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Inorganic Chemistry

Jesús A Luque-Urrutia, Albert Poater
The hydrogenation of nitrous oxide by PNP pincer ruthenium complexes supposes a promising way to functionalize a hazardous gas and reduce the greenhouse effect, generating dinitrogen and water. Here, by DFT calculations we describe not only the whole mechanism for such a green transformation but we unravel the fundamental role of water, without which the reaction could not go forward. Water assists mandatorily in the H transfer to generate the hydroxyl group together with the release of dinitrogen.
November 17, 2017: Inorganic Chemistry
Ram Krishna Hona, Ashfia Huq, Farshid Ramezanipour
The ability to control the electrical conductivity of solid-state oxides using structural parameters has been demonstrated. A correlation has been established between the electrical conductivity and structural order in a series of oxygen-deficient perovskites using X-ray and neutron diffraction, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and electrical conductivity studies at a wide temperature range, 25-800 °C. The crystal structure of CaSrFeCoO6-δ has been determined, and its stark contrast to Ca2FeCoO6-δ and Sr2FeCoO6-δ has been demonstrated...
November 17, 2017: Inorganic Chemistry
Gouri Chakraborty, Sanjay K Mandal
Utilizing flexible bis(tridentate)polypyridyl ligands, the two new luminescent 2D metal organic frameworks {Zn2(tpbn)(2,6-NDC)2}n (1) and {[Zn2(tphn)(2,6-NDC)2]·4H2O}n (2), where tpbn = N,N',N″,N‴-tetrakis(2-pyridylmethyl)-1,4-diaminobutane, tphn = N,N',N″,N‴-tetrakis(2-pyridylmethyl)-1,6-diaminohexane, and 2,6-H2NDC = 2,6-naphthalenedicarboxylic acid, have been isolated in good yields under solvothermal conditions. Their solid-state molecular structures have been determined by single-crystal X-ray diffractometry...
November 17, 2017: Inorganic Chemistry
Nicholas M Hein, Fraser S Pick, Michael D Fryzuk
A low-coordinate iron hydride complex bearing an unsymmetrical NpN (enamido-phosphinimine) ligand scaffold was synthesized and fully characterized. Insertion reactivity with azobenzene, 3-hexyne, and 1-azidoadamantane was explored, and the isolated products were analogous to previously reported β-diketiminate iron hydride insertion products. Surprisingly, the NpN iron hydride displays unprecedented reactivity toward hexafluorobenzene, affording an NpN iron fluoride complex and pentafluorobenzene as products...
November 16, 2017: Inorganic Chemistry
Saptarshi Biswas, Shuwen Ma, Stefano Nuzzo, Brendan Twamley, Andrew T Russell, James A Platts, František Hartl, Robert J Baker
A series of complexes [Et4N][Ln(NCS)4(H2O)4] (Ln = Pr, Tb, Dy, Ho, Yb) have been structurally characterized, all showing the same structure, namely a distorted square antiprismatic coordination geometry, and the Ln-O and Ln-N bond lengths following the expected lanthanide contraction. When the counterion is Cs(+), a different structural motif is observed and the eight-coordinate complex Cs5[Nd(NCS)8] isolated. The thorium compounds [Me4N]4[Th(NCS)7(NO3)] and [Me4N]4[Th(NCS)6(NO3)2] have been characterized, and high coordination numbers are also observed...
November 16, 2017: Inorganic Chemistry
K Michael Schäfer, Leonie Reinders, Jan Fiedler, Mark R Ringenberg
Recently we had reported the noninnocent behavior of 1,1'-bis(diphenylphosphino)ferrocene (dppf) in Fe(CO)3dppf [Ringenberg et al., Inorg. Chem., 2017, 56, 7501]. Moving to the left in the periodic table, HMn(CO)3(dRpf) where dRpf = dppf (1H) and 1,1'-bis(diisopropylphosphino)ferrocene (dippf) (2H) were synthesized. The hydride ligand was removed by protonation with [(Et2O)2H][B(Ar(F))4] ([B(Ar(F))4](-) = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate), resulting in the rapid evolution of H2 followed by the formation of an Fe→Mn interaction...
November 16, 2017: Inorganic Chemistry
P Modak, Ashok K Verma
A study of the bonding and electronic properties of intermetallics under pressure is crucial in the design and development of novel materials for useful applications. These properties are largely controlled by the underlying crystal structures. Here we investigated the high-pressure structural behavior of PtIn2 using crystal structure search calculations, which efficiently combine evolutionary algorithms and state-of-the-art density functional theory. Three new crystal structures, namely, Fe2B-type (I4/mcm, Z = 2), cotunnite-type (Pnma, Z = 4), and monoclinic (C2/m, Z = 2), are proposed at about 9...
