Fe II Complexes with Triple N 1, N 2‐Triazole Bridge Schiff Base Ligand: Antiferromagnetic Dimer vs. Spin Conversion Trimer

The unusual structure of Ruminococcin C1 antimicrobial peptide confers clinical properties.

The emergence of superbugs developing resistance to antibiotics and the resurgence of microbial infections have led scientists to start an antimicrobial arms race. In this context, we have previously identified an active RiPP, the Ruminococcin C1, naturally produced by Ruminococcus gnavus E1, a symbiont of the healthy human intestinal microbiota. This RiPP, subclassified as a sactipeptide, requires the host digestive system to become active against pathogenic Clostridia and multidrug-resistant strains. Here, we report its unique compact structure on the basis of four intramolecular thioether bridges introduced post-translationally by a specific radical-SAM sactisynthase. This structure con…

Vibrational spectrum of the spin crossover complex [Fe(phen)(2)(NCS)(2)] studied by IR and Raman spectroscopy, nuclear inelastic scattering and DFT calculations.

The vibrational modes of the low-spin and high-spin isomers of the spin crossover complex [Fe(phen)(2)(NCS)(2)] (phen = 1,10-phenanthroline) have been measured by IR and Raman spectroscopy and by nuclear inelastic scattering. The vibrational frequencies and normal modes and the IR and Raman intensities have been calculated by density functional methods. The vibrational entropy difference between the two isomers, DeltaS(vib), which is--together with the electronic entropy difference DeltaS(el)--the driving force for the spin-transition, has been determined from the measured and from the calculated frequencies. The calculated difference (DeltaS(vib) = 57-70 J mol(-1) K(-1), depending on the m…

Structure and mixed spin state of the chloroiron(III) complex of 2,3,7,8,12,13,17,18-octaphenyl-5,10,15,20-tetraphenylporphyrin, Fe(dpp)Cl

Abstract The chloroiron(III) complex Fe(dpp)Cl (1) of the peripherally crowded 2,3,7,8,12,13,17,18-octaphenyl-5,10,15,20-tetraphenylporphyrin or dodecaphenylporphyrin (dpp), has been synthesized and characterized by X-ray crystallography, normal-coordinate structural decomposition analysis (NSD), EPR and Mossbauer spectroscopy and magnetic susceptibility measurements. The dpp ligand present in the crystal structure of this molecule is predominantly saddle-shaped. It is also ruffled and slightly domed according to an analysis of the out-of-plane distortions performed by using NSD. This saddle deformation is significantly smaller than those observed in the chloroiron(III) complexes of the β-p…

Dynamics of Metal Centers Monitored by Nuclear Inelastic Scattering

Nuclear inelastic scattering of synchrotron radiation has been used now since 10 years as a tool for vibrational spectroscopy. This method has turned out especially useful in case of large molecules that contain a M\"ossbauer active metal center. Recent applications to iron-sulfur proteins, to iron(II) spin crossover complexes and to tin-DNA complexes are discussed. Special emphasis is given to the combination of nuclear inelastic scattering and density functional calculations.

Vibrational properties of 1D- and 3D polynuclear spin crossover Fe(II) urea-triazoles polymer chains and quantification of intrachain cooperativity

Abstract The vibrational dynamics of the iron centres in 1D and 3D spin crossover Fe(II) 4-alkyl-urea triazole chains have been investigated by synchrotron based nuclear inelastic scattering. For the 1D system, the partial density of phonon states has been modelled with density functional theory methods. Furthermore, spin dependent iron ligand distances and vibrational modes were obtained. The previously introduced intramolecular cooperativity parameter H coop (Rackwitz et al, Phys. Chem. Chem. Phys. 2013, 15, 15450) has been determined to −31 kJ mol−1 for [Fe(n-Prtrzu)3(tosylate)2] and to +27 kJ mol−1 for [Fe(n-Prtrzu)3(BF4)2]. The change of sign in H coop is in line with the incomplete an…

