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Inorganic Chemistry

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https://www.readbyqxmd.com/read/28430438/controllable-synthesis-of-lindqvist-alkoxopolyoxovanadate-clusters-as-heterogeneous-catalysts-for-sulfoxidation-of-sulfides
#1
Ji-Kun Li, Jing Dong, Chuan-Ping Wei, Song Yang, Ying-Nan Chi, Yan-Qing Xu, Chang-Wen Hu
Six alkoxohexavanadate-based Cu- or Co-POVs [Cu(dpa)(acac)(H2O)]2[V6O13(OMe)6] (1), [Cu(phen)(acac)(MeOH)]2[V6O13(OMe)6] (2), [Co(dpa)(acac)2]2[V6O13(OMe)6]·2MeOH (3), [Co(phen)(acac)2]2[V6O13(OMe)6] (4), [Cu(dpa)(acac)]2[V(IV)2V(V)4O12(OMe)7] (5), and [Cu(dpa)(acac)(MeOH)]2[V(IV)2V(V)4O11(OMe)8] (6) (POV = polyoxovanadate; dpa = 2,2'-dipyridine amine; phen = 1,10-phenanthroline; acac = acetylacetone anion) have been synthesized by controlling the reaction conditions and characterized by single-crystal X-ray diffraction and powder X-ray diffraction analyses, FT-IR spectroscopy, element analyses, and X-ray photoelectron spectroscopy...
April 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28430423/hafnium-based-contrast-agents-for-x-ray-computed-tomography
#2
Markus Berger, Marcus Bauser, Thomas Frenzel, Christoph Stephan Hilger, Gregor Jost, Silvia Lauria, Bernd Morgenstern, Christian Neis, Hubertus Pietsch, Detlev Sülzle, Kaspar Hegetschweiler
Heavy-metal-based contrast agents (CAs) offer enhanced X-ray absorption for X-ray computed tomography (CT) compared to the currently used iodinated CAs. We report the discovery of new lanthanide and hafnium azainositol complexes and their optimization with respect to high water solubility and stability. Our efforts culminated in the synthesis of BAY-576, an uncharged hafnium complex with 3:2 stoichiometry and broken complex symmetry. The superior properties of this asymmetrically substituted hafnium CA were demonstrated by a CT angiography study in rabbits that revealed excellent signal contrast enhancement...
April 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28430422/gauging-donor-acceptor-properties-and-redox-stability-of-chelating-click-derived-triazoles-and-triazolylidenes-a-case-study-with-rhenium-i-complexes
#3
Lisa Suntrup, Sinja Klenk, Johannes Klein, Sebastian Sobottka, Biprajit Sarkar
Bidentate ligands containing at least one triazole or triazolylidene (mesoionic carbene, MIC) unit are extremely popular in contemporary chemistry. One reason for their popularity is the similarities as well as differences in the donor/acceptor properties that these ligands display in comparison to their pyridine or other N-heterocyclic carbene counterparts. We present here seven rhenium(I) carbonyl complexes where the bidentate ligands contain combinations of pyridine/triazole/triazolylidene. These are the first examples of rhenium(I) complexes with bidentate 1,2,3-triazol-5-ylidene-containing ligands...
April 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28430421/flexibility-of-the-carbodiphosphorane-ph3p-2c-structural-characterization-of-a-linear-form
#4
Patrick J Quinlivan, Gerard Parkin
X-ray diffraction studies demonstrate that crystals of the carbodiphosphorane, (Ph3P)2C, obtained from solutions in benzene, exhibit a linear P-C-P interaction. This observation is in contrast to the highly bent structures that have been previously reported for this molecule, thereby providing experimental evidence that the coordination geometry at zerovalent carbon may be very flexible. Density functional theory calculations support the experimental observations by demonstrating that the energy of (Ph3P)2C varies relatively little over the range 130-180°...
