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European Journal of Inorganic Chemistry

Mehdi Elsayed Moussa, Stefan Welsch, Matthias Lochner, Eugenia V Peresypkina, Alexander V Virovets, Manfred Scheer
A multicomponent approach of the P n ligand complex [Cp*Fe(η5 -P5 )] ( 1 : Cp* = η5 -C5 Me5 ) with the ditopic organic linkers 4,4'-bipyridine ( 2 ) or trans -1,2-di(pyridine-4-yl)ethene ( 3 ) in the presence of CuI salts of the anions [BF4 ]- and [PF6 ]- or the coordinating anion Br- , leads to the formation of four novel organometallic-organic hybrid polymers: the cationic 1D polymeric compounds [Cu4 {Cp*Fe(µ3 ,η5:1:1 -P5 )}2 (µ,η1:1 -C10 H8 N2 )4 (CH3 CN)4 ] n [BF4 ]4n ( 4 ) and [Cu4 {Cp*Fe(µ3 ,η5:1:1 -P5 )}2 (µ,η1:1 -C10 H8 N2 )4 (CH3 CN)4 ] n [PF6 ]4n ( 5 ) as well as the unique neutral threefold 2D → 2D interpenetrated networks [Cu2 Cl2 {Cp*Fe(µ3 ,η5:1:1 -P5 )}(µ,η1:1 -C12 H10 N2 )] n ( 6 ) and [Cu2 Br2 {Cp*Fe(µ3 ,η5:1:1 -P5 )}(µ,η1:1 -C10 H8 N2 )] n ( 7 )...
June 22, 2018: European Journal of Inorganic Chemistry
Linda S Jongbloed, Nicolas Vogt, Aaron Sandleben, Bas de Bruin, Axel Klein, Jarl Ivar van der Vlugt
Based on previous work related to the design and application of rigid tridentate phosphine-pyridine-phenyl coordination offered by a PNC-pincer ligand upon cyclometalation to nickel, the synthesis, spectroscopic and solid state characterization and redox-reactivity of two NiII (PNC) complexes featuring either a methyl ( 2CH3 ) or CF3 co-ligand ( 2CF3 ) are described. One-electron oxidation is proposed to furnish C-C reductive elimination, as deduced from a combined chemical, electrochemical, spectroscopic and computational study...
June 7, 2018: European Journal of Inorganic Chemistry
Fenna F van de Watering, Wowa Stroek, Jarl Ivar van der Vlugt, Bas de Bruin, Wojciech I Dzik, Joost N H Reek
We report the coordination chemistry of indole based tripodal tetraphosphine ligands to iron(II), cobalt(II) and nickel(II). These complexes are formed by simple synthetic protocols and were characterized by a combination of spectroscopic techniques and single-crystal X-ray analysis. The molecular structures as determined by X-ray diffraction show that the geometry of the nickel and cobalt complexes are distorted trigonal bipyramidal. The monocationic iron(II) complexes also have distorted trigonal bipyramidal geometries, but the dicationic analogue has an octahedral geometry...
March 22, 2018: European Journal of Inorganic Chemistry
Emma Folkertsma, Sanne H Benthem, Johann T B H Jastrzebski, Martin Lutz, Marc-Etienne Moret, Robertus J M Klein Gebbink
In this study, the selective 1,2-addition of diethylzinc to the ketone functionality of BMdiPh IK [bis(1-methyl-4,5-diphenylimidazolyl)ketone] is shown. The reaction product is isolated in a dimeric form with a planar Zn2 (µ-O)2 -motif keeping the two monomers together. This compound can serve as a model for reactive intermediates in the catalytic alkylation of ketones with diorganozinc reagents. Hydrolysis of this binuclear zinc compound leads to isolation of the C-alkylated product in 89 % yield. A reaction pathway is proposed in which BMdiPh IK initially coordinates to diethylzinc as a bidentate bis(nitrogen) ligand...
March 14, 2018: European Journal of Inorganic Chemistry
Valentina Borghesani, Bruno Alies, Christelle Hureau
In the present micro-review, we describe the Cu(II) binding to several forms of amyloid-β peptides, the peptides involved in Alzheimer's disease. It has indeed been shown that in addition to the "full-length" peptide originating from the precursor protein after cleavage at position 1, several other shorter peptides do exist in large proportion and may be involved in the disease as well. Cu(II) binding to amyloid-β peptides is one of the key interactions that impact both the aggregating properties of the amyloid peptides and the Reactive Oxygen Species (ROS) production, two events linked to the etiology of the disease...
