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Computational study on vapor phase coupling reaction between diiso(thio)cyanates with diamines, diols, and dithiols
Author(s) -
Lee Jae Young,
Kim Ahhyun,
Oh WooSuk,
Shong Bonggeun
Publication year - 2017
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25341
Subject(s) - chemistry , thio , bifunctional , reactivity (psychology) , yield (engineering) , transition state , nucleophile , computational chemistry , photochemistry , inorganic chemistry , organic chemistry , thermodynamics , catalysis , medicine , physics , alternative medicine , pathology
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 NH 2 /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/Brønsted 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.