Structure, Stability, and Cycloaddition Reactions of Nitrile Selenides

2014 ◽  
Vol 67 (3) ◽  
pp. 444 ◽  
Author(s):  
Tibor Pasinszki ◽  
Melinda Krebsz ◽  
Balázs Hajgató
Keyword(s):  
Gas Phase ◽  
Quantum Chemical ◽  
Room Temperature ◽  
Equilibrium Structure ◽  
Solid Matrix ◽  
Structure Stability ◽  
Chemical Methods ◽  
Bimolecular Reactions ◽  
Dilute Gas ◽  
Quantum Chemical Methods

The equilibrium structure, unimolecular reactions, and bimolecular reactions of nitrile selenides (XCNSe, where X = H, F, Cl, Br, CN, CH3) have been investigated using CCSD(T), CCSD(T)//B3LYP, and MR-AQCC//UB3LYP quantum-chemical methods. Nitrile selenides are demonstrated to be stable under isolated conditions at ambient temperature, i.e. in the dilute gas phase or in an inert solid matrix, but unstable in the condensed phase or solutions owing to bimolecular reactions. FCNSe and CH3CNSe cycloaddition with ethynes, ethenes, and nitriles was studied using the MR-AQCC//UB3LYP method. Cycloaddition was predicted to be facile at room temperature with small dipolarophiles.

Structure, Stability, and Generation of CH3CNS

2010 ◽  
Vol 63 (12) ◽  
pp. 1686 ◽  
Author(s):  
Melinda Krebsz ◽  
Balázs Hajgató ◽  
Gábor Bazsó ◽  
György Tarczay ◽  
Tibor Pasinszki
Keyword(s):  
Uv Irradiation ◽  
Broad Band ◽  
Solid Matrix ◽  
Structure Stability ◽  
Ground State Structure ◽  
Bimolecular Reactions ◽  
Dilute Gas ◽  
Quantum Chemical Methods ◽  
The Matrix ◽  
Solid Argon

The unstable acetonitrile N-sulfide molecule CH3CNS has been photolytically generated in inert solid argon matrix from 3,4-dimethyl-1,2,5-thiadiazole by 254-nm UV irradiation, and studied by ultraviolet spectroscopy and mid-infrared spectroscopy. The molecule is stable in the matrix to 254-nm UV irradiation, but decomposes to CH3CN and a sulfur atom when broad-band UV irradiation is used. Chemiluminescence due to S2 formation from triplet sulfur atoms was detected on warming the matrix to ∼20–25 K. The ground-state structure and potential uni- and bimolecular reactions of CH3CNS are investigated using B3LYP, CCSD(T), and MR-AQCC quantum-chemical methods. CH3CNS is demonstrated to be stable under isolated conditions at room temperature, i.e. in the dilute gas phase or in an inert solid matrix, but unstable owing to bimolecular reactions, i.e. in the condensed phase.

scholarly journals A quantum chemical study on gas phase decomposition pathways of triethylgallane (TEG, Ga(C2H5)3) and tert-butylphosphine (TBP, PH2(t-C4H9)) under MOVPE conditions

2014 ◽  
Vol 16 (32) ◽  
pp. 17018-17029 ◽  
Author(s):  
Andreas Stegmüller ◽  
Phil Rosenow ◽  
Ralf Tonner
Keyword(s):  
Gas Phase ◽  
Quantum Chemical ◽  
Quantum Chemical Study ◽  
Chemical Study ◽  
Phase Decomposition ◽  
Chemical Methods ◽  
Decomposition Products ◽  
Elementary Reactions ◽  
Quantum Chemical Methods ◽  
Precursor Molecules

Gas phase decomposition products of MOVPE precursor molecules TEG and TBP were identified via thermodynamic and kinetic data from a catalogue of 61 elementary reactions as calculated by quantum chemical methods.

scholarly journals Gas-phase structures of sterically crowded disilanes studied by electron diffraction and quantum chemical methods: 1,1,2,2-tetrakis(trimethylsilyl)disilane and 1,1,2,2-tetrakis(trimethylsilyl)dimethyldisilane

2014 ◽  
Vol 43 (26) ◽  
pp. 10175-10182 ◽  
Author(s):  
Jan Schwabedissen ◽  
Paul D. Lane ◽  
Sarah L. Masters ◽  
Karl Hassler ◽  
Derek A. Wann
Keyword(s):  
Electron Diffraction ◽  
Gas Phase ◽  
Quantum Chemical ◽  
Chemical Methods ◽  
Geometric Structures ◽  
Phase Structures ◽  
Quantum Chemical Methods

Structures of the two title disilanes have been determined. The presence of bulky, flexible Me3Si groups dictates many aspects of the geometric structures.

Aplicyanins – brominated natural marine products with superbasic character

2016 ◽  
Vol 71 (8) ◽  
pp. 883-889 ◽  
Author(s):  
Marina D. Kostić ◽  
Vera M. Divac ◽  
Basam M. Alzoubi ◽  
Ralph Puchta
Keyword(s):  
Gas Phase ◽  
Quantum Chemical ◽  
Proton Affinities ◽  
Chemical Methods ◽  
Nucleus Independent Chemical Shift ◽  
Quantum Chemical Methods ◽  
Acetyl Group ◽  
Marine Products ◽  
Nics Calculations ◽  
Proton Sponges

AbstractBy using quantum chemical methods (B3LYP/6-311+G(2df,p)//B3LYP/6-31G(d)), we investigated the structures of aplicyanin A, aplicyanin B, aplicyanin C, aplicyanin D, aplicyanin E, and aplicyanin F along with their protonated structures. The calculated gas phase proton affinities of aplicyanin A, aplicyanin C, and aplicyanin E are around –250 kcal mol−1 and therefore more than 10 kcal mol−1 higher as in typical proton sponges such as 1,8-bis(dimethylamino)naphthalene. The compounds aplicyanin B, aplicyanin D, and aplicyanin F show reduced proton affinities of approximately –240 kcal mol−1 because of the acetyl group being conjugated with the imine N=C moiety. Nucleus-independent chemical shift (NICS) calculations on the same level of theory do not show any peculiarities, and a reasonable correlation between the toxicity of aplicyanins and the gas phase proton affinity is not observed.

Molecular structure of N-chlorosuccinimide studied by gas-phase electron diffraction and quantum-chemical methods

2009 ◽  
Vol 20 (3) ◽  
pp. 435-442 ◽  
Author(s):  
Yuri V. Vishnevskiy ◽  
Natalja Vogt ◽  
Vitaliy I. Korepanov ◽  
Arkadii A. Ivanov ◽  
Lev V. Vilkov ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Electron Diffraction ◽  
Gas Phase ◽  
Quantum Chemical ◽  
Chemical Methods ◽  
Quantum Chemical Methods ◽  
Gas Phase Electron Diffraction
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