January 10, 2018: European Journal of Inorganic Chemistry
Nicolas A Johnson, Samuel R Wolfe, Humayun Kabir, Gabriel A Andrade, Glenn P A Yap, Zachariah M Heiden, James G Moberly, Mark F Roll, Kristopher V Waynant
Redox-active ligands lead to ambiguity in often clearly defined oxidation states of both the metal centre and the ligand. The arylazothioformamide (ATF) ligand class represents a redox-active ligand with three possible redox states (neutral, singly reduced, and doubly reduced). ATF-metal interactions result in strong colorimetric transitions allowing for the use of ATFs in metal detection and/or separations. While previous reports have discussed dissolution of zerovalent metals, the resulting oxidation states of coordination complexes have proved difficult to interpret through X-ray crystallographic analysis alone...
December 22, 2017: European Journal of Inorganic Chemistry
Jia Li, Atanu Banerjee, Debra R Preston, Brian J Shay, Amitiva Adhikary, Michael D Sevilla, Reza Loloee, Richard J Staples, Ferman A Chavez
We previously reported the spin-crossover (SC) properties of [FeII (tacn)2 ](OTf)2 ( 1 ) (tacn = 1,4,7-triazacyclononane) [ Eur. J. Inorg. Chem. 2013 , 2115]. Upon heating under dynamic vacuum, 1 undergoes oxidation to generate a low spin iron(III) complex. The oxidation of the iron center was found to be facilitated by initial oxidation of the ligand via loss of an H atom. The resulting complex was hypothesized to have the formulation [FeIII (tacn)(tacn-H)](OTf)2 ( 2 ) where tacn-H is N -deprotonated tacn...
December 15, 2017: European Journal of Inorganic Chemistry
Marianne E Burnett, Bokola Adebesin, Alexander M Funk, Zoltan Kovacs, A Dean Sherry, Levi A Ekanger, Matthew J Allen, Kayla N Green, S James Ratnakar
The Eu3+/2+ redox couple provides a convenient design platform for responsive p O2 sensors for magnetic resonance imaging (MRI). Specifically the Eu2+ ion provides T 1w contrast enhancement under hypoxic conditions in tissues, whereas, under normoxia, the Eu3+ ion can produce contrast from chemical exchange saturation transfer in MRI. The oxidative stability of the Eu3+/2+ redox couple for a series of tetraaza macrocyclic complexes was investigated in this work using cyclic voltammetry. A series of Eu-containing cyclen-based macrocyclic complexes revealed positive shifts in the Eu3+/2+ redox potentials with each replacement of a carboxylate coordinating arm of the ligand scaffold with glycinamide pendant arms...
November 24, 2017: European Journal of Inorganic Chemistry
Zohreh Hashami, Andre F Martins, Alexander M Funk, Veronica Clavijo Jordan, Stéphane Petoud, Svetlana V Eliseeva, Zoltan Kovacs
In this work, we describe a novel DOTA (1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid) based ligand with a chromophoric tropone coordinating sidearm ( 1 ). Ln3+ complexes of 1 have one inner sphere water molecule. The r1 relaxivity of Gd 1 is similar to that of the commercial Gd-based MRI agents. The neutral O-donor atom of the tropone moiety slows down the water exchange rate by a factor of 3 compared to GdDOTA. In addition, Nd 1 and Yb 1 complexes exhibit significant NIR emission in aqueous solutions indicating that the tropone unit is an efficient sensitizer for these Ln3+ -ions...
November 23, 2017: European Journal of Inorganic Chemistry
Mehdi Elsayed Moussa, Martin Fleischmann, Eugenia V Peresypkina, Luis Dütsch, Michael Seidl, Gabor Balázs, Manfred Scheer
The reactions of the tetrahedral diphosphorus [Cp2Mo2(CO)4(η(2)-P2)] (1; Cp = C5H5) complex with Ag[Al{OC(CF3)3}4] (AgTEF) (A) and Ag[FAl{OC(C6F5)(C6F10)}3] (AgFAl) (B) were studied. The first reaction led to the formation of the [Ag2(η(2)-1)2(η(1):η(1)-1)2][TEF]2 (2) dimer and the [Ag2(η(1):η(1)-1)3] n [TEF]2n (3) coordination polymer, whereas the second reaction afforded the [Ag2(η(1):η(1)-1)2(η(1)-CH2Cl2)2(η(2)-C7H8)2][FAl]2 (4) or the [Ag2(η(2)-1)2(η(1):η(1)-1)2][FAl]2 (5) dimer and the [Ag2(η(1):η(1)-1)4] n [FAl]2n (6) coordination polymer...