November 16, 2017: Inorganic Chemistry
Xiaoxiao Zhao, Yunpeng Duan, Fei Yang, Wei Wei, Yanqing Xu, Changwen Hu
One-pot mechanochemical synthesis was demonstrated to be an efficient strategy to synthesize host-guest POM⊂rho-ZIF complexes (POM = polyoxometalate; rho-ZIF = zeolitic imidazolate framework with rho topology) with high crystallinity. In this work, the metastable rho-ZIF with large interior cavities and windows was used as host matrix for encapsulating and immobilizing bulky guest molecules with high loading efficiency and chemical stability. As novel catalysts, POM⊂rho-ZIF complexes were found effective for the selective oxidation of a series of sulfides to sulfoxides...
November 16, 2017: Inorganic Chemistry
Mrinal Bhunia, Gonela Vijaykumar, Debashis Adhikari, Swadhin K Mandal
Herein we report the synthesis of two complexes of potassium employing strongly nucleophilic carbenes, such as cyclic "(alkyl)(amino)carbene (cAAC) and abnormal N-heterocyclic carbene (aNHC). Both complexes are dimeric in the solid state and the two potassium centers are bridged by trimethylsilylamide. In these complexes, the carbene- - -K interaction is predominantly electrostatic in character, which has been probed thoroughly by NBO and AIM analyses. Indeed, the delocalization energy of the cAAC lone pair calculated from the second-order perturbation theory was only 5...
November 16, 2017: Inorganic Chemistry
Adam Grzelak, Jakub Gawraczyński, Tomasz Jaroń, Dominik Kurzydłowski, Armand Budzianowski, Zoran Mazej, Piotr J Leszczyński, Vitali B Prakapenka, Mariana Derzsi, Viktor V Struzhkin, Wojciech Grochala
A combined experimental-theoretical study of silver(I) and silver(II) fluorides under high pressure is reported. For Ag(I), the CsCl-type structure is stable to at least 39 GPa; the overtone of the IR-active mode is seen in the Raman spectrum. Its Ag(II)F2 sibling is a unique compound in many ways: it is more covalent than other known difluorides, crystallizes in a layered structure, and is enormously reactive. Using X-ray diffraction and guided by theoretical calculations (density functional theory), we have been able to elucidate crystal structures of high-pressure polymorphs of AgF2...
November 15, 2017: Inorganic Chemistry
Manar M Shoshani, Robert Beck, Xiaoping Wang, Matthew J McLaughlin, Samuel A Johnson
Tetranuclear Ni complexes were synthesized with bonding to BH, NR, and O in atypical surface-like geometries. The previously reported electron-deficient cluster [((i)Pr3P)Ni]5H6 (1) reacts with N-methylmorpholine oxide to give [((i)Pr3P)Ni]4H4(μ4-O) (2), which contains O coordinated in the center of a square-plane arrangement of Ni atoms. Reaction of 1 with benzonitrile gave the square-planar tetranuclear Ni cluster [((i)Pr3P)Ni]4H4(μ4-NCH2Ph) (3), which contains an imido donor in a square-based-pyramidal geometry...
November 15, 2017: Inorganic Chemistry
Olga N Mazaleva, Ilya N Ioffe, Fei Jin, Shangfeng Yang, Erhard Kemnitz, Sergey I Troyanov
The first example of three alternative chlorination-promoted skeletal transformation pathways in the same fullerene cage is presented. Isolated-pentagon-rule (IPR) C102(19) undergoes both Stone-Wales rotations to give non-IPR (#283794)C102Cl20 and C2 losses to form nonclassical C98 and non-IPR C96. X-ray structural characterization of the transformation products and a theoretical study of their formation pathways are reported.
November 15, 2017: Inorganic Chemistry
Mustapha Nechiche, Thierry Cabioc'h, Elad N Caspi, Oleg Rivin, Andreas Hoser, Véronique Gauthier-Brunet, Patrick Chartier, Sylvain Dubois
Ti3[Al1-δCuδ]C2 MAX phase solid solutions have been synthesized by sintering compacted Ti3AlC2-Cu composites produced by mechanical milling. Using X-ray and neutron diffraction techniques, it is demonstrated that the Cu mixing into the Al site is accompanied by lattice distortion, which leads to symmetry reduction from a hexagonal to a monoclinic structure. Such symmetry reduction likely results from this mixing through deviation of the A-site position from the special (0, 0, (1)/4) position within the P63/mmc space group of the original Ti3AlC2 structure...
November 15, 2017: Inorganic Chemistry
Nopondo N Esemoto, Andrius Satraitis, Linda Wiratan, Marcin Ptaszek
A series of a rigid meso-meso directly linked chlorin-chlorin, chlorin-bacteriochlorin, and bacteriochlorin-bacteriochlorin dyads, including free bases as well as Zn(II), Pd(II), and Cu(II) complexes, has been synthesized, and their absorption, emission, singlet oxygen ((1)O2) photosensitization, and electronic properties have been examined. Marked bathochromic shifts of the long-wavelength Qy absorption band and increase in fluorescence quantum yields in dyads, in comparison to the corresponding monomers, are observed...
