The Experts below are selected from a list of 93 Experts worldwide ranked by ideXlab platform
David M Stanbury - One of the best experts on this subject based on the ideXlab platform.
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Acidic aqueous decomposition of Thiocyanogen
Inorganic chemistry, 2004Co-Authors: Jon J Barnett, Michael L Mckee, David M StanburyAbstract:The aqueous reaction of acidic Cl2 with excess SCN- rapidly generates a UV-absorbing intermediate identified as an equilibrium mixture of Thiocyanogen, (SCN)2, and trithiocyanate, (SCN)3-. The decomposition of this mixture can be described as 3(SCN)2 + 4H2O → 5HSCN + H2SO4 + HCN. Under our conditions the decomposition is sufficiently slow that its kinetics can be studied using standard stopped-flow methodology. Over the pH range 0−2 the decomposition rate law is −d[(SCN)2]/dt = (3/2){kdispKhyd2[(SCN)2]2/([SCN-]2[H+]2 + K(SCN)3−[SCN-]3[H+]2 + Khyd[SCN-][H+])} with K(SCN)3− = 0.43 ± 0.29 M-1, Khyd = (5.66 ± 0.77) × 10-4 M2, and kdisp = (6.86 ± 0.95) × 104 M-1 s-1 at 25 °C and μ = 1 M. The K(SCN)3− and Khyd terms are significant enhancements relative to one of the rate laws conventionally cited. In the proposed mechanism, K(SCN)3− refers to the formation of (SCN)3- by association of SCN- with (SCN)2, Khyd refers to the hydrolysis of (SCN)2 to form HOSCN, and kdisp is the rate constant for the bimolecular irr...
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acidic aqueous decomposition of Thiocyanogen
Inorganic Chemistry, 2004Co-Authors: Jon J Barnett, Michael L Mckee, David M StanburyAbstract:The aqueous reaction of acidic Cl2 with excess SCN- rapidly generates a UV-absorbing intermediate identified as an equilibrium mixture of Thiocyanogen, (SCN)2, and trithiocyanate, (SCN)3-. The deco...
John Wood - One of the best experts on this subject based on the ideXlab platform.
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Organic Reactions - Substitution and Addition Reactions of Thiocyanogen
Organic Reactions, 2011Co-Authors: John WoodAbstract:The direct replacement of a hydrogen atom by a thiocyano group through the use of Thiocyanogen is termed thiocyanation. This replacement reaction is limited practically to aromatic amines and phenols. Thiocyanogen reacts with olefinic and acetylenic linkage, the reagent adding to the unsaturated linkage. Thicyanogen reacts with compounds of other types. Thiocyanogen reacts with aromatic compounds that are highly susceptible to substitution with the introduction of a thiocyano groups. Thiocyanation of aromatic amines, phenols is discussed. Addition of Thiocyanogen to olefins and acetylenes, and miscellaneous syntheses are also discussed. Keywords: Thiocyanogen; addition; substitution; phenols; aromatic amines; polynuclear hydrocarbons; olefins; acetylenes; thiocyano compounds; experimental procedures
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substitution and addition reactions of Thiocyanogen
Organic Reactions, 2011Co-Authors: John WoodAbstract:The direct replacement of a hydrogen atom by a thiocyano group through the use of Thiocyanogen is termed thiocyanation. This replacement reaction is limited practically to aromatic amines and phenols. Thiocyanogen reacts with olefinic and acetylenic linkage, the reagent adding to the unsaturated linkage. Thicyanogen reacts with compounds of other types. Thiocyanogen reacts with aromatic compounds that are highly susceptible to substitution with the introduction of a thiocyano groups. Thiocyanation of aromatic amines, phenols is discussed. Addition of Thiocyanogen to olefins and acetylenes, and miscellaneous syntheses are also discussed. Keywords: Thiocyanogen; addition; substitution; phenols; aromatic amines; polynuclear hydrocarbons; olefins; acetylenes; thiocyano compounds; experimental procedures
Eduardo L. Varetti - One of the best experts on this subject based on the ideXlab platform.
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Experimental and theoretical vibrational study of methylene bis(thiocyanate), CH2(SCN)2. A comparison with Thiocyanogen, (SCN)2.
Spectrochimica acta. Part A Molecular and biomolecular spectroscopy, 2013Co-Authors: Leónides Fernández, A.a. Gómez, R.m. Tótaro, A.c. Coronel, Eduardo L. VarettiAbstract:The infrared and Raman spectra of methylene bis(thiocyanate), CH2(SCN)2, were obtained. The observed bands were assigned to the different normal modes of vibration using the results of a DFT calculation of the molecular vibrational properties. These results and the experimental data were used to define a Scaled Quantum Mechanics force field for the molecule. A similar treatment was applied to the Thiocyanogen molecule, (SCN)2, for which the experimental frequencies were already reported in the literature. The sets of internal force constants for both molecules show very similar values.
F. Cataldo - One of the best experts on this subject based on the ideXlab platform.
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13C NMR and FT-IR spectra of Thiocyanogen, S2(CN)2, selenocyanogen, Se2(CN)2, and related compounds
Polyhedron, 2000Co-Authors: F. CataldoAbstract:Abstract The pseudohalogens Thiocyanogen [(SCN)2], sulfur dicyanide [S(CN)2], selenocyanogen [(SeCN)2], selenium dicyanide [Se(CN)2] and selenium diselenocyanate [Se(SeCN)2] have been prepared and studied by 13C NMR spectroscopy for the first time. The 13C NMR results confirm the structure previously assigned to these compounds on the basis of vibrational spectroscopy. Thiocyanogen, sulfur dicyanide, selenocyanogen and selenium dicyanide have been also studied as liquid film on KBr plate in the solid state (KBr pellet) by FT-IR spectroscopy and the data collected have been compared and discussed with previous results recorded on solutions in organic solvents. Good agreement with early results has been obtained. It has been confirmed by solid state 13C NMR–MAS that under mild conditions selenocyanogen disproportionates into selenium dicyanide and selenium diselenocyanate. By heating selenocyanogen above 180°C it polymerizes irreversibly into a brown polymer known as paraselenocyanogen whose FT-IR spectrum is surprisingly very similar to that of paraThiocyanogen or polyThiocyanogen, the product of self-polymerization of Thiocyanogen.
Rosario M Diaz - One of the best experts on this subject based on the ideXlab platform.
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Thiocyanogen insertion into p c bonds of diphosphinomethanide complexes leading to rare functionalized diphosphine and tetraphosphine ligands
Organometallics, 2007Co-Authors: Javier Ruiz, Roberto Quesada, Marilin Vivanco, And Santiago Garciagranda, Rosario M DiazAbstract:The complex fac-[Mn(CNtBu)(CO)3{(PPh2)2C−SCN}] (2) reacts with Thiocyanogen, affording the unstable derivative fac-[Mn(CNtBu)(CO)3{(PPh2)C(SCN)C(SSCN)N(PPh2)}] (3), as a result of the insertion of ...