April 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28429934/bi4tao8cl-nano-photocatalyst-influence-of-local-average-and-band-structure
#5
Swetha S M Bhat, Diptikanta Swain, Mikhail Feygenson, Joerg C Neuefeind, Abhishek K Mishra, Janardhan L Hodala, Chandrabhas Narayana, Ganapati V Shanbhag, Nalini G Sundaram
The average structure, local structure, and band structure of nanoparticles of photocatalyst Bi4TaO8Cl, an Aurivillius-Sillen layered material, has been studied by powder neutron Rietveld refinement, neutron pair distribution function technique, Raman scattering, and density functional theory calculations. A significant local structural deviation of nano-Bi4TaO8Cl was established in contrast to the local structure of bulk-Bi4TaO8Cl. Local structure was further supported by Raman scattering measurements. Through DFT calculations, we identify specific features in the electronic band structure that correlate lower secondary structural distortions in nano-Bi4TaO8Cl...
April 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28429933/remarkably-enhancing-green-excitation-efficiency-for-solar-energy-utilization-red-phosphors-ba2zns3-eu-2-x-co-doped-halide-ions-x-cl-br-i
#6
Tingting Luo, Yun Du, Zhongxian Qiu, Yanmei Li, Xiaofang Wang, Wenli Zhou, Jilin Zhang, Liping Yu, Shixun Lian
Eu(2+)-activated Ba2ZnS3 has been reported as a red phosphor with a broad emission band peaking at 650 nm under blue excitation for white-LED. In this study, Ba2ZnS3:Eu(2+), X(-) (X = F, Cl, Br, I) phosphors doped with halide ions were prepared by traditional high-temperature solid-state reaction. Phase identification of powders was performed by X-ray powder diffraction analysis, confirming the existence of single-phase Ba2ZnS3 crystals without dopant. The corresponding excitation spectra showed an additional broad band in the green region peaking at 550 nm when the phosphor was halogenated except by the smallest F(-)...
April 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28429931/heterobimetallic-nitrido-complexes-of-group-8-metalloporphyrins
#7
Wai-Man Cheung, Wai-Hang Chiu, Matthew de Vere-Tucker, Herman H-Y Sung, Ian D Williams, Wa-Hung Leung
Heterobimetallic nitrido porphyrin complexes with the [(L)(por)M-N-M'(LOEt)Cl2] formula {por(2-) = 5,10,15,20-tetraphenylporphyrin (TPP(2-)) or 5,10,15,20-tetra(p-tolyl)porphyrin (TTP(2-)) dianion; LOEt(-) = [Co(η(5)-C5H5){P(O)(OEt)2}3](-); M = Fe, Ru, or Os; M' = Ru or Os; L = H2O or pyridine} have been synthesized, and their electrochemistry has been studied. Treatment of trans-[Fe(TPP)(py)2] (py = pyridine) with Ru(VI) nitride [Ru(LOEt)(N)Cl2] (1) afforded Fe/Ru μ-nitrido complex [(py)(TPP)Fe(μ-N)Ru(LOEt)Cl2] (2)...
