- Fixation of CO2 by magnesium cations: A reinterpretation
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(Chemical Equation Presented) OCO or NCO? The case of irreversible CO 2 coordination to Mg cations has been revisited and reinterpreted as a more straightforward case of reaction of CO2 with silazanate ligands and formation of coordinated NCO ligands on the basis of DFT calculations, NMR, and chemical-degradation experiments.
- Phull, Harminder,Alberti, Davide,Korobkov, Ilia,Gambarotta, Sandro,Budzelaar, Peter H. M.
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- A novel visible light-driven silver isocyanate photocatalyst: superior stability enhanced by intrinsic resonance effect
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Silver isocyanate (AgNCO), a novel visible-light sensitive semiconductor photocatalyst, is prepared based on an intrinsic resonance effect strategy through a simple precipitation process. The as-prepared photocatalyst exhibits photocatalytic degradation ability under visible light. Importantly, it also shows excellent photocatalytic stability, which is a crucial problem to overcome in Ag-based photocatalysts. The existence of an intrinsic resonance effect and its crystal structure may be the main reasons for the superior photocatalytic stability of the AgNCO photocatalyst. The possible transferred and separated behavior of charge carriers and the reason for outstanding photocatalytic stability are illustrated in detail. This study develops a new design idea for exploiting stable Ag-based photocatalysts under visible light irradiation.
- Fan, Shuo,Chen, Gang,Li, Chunmei,Lv, Chade,Han, Zhonghui,Rao, Jiancun,Hu, Yidong,Zhang, Congmin
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- VIBRATIONAL STUDY ON AgNCO SINGLE CRYSTAL
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AgNCO shows polymorphic behaviour as revealed by X-ray studies.In this communication we present single crystal IR transmission spectra of the well established a-form.Under certain preparation conditions a new form (b-form) was isolated.Powder Raman and X-ray data are presented and discussed comparatively.A suggestion of order-dis-order appearance in the anionic lattice is made.
- Popitsch, A.,Nachbaur, E.,Fritzer, H. P.
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- Crystal structure and dimorphism of silicon tetraisocyanate Si(NCO) 4
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Silicon tetraisocyanate Si(NCO)4 was obtained by reacting SiCl4 and AgNCO in boiling toluene. The colourless liquid was analyzed by Raman and NMR spectroscopy. Structural studies on solid Si(NCO) 4 (melting point: +26°C) have revealed it to exist in two polymorphic modifications. According to the results of single-crystal X-ray diffraction, at T = -173°C, α-Si(NCO)4 exhibits triclinic symmetry (Pβar{1}$; a = 10.05(5), b = 10.50(2), c = 14.32(1) A, α = 91.62(1)°, β = 92, 32(1)°, γ = 99.68(1)°; V = 1488.56(3) A3; Z = 8). Above T = -33°C, a monoclinic phase evolves, β-Si(NCO)4 (P21/c; a = 10.78(3), b = 7.11(1), c = 10.27(5) A, β = 99, 06(9)°; V = 777.39(1) A3; Z = 4). The charge distribution was studied for both polymorphs. In the solid state, Si(NCO)4 is a tetrahedral molecule with the Si-N=C=O linkages bent at the nitrogen atoms. Copyright
- Schmidt, Carsten Ludwig,Jansen, Martin
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- Synthesis and structures of triorganotelluronium pseudohalides
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The syntheses of [(CH3)3Te]X {X = N3 (1), OCN (2), SCN (3), SeCN (4), [Ag(CN)2] (5)} and [(C6H5)3Te]X {X = N3 (6), SeCN (7), [Ag(CN)2] (8)}, their NMR spectroscopic data, vibrational spectra and single crystal structures are described. Compounds 1-4 are the first trimethyltelluronium pseudohalides, while the known compounds 6 and 7 have been prepared for completion of their analytical and structural properties. The occurrence of intermolecular Te···N, Te···O, Te···S and Te···Se contacts is thoroughly studied. The dicyanoargentates 5 and 8 were obtained in an attempt to prepare telluronium cyanides. Low-temperature 13C NMR spectroscopy of the [Ag(CN)2]- ion in solution has been carried out, with determination of the 13C-107/109Ag coupling. Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002.
