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Dalton Transactions: An International Journal of Inorganic Chemistry

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https://read.qxmd.com/read/30778497/a-new-approach-to-enhancing-the-co-2-capture-performance-of-defective-uio-66-via-post-synthetic-defect-exchange
#1
Athanasios Koutsianos, Ewa Kazimierska, Andrew R Barron, Marco Taddei, Enrico Andreoli
Zirconium-based metal-organic frameworks (Zr-MOFs) are a subclass of MOFs known for their remarkable stability, especially in the presence of water. This makes them extremely attractive for practical applications, including CO2 capture from industrial emission sources; however, the CO2 adsorption capacity of Zr-MOFs is moderate compared to that of the best performing MOFs reported to date. Functionalization of Zr-MOFs with amino groups has been demonstrated to increase their affinity for CO2. In this work, we assessed the potential of post-synthetic defect exchange (PSDE) as an alternative approach to introduce amino functionalities at missing-cluster defective sites in formic acid modulated UiO-66...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778494/catalytic-intramolecular-hydroamination-of-aminoallenes-using-titanium-complexes-of-chiral-tridentate-dianionic-imine-diol-ligands
#2
Fanrui Sha, Benjamin S Mitchell, Christopher Z Ye, Chase S Abelson, Eric W Reinheimer, Pierre LeMagueres, Joseph D Ferrara, Michael K Takase, Adam R Johnson
Alkylation of d- or l-phenylalanine or valine alkyl esters was carried out using methyl or phenyl Grignard reagents. Subsequent condensation with salicylaldehyde, 3,5-di-tert-butylsalicylaldehyde, or 5-fluorosalicylaldehyde formed tridentate, X2L type, Schiff base ligands. Chiral shift NMR confirmed retention of stereochemistry during synthesis. X-ray crystal structures of four of the ligands show either inter- or intramolecular hydrogen bonding interactions. The ligands coordinate to the titanium reagents Ti(NMe2)4 or TiCl(NMe2)3 by protonolysis and displacement of two equivalents of HNMe2...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778490/a-high-entropy-b-4-hfmo-2-tati-c-and-sic-ceramic-composite
#3
Hanzhu Zhang, Daniel Hedman, Peizhong Feng, Gang Han, Farid Akhtar
A multicomponent composite of refractory carbides, B4C, HfC, Mo2C, TaC, TiC and SiC, of rhombohedral, face-centered cubic (FCC) and hexagonal crystal structures is reported to form a single phase B4(HfMo2TaTi)C ceramic with SiC. The independent diffusion of the metal and nonmetal atoms led to a unique hexagonal lattice structure of the B4(HfMo2TaTi)C ceramic with alternating layers of metal atoms and C/B atoms. In addition, the classical differences in the crystal structures and lattice parameters among the utilized carbides were overcome...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778461/a-molecular-noble-metal-free-system-for-efficient-visible-light-driven-reduction-of-co-2-to-co
#4
Lingjing Chen, Yanfei Qin, Gui Chen, Mingya Li, Lirong Cai, Yongfu Qiu, Hongbo Fan, Marc Robert, Tai-Chu Lau
A new pentadentate quinoline-pyridine ligand and its iron (1), cobalt (2) and nickel (3) complexes have been synthesized and characterized. The iron complex exhibits excellent photocatalytic activity towards CO2-to-CO conversion with a TON(CO) of 544 and a selectivity of 99.3% using the commercially available organic dye purpurin as the photosensitiser and BIH as the electron donor. In contrast, the cobalt and nickel complexes result in very low activity for CO production with a TON of only 8 and 15, respectively...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778458/-diphenylphosphino-alkylaldehyde-affords-hydride-or-alkyl-diphenylphosphino-alkylacyl-rhodium-iii-or-diphenylphosphino-alkylester-complexes-theoretical-and-experimental-diastereoselectivity
#5
Susan Azpeitia, Montserrat Barquín, Claudio Mendicute-Fierro, Miguel A Huertos, Antonio Rodríguez-Diéguez, Jose M Seco, Eider San Sebastian, Lourdes Ibarlucea, María A Garralda
The reaction of [RhCl(COD)]2 (COD = 1,5-cyclooctadiene) with racemic PPh2(CH(Ph)CH2CHO) and pyridine (py) led to the oxidative addition of the aldehyde, and a single geometric isomer of [RhHCl(PPh2(CH(Ph)CH2CO))(py)2] (1), with hydride trans to chloride, was obtained as a mixture of two diastereomers in a 95 : 5 ratio; this was in agreement with density functional theory (DFT) calculations. In a chloroform solution, the exchange of hydride by chloride yielded [RhCl2(PPh2(CH(Ph)CH2CO))(py)2] (2) as a mixture of a kinetically preferred species, trans-py-2a, and two diastereomers, cis-Cl-2b' and cis-Cl-2b, with cis pyridines and a chloride trans to acyl; as predicted by the DFT calculations, the latter was the major species...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778457/europium-and-ytterbium-complexes-with-o-iminoquinonato-ligands-synthesis-structure-and-magnetic-behavior
