Nature and physical origin of CH/π interaction: significant difference from conventional hydrogen bonds

Tsuzuki, Seiji; Fujii, Asuka

doi:10.1039/b718656h

Cited by 322 publications

(313 citation statements)

References 107 publications

Supporting

Mentioning

295

Contrasting

Unclassified

Order By: Relevance

“…1,2,4 The detailed nature of such interactions remains insufficiently understood, and may include aspects such as charge transfer contributions from the π system to C-H antibonding orbitals, as well as London dispersion. [5][6][7][8] Deeper understanding will benefit from quantitative characterization of systems such as the bimolecular complexes presented here.…”

Section: Introductionmentioning

confidence: 99%

“…20,21 Again a linear correlation with the average molecular polarizabilities was found. 6,7 Currently, we are extending measurement of D 0 (S 0 ) values to more complex and chemically relevant cases such as 1-naphthol (1-NpOH) with hydrocarbons. In these complexes, the 1-NpOH can act as a non-classical H-bond donor to the alkane, or the alkane can act as a CH/π donor.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Maity

Knochenmuss

Holzer

et al. 2016

The Journal of Chemical Physics

View full text Add to dashboard Cite

Articles you may be interested inInfluences of the propyl group on the van der Waals structures of 4-propylaniline complexes with one and two argon atoms studied by electronic and cationic spectroscopy J. Chem. Phys. 143, 034308 (2015); 10.1063/1.4927004The weak hydrogen bond in the fluorobenzene-ammonia van der Waals complex: Insights into the effects of electron withdrawing substituents on π versus in-plane bonding J. Chem. Phys. 126, 154319 (2007) The 1-naphthol·cyclopropane intermolecular complex is formed in a supersonic jet and investigated by resonant two-photon ionization (R2PI) spectroscopy, UV holeburning, and stimulated emission pumping (SEP)-R2PI spectroscopy. Two very different structure types are inferred from the vibronic spectra and calculations. In the "edge" isomer, the OH group of 1-naphthol is directed towards a C-C bond of cyclopropane, the two ring planes are perpendicular. In the "face" isomer, the cyclopropane is adsorbed on one of the π-aromatic faces of the 1-naphthol moiety, the ring planes are nearly parallel. Accurate ground-state intermolecular dissociation energies D 0 were measured with the SEP-R2PI technique. The D 0 (S 0 ) of the edge isomer is bracketed as 15.35 ± 0.03 kJ/mol, while that of the face isomer is 16.96 ± 0.12 kJ/mol. The corresponding excited-state dissociation energies D 0 (S 1 ) were evaluated using the respective electronic spectral shifts. Despite the D 0 (S 0 ) difference of 1.6 kJ/mol, both isomers are observed in the jet in similar concentrations, so they must be separated by substantial potential energy barriers. Intermolecular binding energies, D e , and dissociation energies, D 0 , calculated with correlated wave function methods and two dispersion-corrected density-functional methods are evaluated in the context of these results. The density functional calculations suggest that the face isomer is bound solely by dispersion interactions. Binding of the edge isomer is also dominated by dispersion, which makes up two thirds of the total binding energy. Published by AIP Publishing. [http://dx

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Maity

Knochenmuss

Holzer

et al. 2016

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Considered as the weakest form of hydrogen bonding, C-H/π interactions are largely dispersive in nature, and are very probably much more common in organic and organometallic chemistry than would be apparent from many simple models. 35 In the present system, this appears to be crucial for stereselectivity.…”

Section: Scheme 6 Postulated Catalytic Cycle Using Dmd and Catalyst Imentioning

confidence: 71%

Delineating Origins of Stereocontrol in Asymmetric Pd-Catalyzed α-Hydroxylation of 1,3-Ketoesters

et al. 2010

View full text Add to dashboard Cite

Abstract. Systematic studies of reaction conditions and subsequent optimization led to the identification of important parameters for stereoselectivity in the asymmetric α-hydroxylation reaction of 1,3-ketoesters. Enantioselectivities of up to 98% can be achieved for cyclic substrates and 88% for acyclic ketoesters. Subsequently, the combination of cyclic/acyclic ketoester, catalyst and oxidant was found to have a profound effect on reaction rates. The stereochemistry of the reaction contradicts that observed for other similar electrophilic substitution reactions.This was rationalized by transition state modeling, which revealed a number of cooperative weak interactions between oxidant, ligand and counterion, together with C-H/π interactions that cumulatively account for the unusual stereoselectivity.2

show abstract

“…time P tot partial pressure ratio encapsulation ratio equilibrium constant entry ( literature [21]. In the temperature range above 170 • C, D 2 showed slightly stronger binding affinity than H 2 presumably due to quantum effect [13].…”

Section: Resultsmentioning

confidence: 99%

Recognition of hydrogen isotopomers by an open-cage fullerene

Murata

Chuang

Tanabe

et al. 2013

Phil. Trans. R. Soc. A.

View full text Add to dashboard Cite

We present our study on the recognition of hydrogen isotopes by an open-cage fullerene through determination of binding affinity of isotopes H 2 /HD/D 2 with the open-cage fullerene and comparison of their relative molecular sizes through kinetic-isotope-release experiments. We took advantage of isotope H 2 /D 2 exchange that generated an equilibrium mixture of H 2 /HD/D 2 in a stainless steel autoclave to conduct high-pressure hydrogen insertion into an open-cage fullerene. The equilibrium constants of three isotopes with the open-cage fullerene were determined at various pressures and temperatures. Our results show a higher equilibrium constant for HD into open-cage fullerene than the other two isotopomers, which is consistent with its dipolar nature. D 2 molecule generally binds stronger than H 2 because of its heavier mass; however, the affinity for H 2 becomes larger than D 2 at lower temperature, when size effect becomes dominant. We further investigated the kinetics of H 2 /HD/D 2 release from open-cage fullerene, proving their relative escaping rates. D 2 was found to be the smallest and H 2 the largest molecule. This notion has not only supported the observed inversion of relative binding affinities between H 2 and D 2 , but also demonstrated that comparison of size difference of single molecules through non-convalent kinetic-isotope effect was applicable.

show abstract

Nature and physical origin of CH/π interaction: significant difference from conventional hydrogen bonds

Cited by 322 publications

References 107 publications

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Accurate dissociation energies of two isomers of the 1-naphthol⋅cyclopropane complex

Delineating Origins of Stereocontrol in Asymmetric Pd-Catalyzed α-Hydroxylation of 1,3-Ketoesters

Recognition of hydrogen isotopomers by an open-cage fullerene

Contact Info

Product

Resources

About