April 21, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28426230/photophysics-and-excited-state-properties-of-cyclometalated-iridium-iii-platinum-ii-and-iridium-iii-iridium-iii-bimetallic-complexes-bridged-by-dipyridylpyrazine
#8
Yang-Jin Cho, So-Yoen Kim, Chang Min Choi, Nam Joon Kim, Chul Hoon Kim, Dae Won Cho, Ho-Jin Son, Chyongjin Pac, Sang Ook Kang
We investigated the electrochemical and excited-state properties of 2,3-bis(2-pyridyl)pyrazine (dpp)-bridged bimetallic complexes, (L)2Ir-dpp-PtCl [1, L = 2-(4',6'-difluorophenyl)pyridinato-N,C(2) (dfppy); 2, L = 2-phenylpyridinato-N,C(2) (ppy)] and [(L)2Ir]2(dpp) [3, L = dfppy; 4, L = ppy] compared to monometallic complexes, (L)2Ir-dpp (5, L = dfppy; 6, L = ppy) and dpp-PtCl (dpp-Pt(II)Cl2; 7). The single-crystal X-ray crystallographic structures of 1, 3, 5, and 6 showed that 1 and 3 have approximately coplanar structures of the dpp unit, while the noncoordinated pyridine ring of dpp in 5 and 6 is largely twisted with respect to the pyrazine ring...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28426215/five-and-six-coordinated-silver-i-complexes-derived-from-2-6-pyridyl-iminodiadamantanes-sustained-release-of-bioactive-silver-toward-bacterial-eradication
#9
Jorge Jimenez, Indranil Chakraborty, Anthony M Del Cid, Pradip K Mascharak
Silver(I) complexes of two designed tridentate ligands, namely, 2,6-(pyridyl)iminoditriazaadamantane (pydTAm) and 2,6-(pyridyl)iminodiadamantane (pydAm), have been synthesized and structurally characterized. [Ag(pydTAm)2](CF3SO3) (1), the hitherto unknown mer isomer of a silver(I) octahedral complex, crystallizes in a highly symmetric body-centered cubic I4̅3m space group. Quite in contrast, the Ag(I) center in the analogous [Ag(pydAm)2](CF3SO3) (2) complex resides in a trigonal-bipyramidal geometry and crystallizes in a triclinic P1̅ space group with two crystallographically independent molecules in the asymmetric unit...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28426213/role-of-mediator-and-effects-of-temperature-on-ortho-c-n-bond-fusion-reactions-of-aniline-using-ruthenium-templates-isolation-and-characterization-of-new-ruthenium-complexes-of-the-in-situ-generated-ligands
#10
Suman K Roy, Debabrata Sengupta, Santi Prasad Rath, Tanushri Saha, Subhas Samanta, Sreebrata Goswami
In this work, ortho-C-N bond fusion reactions of aniline are followed by the use of two different ruthenium mediators. Reaction of aniline with [Ru(III)(terpy)Cl3] (terpy = 2,2':6',2″-terpyridine) resulted in a trans bis-aniline ruthenium(II) complex [1](+) which upon oxidation with H2O2 produced compound [2](+) of a bidentate ligand, N-phenyl-1,2-benzoquinonediimine, due to an oxidative ortho-C-N bond fusion reaction. Complex [1](+) and aniline (neat) at 185 °C produced a bis-chelated ruthenium complex (3)...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28426209/channel-assisted-proton-conduction-behavior-in-hydroxyl-rich-lanthanide-based-magnetic-metal-organic-frameworks
#11
Soumava Biswas, Jayita Chakraborty, Vijay Singh Parmar, Siba Prasad Bera, Nirmal Ganguli, Sanjit Konar
Two new lanthanide-based 3D metal-organic frameworks (MOFs), {[Ln(L)(Ox)(H2O)]n·xH2O} [Ln = Gd(3+) and x = 3 (1) and Dy(3+) and x = 1.5 (2); H2L = mucic acid; OxH2 = oxalic acid] showing interesting magnetic properties and channel-mediated proton conduction behavior, are presented here. Single-crystal X-ray structure analysis shows that, in complex 1, the overall structure originates from the mucate-bridged gadolinium-based rectangular metallocycles. The packing view reveals the presence the two types of hydrophilic 1D channels filled with lattice water molecules, which are strongly hydrogen-bonded with coordinated water along the a and b axes, whereas for complex 2, the 3D framework originates from a carboxylate-bridged dysprosium-based criss-cross-type secondary building block...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28426207/fe3o4-feni-embedded-nanostructure-and-its-kinetic-law-for-selective-catalytic-reduction-of-p-nitrophenyl-compounds
#12
Dandan Wu, Yanqiao Zhang, Ming Wen, Hao Fang, Qingsheng Wu
