Computational study on vapor phase coupling reaction between diiso(thio)cyanates with diamines, diols, and dithiols
| Autor: | Woo‐Suk Oh, Jae Young Lee, Bonggeun Shong, Ahhyun Kim |
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| Rok vydání: | 2017 |
| Předmět: |
010405 organic chemistry
Thio 02 engineering and technology Activation energy 021001 nanoscience & nanotechnology Condensed Matter Physics Photochemistry 01 natural sciences Atomic and Molecular Physics and Optics Transition state Coupling reaction 0104 chemical sciences chemistry.chemical_compound chemistry Nucleophile Vacuum deposition Yield (chemistry) Physical and Theoretical Chemistry 0210 nano-technology Bifunctional |
| Zdroj: | International Journal of Quantum Chemistry. 117:e25341 |
| ISSN: | 0020-7608 |
| DOI: | 10.1002/qua.25341 |
| Popis: | Coupling between iso(thio)cyanates and amines, alcohols, and thiols to yield (thio)urea/urethane in the gas phase is important for the vacuum deposition processes of functional organic thin films such as molecular layer deposition or chemical vapor deposition. In this study, the kinetics and thermodynamics of 12 reactions between bifunctional reactants containing NCO/NCS and NH2/OH/SH moieties were calculated using double-hybrid density functional theory to find systematic structure–reactivity relationships. The activation energy for the proton-transfer step was correlated with the basicity of the nucleophile/Bronsted acid reactants, while the exothermicity of the coupling reaction depends on whether the other functionality is NCO or NCS. Analysis of the transition states revealed that the location of the transition state is affected by the basicity of the reactants. Vibrational and electronic spectra of the product were obtained to help future experimental investigations. |
| Databáze: | OpenAIRE |
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