Hydrogen bonding and other polar interactions of 1-, 2-, and 4-octyne with organic solvents

1983 ◽  
Vol 61 (9) ◽  
pp. 2044-2047 ◽  
Author(s):  
John H. Hallman ◽  
W. Kirk Stephenson ◽  
Richard Fuchs
Keyword(s):  
Hydrogen Bond ◽  
Bond Formation ◽  
Butyl Ether ◽  
Hexamethylphosphoric Triamide ◽  
Hydrogen Bond Formation ◽  
Enthalpies Of Transfer ◽  
Induced Dipole ◽  
Base Method ◽  
Polar Interactions ◽  
Heats Of Vaporization

The heats of vaporization of 1-octyne (10.11 ± 0.02 kcal/mol), 2-octyne (10.63 ± 0.03 kcal/mol), and 4-octyne (10.21 ± 0.02 kcal/mol) have been determined. Heats of solution of the liquid octynes and n-octane have been measured in heptane, cyclohexane, 1,2-dichloroethane, n-butyl ether, ethanol, triethylamine, dimethyl sulfoxide, butyrolactone, dimethylformamide, and hexamethylphosphoric triamide. Enthalpies of transfer from vapor to each solvent have been calculated. Enthalpies of hydrogen bond formation, calculated by the pure base method, become more exothermic in the above solvent order. Correlations with the Taft–Kamlet solvent parameters π* and β indicate that other polar interactions (presumably dipole – induced dipole) are appreciably larger for 1-octyne than for 2- and 4-octyne.

Enthalpies of interaction of polar and nonpolar molecules with aromatic solvents

1982 ◽  
Vol 60 (15) ◽  
pp. 1953-1958 ◽  
Author(s):  
Richard Fuchs ◽  
L. Alan Peacock ◽  
W. Kirk Stephenson
Keyword(s):  
Hydroxyl Group ◽  
Enthalpies Of Solution ◽  
Butyl Ether ◽  
Aromatic Solvent ◽  
Aromatic Solvents ◽  
Induced Dipole ◽  
Or Groups ◽  
Polar Solutes ◽  
Base Method ◽  
Heats Of Vaporization

Enthalpies of solution of representative ketones, phenols, alcohols, and ethers have been determined in α,α,α-trifluorotoluene, benzene, toluene, and mesitylene, and combined with heats of vaporization to give enthalpies of transfer from vapor to the aromatic solvents [ΔH(v→S)]. Comparison of these values with ΔH(v→S) of nonpolar model compounds provides an estimate of the special interactions (dipole – induced dipole or charge transfer, and hydrogen bonding) of the polar solutes with each aromatic solvent. Unless the model compound is perfectly matched, an alternative procedure, the pure base method, is superior for evaluating hydrogen bonding.The special interactions of ketones and ethers with aromatic solvents increase with decreasing π electron density of the solvent. By contrast, m-cresol shows the strongest special interaction with the most electron-rich solvent (mesitylene > toluene > benzene > trifluorotoluene). These results demonstrate that —OH and —OR groups undergo quite different interactions, and that a distinctive interaction occurs between the hydroxyl group and the aromatic ring.Calorimetric heats of vaporization have been measured for the solutes n-butyl ether (10.68 ± 0.02 kcal/mol), 2,2,4,4-tetramethylpentane (9.20 ± 0.03), n-pentane (6.36 ± 0.02), 1-butanol (12.46 ± 0.00), and 2-methyl-2-butanol (11.94 + 0.02).

Enthalpies of hydrogen bond formation of 1-octanol with aprotic organic solvents. A comparison of the solvation enthalpy, pure base, and non-hydrogen-bonding baseline methods

1985 ◽  
Vol 63 (2) ◽  
pp. 342-348 ◽  
Author(s):  
W. Kirk Stephenson ◽  
Richard Fuchs
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Bond Formation ◽  
Enthalpies Of Solution ◽  
Dispersion Interactions ◽  
Butyl Ether ◽  
Hydrogen Bond Formation ◽  
Solvation Enthalpy ◽  
Benzene Toluene ◽  
Good Agreement