July 7, 2017: European Journal of Inorganic Chemistry
Michaela R Carlson, Ryan Gilbert-Wilson, Danielle R Gray, Joyee Mitra, Thomas B Rauchfuss, Casseday P Richers
The reaction of Fe2 (pdt)(CO)6 with two equivalents of Ph2 PC6 H4 NH2 (PNH2 ) affords the amido hydride HFe2 (pdt)(CO)2 (PNH2 )(PNH) {[H 1 H]0 , pdt2- = CH2 (CH2 S- )2 }. Isolated intermediates in this conversion include Fe2 (pdt)(CO)5 -(κ1 -PNH2 ) and Fe2 (pdt)(CO)4 (κ2 -PNH2 ). X-ray crystallographic analysis of [H 1 H]0 shows that the chelating amino/amido-phosphine ligands occupy trans -dibasal positions. The 31 P NMR spectrum indicates that [H 1 H]0 undergoes rapid proton exchange between the amido and amine centers...
July 7, 2017: European Journal of Inorganic Chemistry
Dmytro Havrylyuk, David K Heidary, Leona Nease, Sean Parkin, Edith C Glazer
Ruthenium complexes capable of light-triggered cytotoxicity are appealing potential prodrugs for photodynamic therapy (PDT) and photoactivated chemotherapy (PACT). Two groups of Ru(II) polypyridyl complexes with 2-(2-pyridyl)-benzazole ligands were synthesized and investigated for their photochemical properties and anticancer activity to compare strained and unstrained systems that are likely to have different biological mechanisms of action. The structure-activity relationship was focused on the benzazole core bioisosterism and replacement of coligands in Ru(II) complexes...
March 27, 2017: European Journal of Inorganic Chemistry
Mehdi Elsayed Moussa, Bianca Attenberger, Martin Fleischmann, Andrea Schreiner, Manfred Scheer
The three-component reaction of the tetrahedral diphosphorus complex [Cp2Mo2(CO)4(η(2)-P2)] (1), with Ag[BF4] (2) in the presence of 2,2'-bipyrimidine (3) leads to the formation of the two novel two-dimensional networks 4 and 5. Compound 4 is a new two-dimensional organometallic-organic hybrid polymer, while derivative 5 represents a unique two-dimensional organometallic-inorganic-organic hybrid polymer. These results show the possibility of synthesizing a new class of coordination polymers, which could not be obtained from two-component reactions with organic molecules in addition of metal ions...
October 2016: European Journal of Inorganic Chemistry
Sarina M Bellows, William W Brennessel, Patrick L Holland
This contribution explores the influences of incorporating electron-withdrawing CF3 and halide groups into β-diketiminate iron complexes of tetrazene and isocyanide. The synthesis of a new halogenated β-diketimine (L(CF3,Cl)H) was accomplished via two different methods, including a novel microwave-assisted synthesis that improves the yield of the difficult condensation. Treatment of an iron(II) complex of this ligand with reductant and azide gives two diiron complexes with novel tetrazenes as bridging ligands...
July 2016: European Journal of Inorganic Chemistry
Hannah E Colmer, Charles G Margarit, Jeremy M Smith, Timothy A Jackson, Joshua Telser
Six-coordinate Mn(III) complexes are typically high-spin (S = 2), however, the scorpionate ligand, both in its traditional, hydridotris(pyrazolyl)borate form, Tp(-) and Tp*(-) (the latter with 3,5-dimethylpyrazole substituents) and in an aryltris(carbene)borate (i.e., N-heterocyclic carbene, NHC) form, [Ph(MeIm)3B](-), (MeIm = 3-methylimidazole) lead to formation of bis(scorpionate) complexes of Mn(III) with spin triplet ground states; three of which were investigated herein: [Tp2Mn]SbF6 (1SBF6), [Tp*2Mn]SbF6 (2SBF6), and [{Ph(MeIm)3B}2Mn]CF3SO3 (3CF3SO3)...