#6
Svetlana V Klementyeva, Anton N Lukoyanov, Mikhail Yu Afonin, Max Mörtel, Anton I Smolentsev, Pavel A Abramov, Alyona A Starikova, Marat M Khusniyarov, Sergey N Konchenko
Complexes of divalent ytterbium (1) and europium (2) with a dianionic o-amidophenolate ligand were prepared by both the direct reduction of 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone (dpp-IQ) and the salt metathesis reaction of potassium o-amidophenolate with LnI2 (Ln = Yb, Eu). Oxidation of o-amidophenolates 1, 2 with one equivalent of dpp-IQ as well as the salt metathesis reaction of potassium o-iminosemiquinolate with LnI2 afforded ligand mixed-valent o-iminosemiquinonato-amidophenolato complexes of trivalent ytterbium (3) and europium (4)...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778456/hexavacant-%C3%AE-dawson-type-phosphotungstates-supporting-an-edge-sharing-bis-square-pyramidal-o-2-m-%C3%AE-3-o-2-%C3%AE-oac-mo-2-core-m-mn-2-co-2-ni-2-cu-2-or-zn-2
#7
Kosuke Suzuki, Takuo Minato, Naoto Tominaga, Ichiro Okumo, Kentaro Yonesato, Noritaka Mizuno, Kazuya Yamaguchi
In aqueous media, the introduction of additional metal species into polyoxometalates (POMs) with multiple vacant sites, such as a hexavacant Dawson-type phosphotungstate, which is of interest for the synthesis of novel metal oxide clusters, is generally difficult because they easily undergo self-condensation and/or structural decomposition. In this study, we succeeded in developing a novel synthetic method to obtain metal-substituted γ-Dawson-type phosphotungstate monomers by introducing metal species into an organic solvent-soluble lacunary phosphotungstate, TBA4H10[α-P2W12O48] (I) (TBA = tetra-n-butylammonium), in organic media...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778455/synthesis-of-new-mn-19-analogues-and-their-structural-electrochemical-and-catalytic-properties
#8
Elodie Chevallot-Beroux, Ayuk M Ako, Wolfgang Schmitt, Brendan Twamley, Joseph Moran, Boudon Corinne, Laurent Ruhlmann, Samir Mameri
We report the synthesis and structural characterisation of new Mn19 and Mn18M analogues, [MnIII12MnII7(μ4-O)8(μ3-OCH3)2(μ3-Br)6(HLMe)12(MeOH)6]Br2 (2) and [MnIII12MnII6Sr(μ4-O8(μ3-Cl)8(HLMe)12(MeCN)6]Cl2 cluster (3), where H3LMe is 2,6-bis(hydroxymethyl)-p-cresol. The electrochemistry of 2 and 3 has been investigated and their activity as catalysts in the oxidation of benzyl alcohol has been evaluated. Selective oxidation of benzyl alcohol to benzaldehyde by O2 was achieved using 1 mol% of catalyst with conversions of 74% (2) and 60% (3) at 140 °C using TEMPO as a co-catalyst...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778453/in-situ-topotactic-formation-of-2d-2d-direct-z-scheme-cu-2-s-zn-0-67-cd-0-33-s-in-plane-intergrowth-nanosheet-heterojunctions-for-enhanced-photocatalytic-hydrogen-production
#9
Jingjing Shi, Shuangde Li, Fengming Wang, Lina Gao, Yanmei Li, Xiaorang Zhang, Jun Lu
Zinc cadmium sulfide solid solution (ZnxCd1-xS) photocatalysts have received significant attention in energy and environmental applications because of their wide and strong visible light absorption range. However, the high photogenerated electron-hole pair recombination rate is an innate problem for their application. In this study, Cu2S/Zn0.67Cd0.33S (CZCS) nanosheet heterojunctions were fabricated by the in situ topotactic hydrothermal transformation of CuZnCdAl layered double hydroxide (LDH) precursors. Structural and morphological characterization indicated that the CZCS nanosheets were 2D/2D atomic-level in-plane heterojunctions with matched crystalline orientation because of their intergrowth structure originating from the topotactic sulfurization of CuZnCdAl LDH precursors...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778451/structure-of-sirohydrochlorin-ferrochelatase-sirb-the-last-of-the-structures-of-the-class-ii-chelatase-family
#10
Takashi Fujishiro, Yukino Shimada, Ryosuke Nakamura, Miho Ooi
