74-90-8Relevant articles and documents
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Howard,Hilbert
, p. 1918,1921, 1922 (1938)
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Observation of high vibrational excitation in HCN molecules produced from 193 nm photolysis of 1,3,5-triazine
Goates, S. R.,Chu, J. O.,Flynn, G. W.
, p. 4521 - 4525 (1984)
Infrared emission from the ν2 bending mode and ν3 C-H stretching mode of HCN have been observed following 193 nm pulsed excimer laser photolysis of 1,3,5-triazine.Using a simple harmonic oscillator analysis, the number of ν2 bending quanta produced in HCN from photolysis of sym-triazine was found to be 70 times larger than the number of ν3 C-H stretching quanta.The combination of a high density of bending vibrational states in HCN and favorable geometry changes which occur in going from 1,3,5-triazine to three HCN molecules, appear to give an unusually pure distribution which maximizes vibrational energy in the HCN bending mode.
Andrussow
, (1938)
King, C. M.,Nixon, E. R.
, p. 1685 - 1695 (1968)
Multicomponent reaction of conjugated enynones with malononitrile and sodium alkoxides: Complex reaction mechanism of the formation of pyridine derivatives
Kuznetcova, Anastasiya V.,Odin, Ivan S.,Golovanov, Alexander A.,Grigorev, Iakov M.,Vasilyev, Aleksander V.
, p. 4516 - 4530 (2019)
Reaction of conjugated enynones,1,5-diarylpent-2-en-4-yn-1-ones, with malononitrile and sodium alkoxides in the corresponding alcohols at room temperature for 3–23 h results in the formation of two types of compounds (E)-/(Z)-6-aryl-4-(2-arylethenyl)-2-alkoxypyridine-3-carbonitriles (substituted nicotinonitriles), as the major reaction products in yields up to ca. 40–80%, and 6-aryl-4-arylethynyl-2-alkoxypyridines, as the minor reaction products in yields of 5–17%. Plausible mechanism of this complex and multistep reaction is discussed. The obtained pyridines possess fluorescent properties.
Yates,Heider
, p. 4153 (1952)
Investigations of Small Carbon Cluster Ion Structures by Reactions with HCN
Parent, Denise C.,McElvany, Stephen W.
, p. 2393 - 2401 (1989)
The results of a detailed study of the primary and secondary reactions of carbon cluster ions, Cn(1+) (3=20), with HCN are used as a probe of the structures of small carbon cluster ions.The experiments were performed in a Fourier transform ICR mass spectrometer (FTMS), using direct laser vaporization of graphite to form the carbon cluster ions.The only ionic products observed for the HCN reactions were CnX(1+) (primary reaction product) and CnXY(1+) (secondary reaction product) where X and Y = H, CN, or HCN.Radiative association is an important reaction channel.Products resulting from fragmentation of the reactant carbon cluster ion were not observed.Evidence for two structural forms of the n = 7-9 cluster ions is presented.The anomalous behavior of C7(1+) is interpreted by an isomerization mechanism.Low-energy collision-induced dissociation studies of the primary product ions support a mechanism of carbene insertion into the H-CN bond and formation of covalently bonded products.In contrast, the HCN associates weakly with most primary product ions.
Analysis of products from a C2H2/N2 microwave discharge: New nitrile species
Fujii, Toshihiro
, p. 733 - 740 (1999)
The production of gaseous hydrocarbons, nitriles, amines, and hydrazines in a continuous-flow microwave plasma discharge excited in a 20% C2H2+80% N2 mixture at a pressure of 20 Torr is reported. The product analysis was made by Li+ ion attachment mass spectrometry. A variety of N-containing organics (identified as HCnN (n=1-7), NC(CC)nCN (n=0-2), NC(CH2)nCN (n=0-6), CnH2n-1NH2 (n=0-6), CnH2n+1N(H)NH2 (n=0-5), etc.) were formed and these were tentatively assigned to nitriles, amines, and hydrazines. The mass-spectral analysis exhibited progressions differing by 14 mass units. Reaction schemes were proposed to explain the formation of some molecules.