June 2016: European Journal of Inorganic Chemistry
Peihua Zhao, Danielle L Gray, Thomas B Rauchfuss
The photochemical reaction of Fe2(S2)(CO)6 and Ph2CS affords the perthiolate Fe2(S3CPh2)(CO)6 (1) in good yield. As confirmed crystallographically, 1 contains a previously elusive perthiolate ligand. The related reaction of Fe2(S2)(CO)5-(PPh3) and Ph2CS gave Fe2(S3CPh2)(CO)5(PPh3). Although Fe3S2(CO)9 and Ph2CS failed to efficiently give Fe2(S2CPh2)(CO)6, this compound could be prepared by desulfurization of 1 using PPh3.
June 2016: European Journal of Inorganic Chemistry
Claudia Heindl, Sabine Reisinger, Christoph Schwarzmaier, Lena Rummel, Alexander V Virovets, Eugenia V Peresypkina, Manfred Scheer
Phosphaferrocenes in combination with coinage metal salts proved to be excellent building blocks in supramolecular chemistry for the buildup of oligomeric and polymeric assemblies. The synthesis of a series of novel phosphaferrocenes containing the 1,3-P2C3 iPr3 and/or the 1,2,4-P3C2 iPr2 ligand is described herein. The self-assembly processes of the 1,3-diphospha-, 1,2,4-triphospha-, and 1,1',2,3',4-pentaphosphaferrocenes with Cu(I) halides led to the formation of 1D or 2D polymers. With [Cp*Fe(η(5)-P2C3 iPr3)] (Cp* = η(5)-C5Me5), infinite chains are formed, whereas with [(η(5)-P3C2 iPr2)Fe(η(5)-P2C3 iPr3)] 1D ladderlike structures are obtained...
February 2016: European Journal of Inorganic Chemistry
Andrew R Jupp, Michael B Geeson, John E McGrady, Jose M Goicoechea
A synthesis of the 2-phosphathioethynolate anion, PCS(-), under ambient conditions is reported. The coordination chemistry of PCO(-), PCS(-) and their nitrogen-containing congeners is also explored. Photolysis of a solution of W(CO)6 in the presence of PCO(-) [or a simple ligand displacement reaction using W(CO)5(MeCN)] affords [W(CO)5(PCO)](-) (1). The cyanate and thiocyanate analogues, [W(CO)5(NCO)](-) (2) and [W(CO)5(NCS)](-) (3), are also synthesised using a similar methodology, allowing for an in-depth study of the bonding properties of this family of related ligands...
February 2016: European Journal of Inorganic Chemistry
Benjamin D Neisen, Pavlo Solntsev, Mohammad R Halvagar, William B Tolman
Reaction of a macrocyclic ligand precursor comprising two bis(carboxamido)pyridine units (H4L4) connected by ethylene linkers with NMe4OH and CuX2 (X = Cl, OAc, or OTf) yielded monocopper complexes [NMe4][(H2L4)Cu(X)] (X = Cl (3), OAc (4), or OH (5)), in contrast to previous work using a related ligand with ortho-phenylene linkers wherein dicopper compounds were isolated. X-ray structures of the complexes revealed hydrogen bonding from the free carboxamide N-H groups in the doubly protonated form of the ligand (H2L4(-) ) to the monodentate fourth ligand coordinated to the Cu(II) ion...
December 2015: European Journal of Inorganic Chemistry
Sonja Herres-Pawlis, Roxana Haase, Pratik Verma, Alexander Hoffmann, Peng Kang, T Daniel P Stack
A series of new hybrid peralkylated-amine-guanidine ligands based on a 1,3-propanediamine backbone and their Cu-O2 chemistry is reported. The copper(I) complexes react readily with O2 at low temperatures in aprotic solvents with weakly coordinating anions to form exclusively bis(μ-oxo) dicopper species (O). Variation of the substituents on each side of the hybrid bidentate ligand highlights that less sterically demanding amine and guanidine substituents increase not only the thermal stability of the formed O cores but enhance inner-sphere phenolate hydroxylation pathways...
November 2015: European Journal of Inorganic Chemistry
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