The crystal structure of Bacillus subtilis SirB, which catalyses the insertion of Fe2+ into the substrate sirohydrochlorin (SHC) in siroheme biosynthesis, is reported herein as the last of the structures of class II chelatases. The structure of SirB with Co2+ showed that the active site of SirB is located at the N-terminal domain with metal-binding amino acid residues His10, Glu43, and His76, which was also predicted for CbiX, but is distinct from the C-terminal active sites of CbiK and HemH. The biosynthetic model reactions using SirB, Co2+ and uroporphyrin I or protoporphyrin IX as a SHC analogue revealed that SirB showed chelatase activity for uroporphyrin I, but not for protoporphyrin IX...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778450/phenothiazines-and-phenoxazines-as-electron-transfer-mediators-for-ferritin-iron-release
#11
Prashanth Kumar Koochana, Abhinav Mohanty, Biswamaitree Subhadarshanee, Suresh Satpati, Rajat Naskar, Anshuman Dixit, Rabindra K Behera
Intracellular ferritin stores iron as ferrihydrite and releases it for various cellular metabolic activities. The reductive approach, one of the possible mechanisms of iron mobilization from ferritin nanocages, requires electron transfer (ET) from reducing agent(s) to the protein encapsulated iron. In vitro, the rate of ET from the physiological reducing agent, NADH, to mineralized ferritin is very slow resulting in a smaller amount of iron release. Therefore, medically relevant phenothiazine (TH/MB/MG/TDB) and phenoxazine (BCB/CRV/NB) dyes were used as ET mediators to facilitate the electron relay and to evaluate their iron releasing ability from ferritin...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30778449/selective-synthesis-of-benzoquinones-over-cu-ii-containing-propylsalicylaldimine-functionalized-mesoporous-solid-catalysts
#12
Manickam Selvaraj, Mohammed A Assiri
The major product, 2,3,5-trimethyl-1,4-benzophenone (TMB[double bond, length as m-dash]O), was synthesised by an eco-friendly liquid-phase oxidation of 2,3,6-trimethylphenol (TMP-OH) over Cu(ii)-containing propylsalicylaldimine (CSA) functionalized mesoporous solid catalysts, namely, CSASBA-15(0.2), CSASBA-15(0.1) and CSAMCM-41(0.2), synthesized using various amounts of copper in a simple post-grafting method using different mesoporous silica materials, e.g., thick-silica walled SBA-15 and thin-silica walled MCM-41...
February 19, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30776044/a-biocompatible-redox-mri-probe-based-on-a-mn-ii-mn-iii-porphyrin
#13
Sara M A Pinto, Mário J F Calvete, Mariana E Ghica, Sérgio Soler, Iluminada Gallardo, Agnès Pallier, Mariana B Laranjo, Ana M S Cardoso, M Margarida C A Castro, Christopher M A Brett, Mariette M Pereira, Éva Tóth, Carlos F G C Geraldes
For the development of redox responsive MRI probes based on the MnIII/MnII couple, stable complexation of both reduced and oxidized forms of the metal ion and appropriate tuning of the redox potential in the biologically relevant range are key elements. The water soluble fluorinated Mn-porphyrin derivative Mn-3 satisfies both requirements. In aqueous solutions, it can reversibly switch between MnIII/MnII oxidation states. In the presence of ascorbic acid or β-mercaptoethanol, the MnIII form undergoes reduction, which is slowly but fully reversed in the presence of air oxygen...
February 18, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30776043/new-pt%C3%A2-m-m-ag-or-tl-complexes-based-on-anionic-cyclometalated-pt-ii-complexes
#14
David Campillo, Úrsula Belío, Antonio Martín
Anionic cyclometalated complexes (NBu4)[Pt(CNC)X] (X = Cl (1), CN (2), or S-2py (pyridine-2-thiolate) (3); -CNC- = 2,6-di(phen-2-ide)-pyridine) have been used as precursors in the synthesis of heteropolynuclear Pt-Ag or Pt-Tl complexes containing donor-acceptor metal-metal bonds. Their reaction with AgClO4 or [Ag(OClO3)(PPh3)] produces complexes in which the nuclearity and structure seem to be determined by the ability of the ligand X to form bridges between the metals. Thus, the characteristic linear bridging of the cyano ligand leads to the formation of an octanuclear [{Pt(CNC)(μ-CN)}4Ag4] (4) or tetranuclear [{Pt(CNC)(μ-CN)}2{Ag(PPh3)}2] (6) complex, with CN bridges between different "Pt-Ag" units...
February 18, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30776039/emergence-of-complex-chiral-coordination-clusters-cuna-12-by-using-multiple-ligands-under-oxidizing-conditions
#15
Wei Meng, Hongfang Ye, Shuai Liu, Feng Xu, Weijian Xu
Two chiral coordination clusters {CuII48Na12}, which can only be revealed by synchrotron single-crystal X-ray diffraction, were assembled unexpectedly from a system resembling the long-studied Fehling's solution. As the intricate structures themselves indicate, the ingenuity of using multiple ligands should inspire new strategies to fabricate new compounds.