Enthalpies of solution (ΔHs) of 1-octanol and five model compounds (di-n-butyl ether, n-heptyl methyl ether, 1-fluoro-octane, 1-chlorooctane, and n-octane) have been determined in 13 solvents (heptane, cyclohexane, CCl4, 1,1,1-trichloro-ethane, 1,2-dichloroethane, triethylamine, butyl ether, ethyl acetate, DMF, DMSO, benzene, toluene, mesitylene), and combined with heats of vaporization to give enthalpies of transfer from vapor to solvent (ΔH(v → S)). These values have been used to calculate the enthalpy of hydrogen bond formation (ΔHh) of 1-octanol with each solvent, using the pure base (PB), solvation enthalpy (SE), and non-hydrogen-bonding baseline (NHBB) methods. Evidence is presented suggesting that (a) the SE method is susceptible to mismatches of the 1-octanol vs. model polar and dispersion interactions, (b) the PB method is sensitive to polar interaction mismatches, whereas (c) the NHBB method compensates for both polar and dispersion interactions mismatches. The (apparent) ΔHh values determined by the SE and PB methods may be as much as several kcal/mol (nearly 50%) too large, because of the inclusion of other polar and dispersion interactions. The NHBB method is therefore preferred for determining enthalpies of H-bond formation from calorimetric data. However, apparent ΔHh values from the SE and PB methods can be incorporated into total solvatochromic equations using Taft–Kamiet π*, β, and ξ parameters, to provide enthalpies of H-bond formation in good agreement with ΔHh (NHBB).

Enthalpies of interaction of ketones with organic solvents

1985 ◽  
Vol 63 (2) ◽  
pp. 336-341 ◽  
Author(s):  
W. Kirk Stephenson ◽  
Richard Fuchs
Keyword(s):  
Organic Solvents ◽  
Bond Formation ◽  
Butyl Alcohol ◽  
Enthalpies Of Solution ◽  
Butyl Ether ◽  
Hydrogen Bond Formation ◽  
Linear Relationships ◽  
Benzene Toluene ◽  
Polar Interactions ◽  
Alcohol Solvents

Enthalpies of solution (ΔHS) of a series of ketones (acetone, 2-butanone, 2-heptanone, 2-nonanone, 5-nonanone, 2,2,4,4-tetramethyl-3-pentanone, cyclohexanone) and alkane model compounds (n-heptane, n-nonane, 2,2,4,4-tetramethylpentane, cyclohexane) have been determined in 17 organic solvents (n-heptane, cyclohexane, CCl4, α,α,α,-trifluorotoluene, 1,2-dichloroethane, triethylamine, butyl ether, ethyl acetate, DMF, DMSO, benzene, toluene, mesitylene, 1-octanol, methanol, t-butyl alcohol, 2,2,2-trifluoroethanol), and combined with heats of vaporization to give enthalpies of transfer from vapor to solvent (ΔH(v → S)). These values have been used to evaluate ketone–solvent polar interactions (ΔΔH(v → S) = ΔH(v → S)(ketone) − ΔH(v → S)(alkane)). The linear relationships between ΔΔH(v → S) and solvent dipolarity-polarizability (Taft-Kamlet π* parameters) are derived. Based on the deviations from these correlations, ketone–CF3CH2OH enthalpies of hydrogen bond formation have been evaluated. The other alcohol solvents show no evidence of exothermic H-bond formation with ketones.

Enthalpies of interaction of aromatic solutes with organic solvents

1985 ◽  
Vol 63 (9) ◽  
pp. 2529-2534 ◽  
Author(s):  
W. Kirk Stephenson ◽  
Richard Fuchs
Keyword(s):  
Organic Solvents ◽  
Butyl Alcohol ◽  
Model Compounds ◽  
Butyl Ether ◽  
Enthalpies Of Transfer ◽  
Benzene Toluene ◽  
Polar Interactions ◽  
S Model ◽  
Heats Of Vaporization ◽  
Butyl Methyl Ether

Heats of solution of several aromatic solutes (benzene, toluene, mesitylene, nitrobenzene, α,α,α-trifluorotoluene, anisole) and model compounds (n-butyl methyl ether, cyclohexane) in 17 organic solvents (n-heptane, cyclohexane, carbon tetrachloride, 1,2-dichloroethane, α,α,α-trifluorotoluene, triethylamine, butyl ether, ethyl acetate, dimethylformamide, dimethyl sulfoxide, benzene, toluene, mesitylene, t-butyl alcohol, 1-octanol, methanol, 2,2,2-trifluoroethanol) have been combined with solute heats of vaporization to give enthalpies of transfer from vapor to solvent (ΔH(v → S)). Differences between solute and model values (ΔΔH(v → S) = ΔH(v → S) (aromatic solute)–ΔH(v → S) (model) were used to evaluate aromatic solute–solvent polar interactions. Correlations of ΔΔH(v → S) with solvent dipolarity–polarizability (Taft–Kamlet π* parameter) have been determined.

