Supramolecular synthons mediated by weak hydrogen bonding: forming linear molecular arrays via CC–H···NC and CC–H···O2N recognition

Langley, Philip J.; Hulliger, Jürg; Thaimattam, Ram; Desiraju, Gautam R.

doi:10.1039/a807552b

Cited by 58 publications

(46 citation statements)

References 5 publications

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“…Modern crystal engineering has emerged as a wealthy discipline whose success requires an iterative process of synthesis, crystallography and crystal structure analysis. The C"C-HÁÁÁO 2 N and C"C-HÁÁÁNC hydrogen bond motifs have been defined as supramolecular synthons by Desiraju and co-workers [9].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of mono and doubly alkynyl substituted ferrocene and its crystal engineering using –C–H···O supramolecular synthon

Thakur

Adarsh

Chakraborty

et al. 2010

Journal of Organometallic Chemistry

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Section: Introductionmentioning

confidence: 99%

Synthesis of mono and doubly alkynyl substituted ferrocene and its crystal engineering using –C–H···O supramolecular synthon

Thakur

Adarsh

Chakraborty

et al. 2010

Journal of Organometallic Chemistry

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“…They are responsible for conformational preference, crystal packing, host–guest complexation, self‐organization processes, biomolecular structure, and even for chemical reaction 1–3. Such interactions can be classified in a range from strong interactions such as conventional hydrogen bonds 4–6, to weak ones such as unconventional hydrogen bonds 7–9, CH/π interactions 10–12, and π–π stacking 13–16. Recently, weak dimer interactions of halogen atoms (Lewis acids) with neutral or anionic Lewis bases are under active investigation 17–26.…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation on charge‐assisted halogen bonding interactions in the complexes of bromocarbons with some anions

Wang

Zou

et al. 2007

Int J of Quantum Chemistry

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A series of dimeric complexes formed between bromocarbon molecules and two anions (Br Ϫ and CN Ϫ ) have been investigated by using MP2 method. The quantum theory of atoms in molecules (QTAIM) and the second-order perturbation natural bond orbital (NBO) approaches were applied to analyze the electron density distributions of these complexes and to explore the nature of charge-assisted halogen bonding interactions. As anticipated, these interactions are significantly stronger relative to the corresponding neutral ones. The results derived from ab initio calculations described herein reveal a major contribution from the electrostatic interaction on the stability of the systems considered. Beside the electrostatic interaction, the charge-transfer force and the second-order orbital interaction also play an important role in the formation of the complexes, as a NBO analysis suggested. The presence of halogen bonds in the complexes has been identified in terms of the QTAIM methodology, and several linear relationships have been established to provide more insight into charge-assisted halogen bonding interactions.

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“…NMR observations, [19,20] supported by computational studies, [21] on simple aliphatic aldehydes suggest that conformations predominate in which the carbonyl oxygen is eclipsed either by hydrogen or alkyl at the a-position as shown in Fig. 10.…”

Section: Discussionmentioning

confidence: 84%

Steric effects and mechanism in the formation of hemi‐acetals from aliphatic aldehydes

Daw

Regan

Watt

et al. 2013

J of Physical Organic Chem

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a Some physical properties (pK a , log P OW , boiling points) of hexanoic acid 1 (X = COOH) and its seven isomers 2-8 (X = COOH) are reported. Hexanal 1 (X = CHO) and its seven isomeric aldehydes 2-8 (X = CHO) are shown to equilibrate, in methanol solution, with their hemi-acetals. Logarithms of equilibrium constants correlate with values of E s for the isomeric C 5 H 11 substituents, and with logs of relative rates for saponification of the corresponding methyl esters with r = 0.52, reflecting the reduced steric demand of hydrogen compared to oxygen in the quaternization of ester and aldehydic carbonyl groups. Rates of equilibration have also been measured in buffered methanol. For hexanal, with a 2:1 Et 3 N: AcOH buffer, the buffer-independent contribution is dominated by the methoxide catalysed pathway. Rates in this medium have been determined for isomers 1 -8 (X = CHO), and their logarithms do not correlate with logarithms of equilibrium constants for hemi-acetal formation or with substituent steric parameters derived from ester formation or saponification, indicating that the steric changes associated with full quaternization of the carbonyl group are not mirrored in the transition structures for hemi-acetal formation. It is suggested that transition states for hemi-acetal formation are relatively early so that steric interactions are effectively those between the nucleophile and ground state conformations of the aldehydes. A comparison of the entropies of hemi-acetal formation with entropies of activation has provided a basis for a suggested transition structure. Comparisons with acid chloride hydrolyses are made.

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Supramolecular synthons mediated by weak hydrogen bonding: forming linear molecular arrays via CC–H···NC and CC–H···O2N recognition

Cited by 58 publications

References 5 publications

Synthesis of mono and doubly alkynyl substituted ferrocene and its crystal engineering using –C–H···O supramolecular synthon

Synthesis of mono and doubly alkynyl substituted ferrocene and its crystal engineering using –C–H···O supramolecular synthon

Theoretical investigation on charge‐assisted halogen bonding interactions in the complexes of bromocarbons with some anions

Steric effects and mechanism in the formation of hemi‐acetals from aliphatic aldehydes

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