Ab Initio Study of Possible and Preferred Basic Site(s) in PolyfunctionalN,N1-Dimethyl-N-cyanoformamidine

Makowski, Mariusz; Raczyńska, Ewa D.; Chmurzyński, Lech

doi:10.1021/jp002458t

Cited by 30 publications

(37 citation statements)

References 51 publications

(79 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Note that for N‐cyano‐N′,N′‐dimethylformamidine protonation on the CN group has been demonstrated to be preferred over the imino nitrogen by ca . 30 kJ/mol (MP2/(‐31G*//HF/6‐31G* calculations).…”

Section: Nitrogen Substituted Cyanidesmentioning

confidence: 99%

Gas phase basicities of polyfunctional molecules. Part 6: Cyanides and isocyanides

Bouchoux

2017

Mass Spectrometry Reviews

View full text Add to dashboard Cite

This paper gathers structural and thermochemical informations related to the gas-phase basicity of molecules containing cyanides (nitriles) and isocyanides (isonitriles) functional groups. It constitutes the sixth part of a general review devoted to gas-phase basicities of polyfunctional compounds. A large corpus of cyanides and isocyanides molecules is examined under seven major chapters. In the first one, a rapid overview of the definitions and methods leading to gas-phase basicity, GB, proton affinity, PA, and protonation entropy, Δ S°, is given. In the same chapter, several aspects of the gas phase chemistry of protonated cyanides and isocyanides are also presented. Chapters II-VI detail the protonation energetics of aliphatic, unsaturated, and heteroatom substituted (halogens, O, S, N, P) cyanides. A seventh chapter is devoted to isocyanides. Experimental data available in the literature (120 references) were reevaluated according to the presently adopted basicity scale that is the NIST database anchored to PA(NH ) = 853.6 kJ/mol and GB (NH ) = 819 kJ/mol. In this latter source, however, several erroneous values have been identified which were corrected in the present review. Structural and energetic information given by G4MP2 quantum chemistry computations on ca. 60 typical systems are presented. The present review includes the GB, PA, and Δ S° values of ca. 110 cyanides and isocyanides, and, for selected examples, is completed by a set of computed heats of formation (Δ H°) at 0 and 298 K.

show abstract

Section: Nitrogen Substituted Cyanidesmentioning

confidence: 99%

Gas phase basicities of polyfunctional molecules. Part 6: Cyanides and isocyanides

Bouchoux

2017

Mass Spectrometry Reviews

View full text Add to dashboard Cite

show abstract

“…Thus, the protonation of a neutral basic compound B at a specific donor site is written as follows: (10) The PA can be calculated from Eq. (10) as the negative value of difference in enthalpies of product and reactants as follows [46][47][48]:…”

Section: Protonated Speciesmentioning

confidence: 99%

Corrosion Inhibition Perfomance of Four Natural Thiazole Derivatives: Quantum Chemical and Monte Carlo Simulation Studie

Dao¹

2018

JST

View full text Add to dashboard Cite

Some thiazole derivatives: 2-acetyl-thiazole, 2-isobutyl-thiazole, 4-methyl-5-(2-hydroxyethyl)-thiazole, 2,4,5-trimethyl-thiazole used as corrosion inhibitors for iron were calculated at DFT-PBEPBE/6-31+G(d,p) level of theory and by Monte Carlo simulations. Quantum chemical parameters such as EHOMO, ELUMO, and HOMO and LUMO energy gap, chemical potential ( ), electronegativity , global hardness , softness (S), dipole moment and electrophilicity index have been calculated and discussed in detail to evaluate their inhibiting effectiveness. Mulliken-charges distribution and Fukui function were also calculated in order to visualize the reactive sites of the inhibitor molecules. Calculated results show that 2-acetyl-thiazole represents as the most efficient corrosion inhibitor. The -C4=C5-atomic center of thiazole ring demonstrates as the adsorption site in reaction with metallic surface. Corrosion inhibition effectiveness can be classified in decreasing order: ATZ > TMTZ SFR > ISTZ. Adsorption energies and interaction configurations of the four thiazole derivatives on Fe (110) were obtained using the Monte Carlo simulations. The results indicate that sulphur and nitrogen atoms as well as π-electronic systems within the thiazole ring aided the interaction between the inhibitor molecules and the Fe surface. All the four thiazole molecules adsorbed in parallel orientations on Fe (110) surface which ensures strong interactions with Fe. The adsorption energies were in accord with the results obtained using quantum chemical calculations.