Vapochromism induced by intermolecular electron transfer coupled with hydrogen-bond formation in zinc dithiolene complex

2020 ◽  
Vol 8 (42) ◽  
pp. 14939-14947
Author(s):  
So Yokomori ◽  
Shun Dekura ◽  
Tomoko Fujino ◽  
Mitsuaki Kawamura ◽  
Taisuke Ozaki ◽  
...  
Keyword(s):  
Hydrogen Bond ◽  
Electron Transfer ◽  
Bond Formation ◽  
Intermolecular Electron Transfer ◽  
Hydrogen Bond Formation ◽  
Complex Crystal

A novel vapochromic mechanism by intermolecular electron transfer coupled with hydrogen-bond formation was realized in a zinc dithiolene complex crystal.

Diverse mechanisms of carbon-hydrogen bond formation through binuclear reductive elimination reactions

1982 ◽  
Vol 104 (2) ◽  
pp. 619-621 ◽  
Author(s):  
Mario J. Nappa ◽  
Roberto Santi ◽  
Steven P. Diefenbach ◽  
Jack Halpern
Keyword(s):  
Hydrogen Bond ◽  
Bond Formation ◽  
Reductive Elimination ◽  
Hydrogen Bond Formation ◽  
Elimination Reactions

Theoretical analysis of the (HNO)2, (HNO···HNS), and (HNS)2 dimers — A case of red and blue shifts of N–H stretching frequency

2010 ◽  
Vol 88 (8) ◽  
pp. 849-857 ◽  
Author(s):  
Nguyen Tien Trung ◽  
Tran Thanh Hue ◽  
Minh Tho Nguyen
Keyword(s):  
Hydrogen Bond ◽  
Quantum Chemical ◽  
Bond Formation ◽  
Blue Shift ◽  
Proton Donor ◽  
Basis Sets ◽  
Coupled Cluster ◽  
Hydrogen Bond Formation ◽  
Length Contraction ◽  
Moller Plesset

The hydrogen-bonded interactions in the simple (HNZ)2 dimers, with Z = O and S, were investigated using quantum chemical calculations with the second-order Møller–Plesset perturbation (MP2), coupled-cluster with single, double (CCSD), and triple excitations (CCSD(T)) methods in conjunction with the 6-311++G(2d,2p), aug-cc-pVDZ, and aug-cc-pVTZ basis sets. Six-membered cyclic structures were found to be stable complexes for the dimers (HNO)2, (HNS)2, and (HNO–HNS). The pair (HNS)2 has the largest complexation energy (–11 kJ/mol), and (HNO)2 the smallest one (–9 kJ/mol). A bond length contraction and a frequency blue shift of the N–H bond simultaneously occur upon hydrogen bond formation of the N–H···S type, which has rarely been observed before. The stronger the intramolecular hyperconjugation and the lower the polarization of the X–H bond involved as proton donor in the hydrogen bond, the more predominant is the formation of a blue-shifting hydrogen bond.

Internal Hydrogen Bond Formation in a syn-Hydroxyepoxide

Science ◽  
1982 ◽  
Vol 215 (4533) ◽  
pp. 695-696 ◽  
Author(s):  
J. P. GLUSKER ◽  
D. E. ZACHARIAS ◽  
D. L. WHALEN ◽  
S. FRIEDMAN ◽  
T. M. POHL
Keyword(s):  
Hydrogen Bond ◽  
Bond Formation ◽  
Hydrogen Bond Formation ◽  
Internal Hydrogen ◽  
Internal Hydrogen Bond

Influence of Hydrogen Bond Formation on the Photophysics ofN-(2,6-Dimethylphenyl)-2,3-naphthalimide

2004 ◽  
Vol 108 (19) ◽  
pp. 4357-4364 ◽  
Author(s):  
Attila Demeter ◽  
László Ravasz ◽  
Tibor Bérces
Keyword(s):  
Hydrogen Bond ◽  
Bond Formation ◽  
Hydrogen Bond Formation
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