To meet the requirement of high catalytic efficiency toward the reduction of p-nitrophenyl compounds, we designed a new one-dimensional Fe3O4/FeNi embedded-nanostructured catalyst synthesized by a one-pot controlling-growth-reduction process in a solvothermal system, in which Fe3O4 phase was implanted in the base of FeNi alloy. In the Fe3O4/FeNi catalyst system, the Fe3O4 embedded phase attracts the nitro group of p-nitrophenyl compounds by its high-density electrons, which can efficiently promote the activity of amorphous FeNi active centers for selective catalysis toward the reduction of a range of p-nitrophenyl compounds...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28425719/adsorption-of-nitrate-and-bicarbonate-on-fe-hydr-oxide
#13
Nancy Y Acelas, Cacier Hadad, Albeiro Restrepo, César Ibarguen, Elizabeth Flórez
In this work, we used density functional theory calculations to study the resulting complexes of adsorption and of inner- and outer-sphere adsorption-like of bicarbonate and nitrate over Fe-(hydr)oxide surfaces using acidic, neutral, and basic simulated pH conditions. High-spin states that follow the 5N + 1 (N is the number of Fe atoms, each having five unpaired electrons) rule are preferred. Monodentate mononuclear (MM1) surface complexes are shown to lead to the most favorable thermodynamic adsorption for both bicarbonate and nitrate with -63...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28425715/five-fold-ordering-in-high-pressure-perovskites-rmn3o6-r-gd-tm-and-y
#14
Lei Zhang, Yoshitaka Matsushita, Kazunari Yamaura, Alexei A Belik
Cation and anion ordering plays an important role in the properties of materials, in particular, in the properties of perovskite materials. Here we report on unusual 5-fold cation/charge ordering in high-pressure-synthesized (at 6 GPa and ∼1670 K) RMn3O6 perovskites with R = Gd-Tm and Y. R(3+), Mn(2+), and Mn(3+) cations are ordered at the A site in two separate chains consisting of R(3+) and alternating Mn(2+) (in tetrahedral coordination) and Mn(3+) (in square-planar coordination), while Mn(3+) and mixed-valent Mn(3+)/Mn(4+) are ordered at the B site in layers...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28425700/reaction-of-the-tricyanoborate-dianion-b-cn-3-2-with-hgcl2
#15
Eduard Bernhardt, Vera Bernhardt-Pitchougina, Carsten Jenne
The very reactive [B(CN)3](2-) dianion has a strongly nucleophilic boron atom and can be used for the synthesis of tricyanoborates, which otherwise are difficult to access. Herein the reaction of this anion with HgCl2 is reported. The main product is the anionic mercury complex [Hg(B(CN)3)2](2-). Heteronuclear NMR spectroscopic experiments shows that the reaction proceeds via the intermediate [ClHgB(CN)3](2-). Even though [Hg(B(CN)3)2](2-) is the main product, it is difficult to obtain it in pure form, because it slowly decomposes in the presence of water and air to [(NC)HgB(CN)3](-)...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28425699/synthesis-of-npn-coordinated-tantalum-alkyl-complexes-and-their-hydrogenolysis-isolation-of-a-terminal-tantalum-hydride-incorporating-a-doubly-cyclometalated-npn-scaffold
#16
Sonja Batke, Malte Sietzen, Hubert Wadepohl, Joachim Ballmann
The closely related benzylene-linked diaminophosphines PhP(CH2C6H4-o-NHPh)2 (AH2) and PhP(C6H4-o-CH2NHXyl)2 (BH2 with Xyl = 3,5-Me2C6H3) were employed for the synthesis of tantalum(V) alkyls, which were then studied with respect to hydrogenolysis. In the case of AH2, the tantalum trimethyl complex [Ta(A)Me3] (1) and the tantalum hydrocarbyl complex [Ta(A)(CH2SiMe3)(η(2)-EtC≡CEt)] (2) were prepared from the ligand's dilithium salt (A)Li2(diox). Upon hydrogenolysis of 1 and 2, the formation of methane and SiMe4, respectively, was observed, but well-defined tantalum hydrides could not be detected...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28425294/reactivity-of-a-base-stabilized-germanium-i-dimer-toward-group-9-metal-i-chloride-and-dimanganese-decacarbonyl
#17
Muhammad Luthfi Bin Ismail, Fu-Quan Liu, Wai-Leung Yim, Rakesh Ganguly, Yongxin Li, Cheuk-Wai So
The reactivity of the 2-imino-5,6-methylenedioxylphenylgermanium(I) dimer toward group 9 metal(I) chloride and dimanganese decacarbonyl is described. [LGe:]2 (1, L = 2-imino-5,6-methylenedioxylphenyl) underwent a disproportionation reaction with 1.5 equiv of group 9 metal(I) chloride [MCl(cod)]2 (M = Rh, Ir) in toluene to afford a mixture of the group 9 metallogermylene-chlorometal(I) complexes [LGeμ-{M(cod)}2Cl] (M = Rh (2), Ir (4)) and chlorogermylene-chlorometal(I) complexes [L(Cl)GeM(cod)Cl] (M = Rh (3), Ir (5)), respectively...