November 15, 2017: Inorganic Chemistry
Dongsheng Rong, Shida Gong, Chaoyang Wang, Qiong Luo, Qian-Shu Li, Yaoming Xie, R Bruce King, Henry F Schaefer
The photochromic dithionite complex Cp*2Rh2(μ-CH2)2(μ-O2SSO2) (Cp* = η(5)-Me5C5) is of interest because it undergoes an unusual fully reversible unimolecular photochemical rearrangement to the isodithionite complex Cp*2Rh2(μ-CH2)2(μ-O2SOSO). In order to obtain more insight into these systems, a comprehensive density functional theory study has been carried out on isomeric Cp2M2(CH2)2(SO2)2 (M = Rh, Ir) derivatives. The experimentally observed rhodium complexes with coupled sulfur dioxide (SO2) units to give dithionite or isodithionite ligands are surprisingly high-energy kinetic isomers in our analysis, reflecting the need for dithionite rather than SO2 for their synthesis...
November 15, 2017: Inorganic Chemistry
Amanda R Corcos, Michael D Roy, Michelle M Killian, Stephanie Dillon, Thomas C Brunold, John F Berry
The electronic structures of the diruthenium compounds Ru2(ap)4Cl (1, ap = 2-anilinopyridinate) and Ru2(ap)4OTf (2) were investigated with UV-vis, resonance Raman, and magnetic circular dichroism (MCD) spectroscopies; SQUID magnetometry; and density functional theory (DFT) calculations. Both compounds have quartet spin ground states with large axial zero-field splitting of ∼60 cm(-1) that is characteristic of Ru2(5+) compounds having a (π*, δ*)(3) electron configuration and a Ru-Ru bond order of ∼2.5...
November 15, 2017: Inorganic Chemistry
Kai-Yu Cheng, Shi-Cheng Wang, Yu-Sheng Chen, Yi-Tsu Chan
Upon treatment with Zn(II) ions, a series of BINOL-bridged bis(phenanthroline) ligands was self-assembled into [M2L3] metallocages, which were carefully characterized by NMR spectroscopy and ESI-MS spectrometry. Among them, a racemic mixture of the BINOL-bridged bis(phenanthrolines) underwent chiral self-sorting to afford two homochiral metallocages. The narcissistic self-sorting process of the metallocages was observed in the complexation reaction of the constitutionally isomeric bis(phenanthrolines) with varying connection positions...
November 15, 2017: Inorganic Chemistry
Paul Jerabek, Beatriz von der Esch, Hubert Schmidbaur, Peter Schwerdtfeger
The stability and bonding in dinuclear group 11 metal complexes (M = Au, Ag, and Cu) in their +2 oxidation state has been investigated by quantum chemical methods. Two model complexes were selected as representatives of different bonding situations in the dinuclear M(II) complexes, a direct metal-metal bond between two ligand stabilized monomers and ligand-mediated bridged dimer system, making them interesting for a direct comparison and to study the influence of relativistic effects. Relativity substantially stabilizes the direct metal-metal bonded system obtaining the sequence in M-M bond stability Au > Ag > Cu...
November 14, 2017: Inorganic Chemistry
Xin Zhao, Cai-Zhuang Wang, Minsung Kim, Kai-Ming Ho
Fe-cluster-based crystal structures are predicted for chalcogenides Fe3X4 (X = S, Se, Te) using an adaptive genetic algorithm. Topologically different from the well-studied layered structures of iron chalcogenides, the newly predicted structures consist of Fe clusters that are either separated by the chalcogen atoms or connected via sharing of the vertex Fe atoms. Using first-principles calculations, we demonstrate that these structures have competitive or even lower formation energies than the experimentally synthesized Fe3X4 compounds and exhibit interesting magnetic and electronic properties...
November 13, 2017: Inorganic Chemistry
Chang Xu, Wan-Ying Zhang, Qiong Ye, Da-Wei Fu
Switchable materials, due to their potential applications in the fields of sensors, photonic devices, digital processing, etc., have been developed drastically. However, they still face great challenges in effectively inducing multiple molecular switching. Herein organic-inorganic hybrid compounds, an emerging class of hydrosoluble optoelectronic-active materials, welcome a new member with smart unique optical/electrical (fluorescence/dielectric) dual switches (switching ON/OFF), that is, [C5H13NBr][Cd3Br7] (1) in the form of both a bulk crystal and an ultraflexible monodirectional thin film, which simultaneously exhibits fast dielectric/fluorescent dual switching triggered by an optical/thermal/electric signal with a high signal-to-noise ratio of 35 (the highest one in the known optical/dielectric dual molecular switches)...
November 13, 2017: Inorganic Chemistry
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