February 18, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30776035/efficient-and-irreversible-capture-of-strontium-ions-from-aqueous-solution-using-metal-organic-frameworks-with-ion-trapping-groups
#16
Wanjun Mu, Shenzhen Du, Xingliang Li, Qianhong Yu, Rui Hu, Hongyuan Wei, Yuchuan Yang, Shuming Peng
Efficient and irreversible capture of radioactive nuclides is an important environmental protection task when disposing of nuclear wastewater. This paper uses an "ion trapping" concept to design an efficient adsorbent based on a metal-organic framework (MOF), for removal of radioactive strontium from nuclear wastewater. Two functionalized MOFs were achieved by the introduction of sulfate or oxalate into the pore structure of MOF-808, giving MOF-808-SO4 and MOF-808-C2O4, respectively. These functionalized MOF-808 materials exhibit excellent ability to remove Sr2+ from acidic solution due to their particular trapping action, with the maximum Sr2+ adsorption capacities of 176...
February 18, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30776033/tailored-high-cycling-performance-in-a-solid-polymer-electrolyte-with-perovskite-type-li-0-33-la-0-557-tio-3-nanofibers-for-all-solid-state-lithium-ion-batteries
#17
Kang-Qiang He, Jun-Wei Zha, Peng Du, Samson Ho-Sum Cheng, Chen Liu, Zhi-Min Dang, Robert K Y Li
Solid polymer electrolytes (SPEs) have drawn considerable attention owing to their reliable safety performance, electrochemical stability and exceptional flexibility, which make them superior to conventional liquid electrolytes. Here, we report a novel composite electrolyte which is composed of homogeneously dispersed Li ion-conducting Li0.33La0.557TiO3 (LLTO) nanowires in a poly(ethylene oxide) (PEO)/LiClO4 matrix. It is demonstrated that only 3 wt% LLTO nanofibers are needed for the optimal performance of SPEs...
February 18, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30775764/zwitterionic-and-cationic-half-sandwich-iridium-iii-ruthenium-ii-complexes-bearing-sulfonate-groups-synthesis-characterization-and-their-different-biological-activities
#18
Yanjing Yang, Xingxing Ge, Lihua Guo, Teng Zhu, Zhenzhen Tian, Hairong Zhang, Qing Du, Hongwei Peng, Wenli Ma, Zhe Liu
Previous studies on the neutral and cationic half-sandwich iridium(iii) and ruthenium(ii) complexes showed that the charge and the substitution pattern of the bidentate ligands, as well as the nature of the accompanying counteranion have a significant effect on their biological activities. In this contribution, a series of zwitterionic and cationic half-sandwich iridium(iii) and ruthenium(ii) complexes containing sulfonate groups have been prepared and characterized. The different locations of counteranions between these two kinds of complexes exert great influence on the cytotoxic activity towards cancer cells...
February 18, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30775761/bis-salophen-palladium-complex-immobilized-on-fe-3-o-4-sio-2-nanoparticles-as-a-highly-active-and-durable-phosphine-free-catalyst-for-heck-and-copper-free-sonogashira-coupling-reactions
#19
Ali Reza Sardarian, Milad Kazemnejadi, Mohsen Esmaeilpour
New Fe3O4@SiO2 core-shell superparamagnetic nanoparticles functionalized by a bis-salophen Schiff base Pd complex were synthesized and employed as an efficient magnetic nanocatalyst in the Heck and Sonogashira cross coupling reactions. The synthesized nanostructures were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), dynamic light scattering (DLS), energy dispersive X-ray analysis (EDX), X-ray photoelectron spectroscopy (XPS), elemental analysis (CHN), cyclic voltammetry (CV), Brunauer-Emmett-Teller analysis (BET), and UV-vis spectroscopy...
February 18, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
https://read.qxmd.com/read/30775757/telluraporphyrinoids-an-interesting-class-of-core-modified-porphyrinoids
#20
A Alka, Vijayendra S Shetti, Mangalampalli Ravikanth
Core-modified porphyrinoids or heteroporphyrinoids are a class of porphyrinoids in which one or more core pyrrole nitrogen atom(s) of the macrocycles are replaced predominantly by group-16 atoms such as O, S, Se, and Te. Telluraporphyrinoids are distinct and interesting from the rest of the chalcogenide atom(s) containing porphyrinoids owing to the larger size of Te and the consequent properties arising from it. The telluraporphyrinoid chemistry is only sporadically investigated and the developments are rather slow compared to the other lighter group-16 atom containing porphyrinoids...
February 18, 2019: Dalton Transactions: An International Journal of Inorganic Chemistry
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