April 20, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28422498/selective-oxygenation-of-cyclohexene-by-dioxygen-via-an-iron-v-oxo-complex-autocatalyzed-reaction
#18
Muniyandi Sankaralingam, Yong-Min Lee, Wonwoo Nam, Shunichi Fukuzumi
An iron complex with a tetraamido macrocyclic ligand, [(TAML)Fe(III)](-), was found to be an efficient and selective catalyst for allylic oxidation of cyclohexene by dioxygen (O2); cyclohex-2-enone was obtained as the major product along with cyclohexene oxide as the minor product. An iron(V)-oxo complex, [(TAML)Fe(V)(O)](-), which was formed by activating O2 in the presence of cyclohexene, initiated the autoxidation of cyclohexene with O2 to produce cyclohexenyl hydroperoxide, which reacted with [(TAML)Fe(III)](-) to produce [(TAML)Fe(V)(O)](-) by autocatalysis...
April 19, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28422490/redox-tagged-carbon-monoxide-releasing-molecules-corms-ferrocene-containing-mn-c-n-co-4-complexes-as-a-promising-new-corm-class
#19
Benjamin J Aucott, Jonathan S Ward, Samuel G Andrew, Jessica Milani, Adrian C Whitwood, Jason M Lynam, Alison Parkin, Ian J S Fairlamb
This study describes the synthesis and characterization of a new class of ferrocene-containing carbon monoxide-releasing molecules (CORMs, 1-3). The ferrocenyl group is both a recognized therapeutically viable coligand and a handle for informative infrared spectroelectrochemistry. Deoxymyoglobin CO-release assays and in situ infrared spectroscopy confirm compounds 2 and 3 as photoCORMs and 1 as a thermal CORM, attributed to the increased sensitivity of the Mn-ferrocenyl bond to protonation in 1. Electrochemical and infrared spectroelectrochemical experiments confirm a single reversible redox couple associated with the ferrocenyl moiety with the Mn tetracarbonyl center showing no redox activity up to +590 mV vs Fc/Fc(+), though no concomitant CO release was observed in association with the redox activity...
April 19, 2017: Inorganic Chemistry
https://www.readbyqxmd.com/read/28422488/pressure-driven-isostructural-phase-transition-in-innbo4-in-situ-experimental-and-theoretical-investigations
#20
Alka B Garg, Daniel Errandonea, Catalin Popescu, Domingo Martinez-García, Julio Pellicer-Porres, Placida Rodríguez-Hernández, Alfonso Muñoz, Pablo Botella, Vanesa P Cuenca-Gotor, Juan Angel Sans
The high-pressure behavior of technologically important visible-light photocatalytic semiconductor InNbO4, adopting a monoclinic wolframite-type structure at ambient conditions, was investigated using synchrotron-based X-ray diffraction, Raman spectroscopic measurements, and first-principles calculations. The experimental results indicate the occurrence of a pressure-induced isostructural phase transition in the studied compound beyond 10.8 GPa. The large volume collapse associated with the phase transition and the coexistence of two phases observed over a wide range of pressure shows the nature of transition to be first-order...
April 19, 2017: Inorganic Chemistry
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