catalyse the chemical reactions necessary for life. Hydrogenases, enzymes that activate molecular H-2, exclusively utilize Ni and Fe in [NiFe]-, [FeFe]- and [Fe]-hydrogean ...

2019

Stereoselective synthesis of alkenes via base-metal-catalyzed addition reactions to alkynes and activation of hydrogen peroxide and carbon dioxide by iron complexes

Fedor Zhurkin

Alkene functionality can be found in the majority of natural products, drugs, catalysts and organic materials. Therefore, methods of C-C double bond formation constitute a cornerstone of organic synthesis. Selective formation of either (Z)- or (E)-isomer i ...

EPFL2017

Towards artificial methanogenesis: biosynthesis of the [Fe]-hydrogenase cofactor and characterization of the semisynthetic hydrogenase

Xile Hu, Tao Xu, Lichen Bai

The greenhouse gas and energy carrier methane is produced on Earth mainly by methanogenic archaea. In the hydrogenotrophic methanogenic pathway the reduction of one CO2 to one methane molecule requires four molecules of H-2 containing eight electrons. Four ...

Royal Soc Chemistry2017

A Functional Model of [Fe]-Hydrogenase

Rosario Scopelliti, Matthew Wodrich, Xile Hu, Simona Mazza, Tao Xu

[Fe]-Hydrogenase catalyzes the hydrogenation of a biological substrate via the heterolytic splitting of molecular hydrogen. While many synthetic models of [Fe]-hydrogenase have been prepared, none yet are capable of activating H-2 on their own. Here, we re ...

American Chemical Society2016

Bacterial inactivation with iron citrate complex: A new source of dissolved iron in solar photo-Fenton process at near-neutral and alkaline pH

César Pulgarin, Andrzej Sienkiewicz, Cristina del Socorro Lonfat

This study reports the first application of Fe-citrate-based photo-Fenton chemistry for the inactivation of Escherichia coil. Promising results of bacterial inactivation at near-neutral and alkaline pH conditions were obtained, while using low iron concent ...

Elsevier2016

Iron Complexes for Hydrogen Activation and Catalytic Hydrogenation

Simona Mazza

Inspired by Nature several groups have developed structural and functional iron complexes mimicking the active site of the iron-hydrogenases, which show high reactivity in the H2 cleavage. Usually pendant bases have been incorporated onto families of Fe co ...

EPFL2015

Iron Pincer Complexes as Catalysts and Intermediates in Alkyl Aryl Kumada Coupling Reactions

Rosario Scopelliti, Matthew Wodrich, Xile Hu, Gerald Bauer

Iron-catalyzed alkylaryl Kumada coupling has developed into an efficient synthetic method, yet its mechanism remains vague. Here, we apply a bis(oxazolinylphenyl)amido pincer ligand (Bopa) to stabilize the catalytically active Fe center, resulting in isola ...

American Chemical Society2015

Reconstitution of [Fe]-hydrogenase using model complexes

Matthew Wodrich, Xile Hu, Dafa Chen, Tao Xu

[Fe]-Hydrogenase catalyses the reversible hydrogenation of a methenyltetrahydromethanopterin substrate, which is an intermediate step during the methanogenesis from CO2 and H-2. The active site contains an iron-guanylylpyridinol cofactor, in which Fe2+ is ...

Nature Publishing Group2015

Synthesis and Reactivity of Mononuclear Iron Models of [Fe]-Hydrogenase that Contain an Acylmethylpyridinol Ligand

Xile Hu, Dafa Chen, Bowen Hu

[Fe]-hydrogenase has a single iron-containing active site that features an acylmethylpyridinol ligand. This unique ligand environment had yet to be reproduced in synthetic models; however the synthesis and reactivity of a new class of small molecule mimics ...

Wiley-V C H Verlag Gmbh2014

Electronic Elements Governing the Binding of Small Molecules to a [Fe]-hydrogenase Mimic

Matthew Wodrich, Xile Hu

[Fe]-hydrogenase, one of three types of hydrogenases, activates molecular hydrogen. Here, using DFT computations, we examine the electronic elements governing the binding of small ligands to a recently synthesized [Fe]-hydrogenase biomimic. Computed reacti ...

Wiley-Blackwell2013

Reversible protonation of a thiolate ligand in an [Fe]-hydrogenase model complex

Rosario Scopelliti, Xile Hu, Dafa Chen

The thiolate ligand in the five-coordinate model complex 1 of [Fe]-hydrogenase is preferentially and reversibly protonated, even in the presence of an acyl ligand. The results suggest that the Cys176 thiolate ligand in [Fe]-hydrogenase can serve as the int ...

Wiley-VCH Verlag GmbH2012

Synthesis and Characterization of a Series of Model Complexes of the Active Site of [Fe]-Hydrogenase (Hmd)

Rosario Scopelliti, Xile Hu, Dafa Chen

A series of Fe complexes were synthesized and characterized as small molecule mimics for the active site of [Fe]-hydrogenase (Hmd). The collection includes both structurally new compounds and analogues of previously reported models. These complexes contain ...

2011

NMR Study of Ligand Exchange and Electron Self-Exchange between Oxo-Centered Trinuclear Clusters [Fe3(μ3-O)(μ-O2CR)6(4-R´py)3]+/0

André Merbach, Lothar Helm

The syntheses, single crystal X-ray structures, and magnetic properties of the homometallic mu(3)-oxo trinuclear clusters Fe-3(mu(3)-O)(mu-O2CCH3)(6)(4-Phpy)(3) (1) and F(e)3(mu(3)-O)(mu-O(2)CAd)(6)(4-Mepy)(3) (2) are reported (Ad = adamanta ...

American Chemical Society2011

Nitrous Oxide Abatement over Fe-Zeolite : Mechanistic Study of Decomposition and Reactor Development

Bryan Bromley

The use of zeolites for catalytic reactions is a field in continuous development. Since it was demonstrated that metal-zeolites are efficient catalysts for NOx abatement, decomposition of nitrous oxide (N2O) over Fe-containing zeolites has attracted great ...

EPFL2010

Probing the Electronic Structure of the Hemoglobin Active Center in Physiological Solutions

Majed Chergui

Soft-x-ray absorption spectroscopy at the L2,3 edge of the iron center in bovine Hb and hemin under physiol. conditions is reported for the first time. Spectra of the same compds. in solid form are presented for comparison. Striking differences in the elec ...

2009

Mechanism of Pyridine-Ligand Exchanges at the Different Labile Sites of 3d Heterometallic and Mixed Valence μ3-oxo Trinuclear Clusters

André Merbach, Lothar Helm, Rosario Scopelliti, Fabrice Riblet

The syntheses and single crystal X-ray structural analysis of five novel hetero- and homometallic μ3-oxo trinuclear cluster with the formula [FeIII2MII(μ3-O)(μ-O2CCH3)6(4-Rpy)3] · x(4-Rpy) · y(CH3CN) where R ) Ph for 1(Fe2Mn),2(Fe2Fe), 3(Fe2Co), 4(Fe2Ni) a ...

2008

Low-dimensional supramolecular architectures at metal surfaces

Sebastian Stepanow

This thesis is concerned with supramolecular architectures assembled at metal surfaces. The investigations pursued two objectives. On the one hand, the focus was placed on the fabrication of low-dimensional surface-supported network structures by applying ...

EPFL2005