Charge-transfer complexes of hypoglycemic sulfonamide with π-acceptors: Experimental and DFT-TDDFT studies
Soltani, Sara,Magri, Pierre,Rogalski, Marek,Kadri, Mekki
, p. 105 - 116 (2019)
Charge-transfer interactions (CT) between the electron donor gliclazide (GLC) and the π-acceptors 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) and tetracyanoethylene (TCNE) were studied in a chloroform solution and in the solid state. The CT complexes were discussed in terms of formation constants (KCT), molar extinction coefficients (εCT), standard reaction quantities (ΔG° ΔH° and ΔS°), oscillator strength (f), transition dipole moment (μEN), and ionization potential (Ip). The limits of detection (LOD) and limits of quantification (LOQ) have also been reported. The stoichiometry of these complexes was found to be in a 1:1 M ratio. The formed solid CT complexes were also synthesized and characterized using electronic methods, FT-IR, 1H and 13C NMR spectroscopy. Thermogravimetric analysis techniques (TGA/DTA) and differential scanning calorimetry (DSC) were used to determine the thermal stability of the synthesized CT complex. The kinetic parameters (ΔG* ΔH* and ΔS*) were calculated from thermal decomposition data using the Coats-Redfern method. Moreover, density functional theory (DFT) studies are discussed for the charge transfer complex GLC-TCNE, using the B3LYP with 6–311++G (d, p) basis set. The harmonic vibrational frequencies were calculated, and the scaled values have been compared with experimental FT-IR spectra. The calculated 1H and 13C NMR chemical shifts using the GIAO method showed good correlations with the experimental data. The theoretical UV–visible spectrum of the compound and the electronic properties, such as HOMO and LUMO energies, were performed using the time-dependent (TD-DFT) approach with CAM-B3LYP, employing the 6–311++G (d, p) basis set, and good agreement with the theoretical and experimental UV–visible data was found.
Atakan, B.,Jacobs, A.,Wahl, M.,Weller, R.,Wolfrum, J.
, p. 449 - 453 (1989)
Gartaganis,Winkler
, p. 1457,1461 (1956)
Temperature Dependence of the Reaction of Nitrogen Atoms with Methyl Radicals
Marston, George,Nesbitt, Fred L.,Nava, David F.,Payne, Walter A.,Stief, Louis J.
, p. 5769 - 5774 (1989)
The discharge-flow mass spectrometry technique has been used to measure the kinetics of the reaction N + CH3 -> products over the temperature range 200-423 K.The results are as follows (10-11 cm3 s-1): k1(200 K)
Bichowsky
, (1926)
Surface chemistry of CN bond formation from carbon and nitrogen atoms on Pt(111)
Herceg, Eldad,Trenary, Michael
, p. 17560 - 17566 (2005)
The mechanism of CN bond formation from CH3 and NH3 fragments adsorbed on Pt(111) was investigated with reflection absorption infrared spectroscopy (RAIRS), temperature-programmed desorption (TPD), and X-ray photoelectron spectroscopy (XPS). The surface chemistry of carbon-nitrogen coupling is of fundamental importance to catalytic processes such as the industrial-scale synthesis of HCN from CH4 and NH3 over Pt. Since neither CH4 nor NH3 thermally dissociate on Pt(111) under ultrahigh vacuum (UHV) conditions, the relevant surface intermediates were generated through the thermal decomposition of CH 3I and the electron-induced dissociation of NH3. The presence of surface CN is detected with TPD through HCN desorption as well as with RAIRS through the appearance of the vibrational features characteristic of the aminocarbyne (CNH2) species, which is formed upon hydrogenation of surface CN at 300 K. The RAIRS results show that HCN desorption at a??500 K is kinetically limited by the formation of the CN bond at this temperature. High coverages of Cads suppress CN formation, but the results are not influenced by the coadsorbed I atoms. Cyanide formation is also observed from the reaction of adsorbed N atoms and carbon produced from the dissociation of ethylene. ? 2005 American Chemical Society.
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Garner,Matsuno
, p. 1903 (1921)
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Herries, D. G.,Richards, F. M.
, p. 1155 - 1156 (1964)
Suarez, M. Patricia,Loeffler, Daniel G.
, p. 240 - 242 (1986)
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Onyszchuk,Winkler
, p. 368,369 (1955)
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The hexacyanotitanate ion: Synthesis and crystal structure of [NEt4]3[Ti(III)(CN)6]·4MeCN
Entley, William R.,Treadway, Christopher R.,Wilson, Scott R.,Girolami, Gregory S.
, p. 6251 - 6258 (1997)
The hexacyanotitanate salt, [Et4N]3[Ti(CN)6]·4MeCN, has been prepared by addition of tetraethylammonium cyanide to the titanium(III) triflate salt Ti(O3SCF3)3(MeCN)3. The orange crystalline product has been characterized by X-ray diffraction, and the d1 anion is only slightly distorted from ideal O(h) symmetry. The anion resides on a center of symmetry and is characterized by the following parameters: Ti-C = 2.195(2), 2.197(3), and 2.213(3) A?; C-N (av) = 1.141(4) A?; C-Ti-C (cis) = 88.01(9), 88.02(9), 89.02(9), and 89.78(9)°; C-Ti-C (trans) = 180°. In addition to the crystallographic study, details of the IR (ν(CN) = 2071 cm-1), EPR, and UV-vis spectra (Δ(o) = 22800 cm-1) are given. Crystal data for [Et4N]3[Ti(CN)6]·4MeCN are as follows: monoclinic, space group I2/a, a = 18.171(6) A?, b = 12.200(4) A?, c = 20.989(5) A?, β = 91.17(2)°, V = 4652(2) A?3, Z = 4, wR2 = 0.2054 for 3831 data, 27 restraints, and 318 parameters.
Mueller
, p. 3459 (1955)
Characterization of a carbon-nitrogen network solid with NMR and high field EPR
Rovnyak, David,Baldus, Marc,Itin, Boris A.,Bennati, Marina,Stevens, Andrew,Griffin, Robert G.
