The ionic hydrogen bond and ion solvation. 3. Bonds involving cyanides. Correlations with proton affinities

Speller, C. V.; Meot‐Ner, Michael

doi:10.1021/j100270a020

Cited by 38 publications

(36 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“….B were determined by pulsed HPMS. 26 It was observed that these quantities, noted ΔH°D, present inverse linear correlation with absolute value of the proton affinities differences, ΔPA = |PA(RCN)−PA(B)|. Several relationships ΔH°D = f(ΔPA) were proposed depending upon the nature of the bases B.…”

Section: Proton-bond Complexesmentioning

confidence: 99%

“…A number of experimental and computational studies on proton bonded complexes involving cyanides and isocyanides appeared in the last few decades. Dissociation energies of proton bonded complexes RCNH + …B were determined by pulsed HPMS . It was observed that these quantities, noted ΔH° D , present inverse linear correlation with absolute value of the proton affinities differences, ΔPA = |PA(RCN)−PA(B)|.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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: Proton-bond Complexesmentioning

confidence: 99%

Section: Introductionmentioning

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

“…Such functional groups present favorable conditions for the physical adsorption of proteins via electrostatic interactions between surface elements such as anionic end groups (-COO À ) and the protonated amino groups (-NH 3 þ ) of polypeptides. In addition to charge-charge interactions, hydrogen bonds can form between -NH 3 þ and -COO À or other CO-containing surface groups, with Hbond binding energies between 10 and 30 kcal/mol [38,39,42]. Charged amino acid residues on the exterior of the insulin molecule contribute to its hydrophilicity and can be attracted to the ND surface.…”

Section: Physical Adsorptionmentioning

confidence: 99%

Nanodiamond–insulin complexes as pH-dependent protein delivery vehicles

et al. 2009

View full text Add to dashboard Cite

“…15–20 kJ mol −1 as shown above in Table 8, this quantity attains value in the range 50–150 kJ mol −1 if one partner is an ionic specie. This is established from the experimental determination of intermolecular ionic hydrogen bond energies, that is, the enthalpy of the clustering reaction (c), Δ c H 0 : obtained, for a large number of couples of bases A and B, during the last thirty years (Davidson, Sunner, & Kebarle, 1979; Larson & McMahon, 1982; Mautner, 1984; Mautner & Sieck, 1985; Speller & Mautner, 1985) and for which representative examples are reported in Table 9.…”

Section: Structural and Energetic Aspects Of The Protonationmentioning

confidence: 99%

Gas‐phase basicities of polyfunctional molecules. Part 1: Theory and methods

Bouchoux

2007

Mass Spectrometry Reviews

116

197

View full text Add to dashboard Cite

The experimental and theoretical methods of determination of gas-phase basicities, proton affinities and protonation entropies are presented in a tutorial form. Particularities and limitations of these methods when applied to polyfunctional molecules are emphasized. Structural effects during the protonation process in the gas-phase and their consequences on the corresponding thermochemistry are reviewed and classified. The role of the nature of the basic site (protonation on non-bonded electron pairs or on p-electron systems) and of substituent effects (electrostatic and resonance) are first examined. Then, linear correlations observed between gas-phase basicities and ionization energies or substituent constants are recalled. Hydrogen bonding plays a special part in proton transfer reactions and in the protonation characteristics of polyfunctional molecules. A survey of the main properties of intermolecular and intramolecular hydrogen bonding in both neutral and protonated species is proposed. Consequences on the protonation thermochemistry, particularly of polyfunctional molecules are discussed. Finally, chemical reactions which may potentially occur inside protonated clusters during the measurement of gas-phase basicities or inside a protonated polyfunctional molecule is examined. Examples of bond dissociations with hydride or alkyl migrations, proton transport catalysis, tautomerization, cyclization, ring opening and nucleophilic substitution are presented to illustrate the potentially complex chemistry that may accompany the protonation of polyfunctional molecules. # 2007 Wiley Periodicals, Inc., Mass Spec Rev 26:775-835, 2007

show abstract

The ionic hydrogen bond and ion solvation. 3. Bonds involving cyanides. Correlations with proton affinities

Cited by 38 publications

References 0 publications

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

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

Nanodiamond–insulin complexes as pH-dependent protein delivery vehicles

Gas‐phase basicities of polyfunctional molecules. Part 1: Theory and methods

Contact Info

Product

Resources

About