show abstract

“…An impressive number of substituted amidines has been experimentally studied by Raczynska and co‐workers mostly in the 1990s (Borgarello et al, ; Decouzon et al, ; Raczynska et al, , ; Decouzon et al, ; Raczynska et al, ; Raczynska, Maria, & Gal, ; Raczynska, Mishima, & Yahia, ; Makowski, Raczynska, & Chmurzynski, ). The authors obtained GB values from proton transfer equilibrium constant determination on an ICR mass spectrometer.…”

Section: Amidinesmentioning

confidence: 99%

Gas phase basicities of polyfunctional molecules. Part 5: Non‐aromatic sp² nitrogen containing compounds

Bouchoux

Eckert‐Maksić

2016

Mass Spectrometry Reviews

View full text Add to dashboard Cite

This paper constitutes the fifth part of a general review of the gas-phase protonation thermochemistry of polyfunctional molecules (Part 1: Theory and methods, Mass Spectrom Rev 2007, 26:775-835, Part 2: Saturated basic sites, Mass Spectrom Rev 2012, 31:353-390, Part 3: Amino acids, Mass Spectrom Rev 2012, 31:391-435, Part 4: Carbonyl as basic site, Mass Spectrom Rev 2015, 34:493-534). This part is devoted to non-aromatic molecules characterized by a lone pair located on a sp nitrogen atom, it embraces functional groups such as imines, amidines, guanidines, diazenes, hydrazines, oximes, and phosphazenes. Specific examples are examined under five major chapters. In the first one, aliphatic and unsaturated (conjugated and cyclic) imines, hydrazones, and oximes are considered. A second chapter describes the protonation energetic of aliphatic, conjugated, or cyclic amidines. Guanidines, polyguanides, and biomolecules containing guanidine were examined in the third chapter. A fourth chapter describes the particular case of the phosphazene molecules. Finally, diazenes and azides were considered in the last chapter. Experimental data were re-evaluated according to the presently adopted basicity scale, i.e., PA(NH ) = 853.6 kJ/mol, GB (NH ) = 819 kJ/mol. Structural and energetic information given by G4MP2 quantum chemistry computations on typical systems are presented. © 2016 Wiley Periodicals, Inc. Mass Spec Rev 37:139-170, 2018.

show abstract

Ab Initio Study of Possible and Preferred Basic Site(s) in PolyfunctionalN,N¹-Dimethyl-N-cyanoformamidine

Cited by 30 publications

References 51 publications

Gas phase basicities of polyfunctional molecules. Part 6: Cyanides and isocyanides

Gas phase basicities of polyfunctional molecules. Part 6: Cyanides and isocyanides

Corrosion Inhibition Perfomance of Four Natural Thiazole Derivatives: Quantum Chemical and Monte Carlo Simulation Studie

Gas phase basicities of polyfunctional molecules. Part 5: Non‐aromatic sp² nitrogen containing compounds

Contact Info

Product

Resources

About

Ab Initio Study of Possible and Preferred Basic Site(s) in PolyfunctionalN,N1-Dimethyl-N-cyanoformamidine

Cited by 30 publications

References 51 publications

Gas phase basicities of polyfunctional molecules. Part 6: Cyanides and isocyanides

Gas phase basicities of polyfunctional molecules. Part 6: Cyanides and isocyanides

Corrosion Inhibition Perfomance of Four Natural Thiazole Derivatives: Quantum Chemical and Monte Carlo Simulation Studie

Gas phase basicities of polyfunctional molecules. Part 5: Non‐aromatic sp2 nitrogen containing compounds

Contact Info

Product

Resources

About

Ab Initio Study of Possible and Preferred Basic Site(s) in PolyfunctionalN,N¹-Dimethyl-N-cyanoformamidine

Gas phase basicities of polyfunctional molecules. Part 5: Non‐aromatic sp² nitrogen containing compounds