, p. 9817 - 9822 (2000)
Considerable attention has been focused on developing a synthetic route to a carbon-nitrogen material with mechanical and thermal properties comparable or superior to those of diamond. To date, no substance with the desired C3N4 stoichiometry in a silicon-nitride crystal lattice has been reported. One of the principal difficulties in the pursuit of ultrahard carbon-nitrogen (CN) solids is the characterization of amorphous CN samples. We describe a solid-state NMR study of a paracyanogen-like solid utilizing 13C-15N adiabatic-passage Hartmann-Hahn cross-polarization (APHH-CP) to perform dipolar filtering and show that this method is well-suited for recoupling 13C-15N in network solids. In addition, high-frequency electron paramagnetic resonance (EPR) indicates a density of electron spins of approximately 1 × 1017 e-/cm3. We conclude by discussing how NMR and EPR data may be useful for optimizing CN-polymer samples as potential precursors for ultrahard carbon nitrogen solids.
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Fosse,Hieulle
, (1922)
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Hasenberg, D.,Schmidt, L. D.
, p. 441 - 453 (1987)
Guernsey et al.
, (1926)
Bassett, H.,Corbet, A. S.
, p. 1358 - 1358 (1924)
Facile Synthesis of the Dicyanophosphide Anion via Electrochemical Activation of White Phosphorus: An Avenue to Organophosphorus Compounds
Liu, Liu Leo,Mei, Yanbo,Yan, Zeen
supporting information, p. 1517 - 1522 (2022/02/01)
Organophosphorus compounds (OPCs) have gained tremendous interest in the past decades due to their wide applications ranging from synthetic chemistry to materials and biological sciences. We describe herein a practical and versatile approach for the trans
Large Faraday Rotation in Optical-Quality Phthalocyanine and Porphyrin Thin Films
Nelson, Zachary,Delage-Laurin, Leo,Peeks, Martin D.,Swager, Timothy M.
supporting information, p. 7096 - 7103 (2021/05/29)
The magneto-optical phenomenon known as Faraday rotation involves the rotation of plane-polarized light as it passes through an optical medium in the presence of an external magnetic field oriented parallel to the direction of light propagation. Faraday rotators find applications in optical isolators and magnetic-field imaging technologies. In recent years, organic thin films comprised of polymeric and small-molecule chromophores have demonstrated Verdet constants, which measure the magnitude of rotation at a given magnetic field strength and material thickness, that exceed those found in conventional inorganic crystals. We report herein the thin-film magnetic circular birefringence (MCB) spectra and maximum Verdet constants of several commercially available and newly synthesized phthalocyanine and porphyrin derivatives. Five of these species achieved maximum Verdet constant magnitudes greater than 105 deg T-1 m-1 at wavelengths between 530 and 800 nm. Notably, a newly reported zinc(II) phthalocyanine derivative (ZnPc-OT) reached a Verdet constant of -33 × 104 deg T-1 m-1 at 800 nm, which is among the largest reported for an organic material, especially for an optical-quality thin film. The MCB spectra are consistent with resonance-enhanced Faraday rotation in the region of the Q-band electronic transition common to porphyrin and phthalocyanine derivatives, and the Faraday A-term describes the electronic origin of the magneto-optical activity. Overall, we demonstrate that phthalocyanines and porphyrins are a class of rationally designed magneto-optical materials suitable for applications demanding large Verdet constants and high optical quality.
Trapping of Br?nsted acids with a phosphorus-centered biradicaloid - synthesis of hydrogen pseudohalide addition products
Beer, Henrik,Bl?sing, Kevin,Bresien, Jonas,Chojetzki, Lukas,Schulz, Axel,Stoer, Philip,Villinger, Alexander
supporting information, p. 13655 - 13662 (2020/10/27)
The trapping of classical hydrogen pseudohalides (HX, X = pseudohalogen = CN, N3, NCO, NCS, and PCO) utilizing a phosphorus-centered cyclic biradicaloid, [P(μ-NTer)]2, is reported. These formal Br?nsted acids were generatedin situas gases and passed over the trapping reagent, the biradicaloid [P(μ-NTer)]2, leading to the formation of the addition product [HP(μ-NTer)2PX] (successful for X = CN, N3, and NCO). In addition to this direct addition reaction, a two-step procedure was also applied because we failed in isolating HPCO and HNCS addition products. This two-step process comprises the generation and isolation of the highly reactive [HP(μ-NTer)2PX]+cation as a [B(C6F5)4]?salt, followed by salt metathesis with salts such as [cat]X (cat = PPh4,n-Bu3NMe), which also gives the desired [HP(μ-NTer)2PX] product, with the exception of the reaction with the PCO?salt. In this case, proton migration was observed, finally affording the formation of a [3.1.1]-hetero-propellane-type cage compound, an OC(H)P isomer of a HPCO adduct. All discussed species were fully characterized.