- Klapoetke, Thomas M.,Krumm, Burkhard,Mayer, Peter,Piotrowski, Holger,Schwab, Ingo,Vogt, Martin
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p. 2701 - 2709
(2007/10/03)
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- Some Group 15 Pseudo-halides and the Crystal Structure of Diphenylbismuth(III) Thiocyanate
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A crystal structure determination showed that in diphenylbismuth thiocyanate the thiocyanate group bridges between pairs of bismuth atoms to give infinite chains in which alternate bismuth atoms are co-ordinated to either two nitrogen or two sulfur atoms.The conformation of the resulting chain is a 'rectangular spiral', in contrast to the 'triangular spiral' structure of the related diphenylantimony thiocyanate.Unstable diphenylantimony selenocyanate has also been prepared and the complexity in the C-N stretching region of the IR spectrum suggests a structure similar to that of the thiocyanate analogue.Diphenylarsenic thiocyanate is a liquid at room temperature and a conventional 1,3-thiocyanate-bridged structure is suggested from IR data.
- Forster, Glynis E.,Begley, Michael J.,Sowerby, D. Bryan
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p. 383 - 388
(2007/10/02)
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- Molybdenum Complexes of Bioinorganic Interest: Studies on the Bonding Mode of Cyanate and Azide Ions in (py)4M4X2MoS4 and (phen)2M4X2MoS4 (M=CuI or AgI; X=OCN- or N3-)
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Molybdenum complexes, (py)4M4X2MoS4 and (phen)2M4X2MoS4 (M=CuI, AgI; X=OCN- or N3-), have been synthesised and characterised by elemental analysis, molar conductance, magnetic moment, infrared and electronic spectral studies.End-to-end azide bridging for the azide complexes and oxygen-bonded cyanate terminals for the cyanate complexes have been proposed.The values of quantitative softness of metals (En) and ligands (Em) have been found to support the proposed structure of the complexes.
- Sharma, S. B.,Tewari, I. N.
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p. 714 - 718
(2007/10/02)
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- Synthesis of tetraphenylstannacyclopentadienes (stannoles). 2. Derivatives and adducts of 1,1-dihalo-2,3,4,5-tetraphenylstannoles
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1,1-Dibromo- and 1,1-diiodo-2,3,4,5-tetraphenyl-1-stannacyclopentadiene, dihalotetraphenylstannoles [XYSnC4(C6H5)4], can be derivatized to form a series of disubstituted products in which X = Y = N3, iso-NCO, iso-SCN, OC(O)CH3, SC(S)N(C2H5)2, N(CH3)2, and P(C6H5)2. Fluorination by KF in acetone results in the X = F, Y = Br, or Y = I product only, and lithioamination by LiN[Si(CH3)3]2 yields the X = N[Si(CH3)3]2, Y = Br product only. Attempted synthesis of the dihalostannoles by halogenation of the intermediate tin(II) stannole from 1,4-dilithio-1,2,3,4-tetraphenyl-1,3-butadiene and tin(II) chloride yields only the ring-opened products (4-bromo-1,2,3,4-tetraphenylbutadienyl)tin tribromide or (4-iodo-1,2,3,4-tetraphenylbutadienyl)tin triiodide. Even gentle chlorination of hexaphenylstannole by elemental chlorine cleaves the ring tin-carbon bonds to form cis,cis-1,4-dichloro-1,2,3,4-tetraphenyl-1,3-butadiene and diphenyltin(IV) dichloride, while the action of a glacial acetic acid-acetic anhydride mixture yields tetraphenylfuran and diphenyltin(IV) diacetate. The dihalostannoles form neutral adducts with pyridine, 2,2′-bipyridyl, and 1,10-phenanthroline and the double salt [XSnC4(C6H5)4·terpy] +[X2YSnC4(C6H5) 4]- from 2,2′,2″-terpyridine where X = Y = Br, I = F, and Y = I. The structures of the substituted stannoles and the adducts of the dihalostannoles are discussed on the basis of tin-119m Mo?ssbauer and infrared spectroscopic evidence.
- Gustavson,Principe,Min Rhee,Zuckerman
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p. 3460 - 3468
(2008/10/08)
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