A comparative study of the physicochemical properties of iron isomaltoside 1000 (Monofer®), a new intravenous iron preparation and its clinical implications

Abstract The treatment of iron deficiency anemia with polynuclear iron formulations is an established therapy in patients with chronic kidney disease but also in other disease areas like gastroenterology, cardiology, oncology, pre/post operatively and obstetrics’ and gynecology. Parenteral iron formulations represent colloidal systems in the lower nanometer size range which have traditionally been shown to consist of an iron core surrounded by a carbohydrate shell. In this publication, we for the first time describe the novel matrix structure of iron isomaltoside 1000 which differs from the traditional picture of an iron core surrounded by a carbohydrate. Despite some structural similaritie…

The 5/2,3/2 Spin Admixture in the Chloroiron(III) Derivative of the Sterically Crowded 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetraphenylporphyrin

Despite similar ring deformations in solution and in the solid state, the chloroiron(III) derivative of 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin ([FeCl(oetpp)], shown schematically) prepared in this study exhibits only a very weak quantum-mechanical admixture of spin S=3/2 (only 4-10 %) with spin S=5/2. In contrast, for the variety of [FeCl(oetpp)] studied earlier by other researchers a 40 % contribution of the S=3/2 state was found.

Mössbauer investigations of the hexachlorantimonate salt of the phenyliron 2,3,7,8,l2,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrinate, [Fe(oetpp)Ph]SbCl6 and X-ray structure of the phenyliron(III) precursor Fe(III)(oetpp)Ph

Abstract The phenyliron derivative, [Fe(oetpp)C6H5)]SbCl6 (2) generated in dichloromethane by oxidation of the phenyliron(III) complex, Fe(III) (oetpp)C6H5 (1) of the 2,3,7,8,12,13,17,18-octaethyl-5,10,15,20-tetraphenylporphyrin with 1 equiv. of phenoxathiinylium hexachloroantimonate, [C12H8OS]SbCl6, was studied by Mossbauer spectroscopy. This compound exhibits an isomer shift δ of 0.13 mm s−1 and a quadrupole splitting ΔEQ of 3.23 mm s−1. The measured magnetic hyperfine pattern obtained in the temperature range 4.2–40 K in a field of 3.5 and 7 T, applied perpendicular to the γ-beam, has been consistently analyzed in the spin Hamiltonian approximation assuming an iron(IV) S=1 electronic con…

Die 5/2,3/2-Spin-Beiträge im Chloroeisen(III)-Derivat des sterisch überfrachteten 2,3,7,8,12,13,17,18-Octaethyl-5,10,15,20-tetraphenylporphyrins

CCDC 1587515: Experimental Crystal Structure Determination

Related Article: Ai-Min Li, Tim Hochdoerffer, Juliusz A. Wolny, Volker Schuenemann, Eva Rentschler|2018|Eur.J.Inorg.Chem.|2018|4190|doi:10.1002/ejic.201800784

CCDC 1587514: Experimental Crystal Structure Determination

Related Article: Ai-Min Li, Tim Hochdoerffer, Juliusz A. Wolny, Volker Schuenemann, Eva Rentschler|2018|Eur.J.Inorg.Chem.|2018|4190|doi:10.1002/ejic.201800784

CCDC 1587516: Experimental Crystal Structure Determination

Related Article: Ai-Min Li, Tim Hochdörffer, Juliusz A. Wolny, Volker Schünemann, Eva Rentschler|2018|Eur.J.Inorg.Chem.||4190|doi:10.1002/ejic.201800784

CCDC 1587517: Experimental Crystal Structure Determination

Related Article: Ai-Min Li, Tim Hochdoerffer, Juliusz A. Wolny, Volker Schuenemann, Eva Rentschler|2018|Eur.J.Inorg.Chem.|2018|4190|doi:10.1002/ejic.201800784