Amine-sulfur dioxide complexes.  Structure of N,N,N',N'-tetramethyl-p-phenylenediamine-bis(sulfur dioxide)

Childs, Jerry D.; Helm, D. van der; Christian, S. D.

doi:10.1021/ic50148a036

Cited by 26 publications

(7 citation statements)

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“…A Cambridge Structural Database (CSD) search on N…S contacts reported 204 hits, out of which a major part of it belongs to the traditional N…S chalcogen bond interacting between two different partners or between two monomeric units via σ‐hole and a few N…S contacts that formed chalcogen bond through π‐hole present above the S atom. It should be noted that SO 2 has been found to be the only π‐hole source (situated only on S) which interacts with different N‐bases as revealed from CSD search [26–27] . A pictorial depiction of different types of N…S contacts present in crystal structures is shown in Supporting information (Figure SI.1).…”

Section: Introductionmentioning

confidence: 94%

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

et al. 2021

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A theoretical study has been carried out on the π‐hole based chalcogen bonding interaction between SO3 and various pyridines (XC5H4N), at the MP2=full/aug‐cc‐pVTZ level, to obtain a better insight into the nature and strength of N…S bond. Our calculations predict two different types of chalcogen bonded complexes: (1) Type‐A complex is formed via lone pair‐ π‐hole (N…S) interaction, and (2) Type‐B complex is stabilized through π‐hole‐π‐electron interaction. The binding energy of the Type‐A complexes varies between −109.78 and ‐81.56 kJ/mol whereas it ranges between −28.93 and −17.82 kJ/mol for Type‐B complexes. The nature of the N…S bond and the changes in its properties on the influence of electron donating and electron withdrawing substituents have been discussed with the help of various computational tools like AIM, NCI, SAPT and NBO analysis. The binding energy of the Type‐A complexes are found to correlate with the basicity parameters such as PA and Vs,min of the substituted pyridines. The binding energies of the pyridine complexes with SF2, SO2, CS2 and OCS are also computed for finding the effect of variation of Vs,max value of the S‐atom on the binding energy. The 2nd order hyperconjugation interaction energy between LP(N) and σ*(S−O)/LP*(S) is well correlated to the binding energy as: −ΔE=0.11E(2) −20.08. The variation in the bond distances and their corresponding vibrational frequencies of both the interacting partners (XC5H4N and SO3) are discussed in detail.

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Section: Introductionmentioning

confidence: 94%

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

et al. 2021

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“…[18] In contrast, reactions of SO 2 with salts that contain strongly coordinating anions, such as the alkali-metalc hlorides, have only scarcely been investigatedowing to their low solubility in SO 2 . [4] Organic compounds, for example, amines [19] and glycols, [20] are easily miscible with SO 2 and find applicationsa s absorber materials for flue-gas desulfurization. [21] In particular, room-temperature ionic liquids basedo na lkylammonium salts have proved to be valuable for the reversibler emoval of sulfur from flue gas.…”

Section: Introductionmentioning

confidence: 99%

Crown Ether Complexes of Alkali‐Metal Chlorides from SO₂

Kirsten

Rudel

Buchner

et al. 2017

Chemistry A European J

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The structures of alkali-metal chloride SO solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) ]Cl⋅4 SO (3) and [M(12-crown-4) (SO )]Cl⋅4 SO (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO -solvated alkali-metal chlorides [MCl⋅3 SO ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO at ambient temperature was revealed by IR spectroscopy of the neat compounds.

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“…More recently, the crystalline structure of the molecular complex formed by N,N,N',N'-tetramethyl-p-phenylenediamine and sulphur dioxide was determined. 7 In contrasting with the limited knowledge of the structure of such compounds, some of them have found interesting applications as polymerization catalysts' and some aromatic amines proved to be very efficient in the removal of sulphur dioxide from effluent gasesg We have been involved in the vibrational spectroscopy of sulphur dioxide molecular complexes'091' and decided to extend our studies, investigating the interaction of SO, with aniline (ANI), N-methylaniline (NMA), N,N-dimethylaniline (DMA), N , Ndiet hylaniline (DEA), p-phenylenediamine (PPD) and ,V,N,N',N'-tetramethyl-p-phenylenediamine (TPD) by means of Raman and infrared spectroscopy and, in favourable cases, to explore the Raman pre-resonance effect, since in all cases an intense absorption band is present in the near-UV region. ANI, NMA, DMA and DEA were used after distillation of the commercial products over zinc powder.…”

Section: Introduction Experimentalmentioning

confidence: 99%

Raman and infrared spectra of some aromatic amine–sulphur dioxide molecular complexes

Faria

Santos

1988

J Raman Spectroscopy

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The Raman and infrared spectra of the molecular complexes formed by sulphur dioxide and aniline, Nmethylaniline (NMA), N,N-dimethylaniline (DMA), N,N-diethylaniline (DEA), p-phenylenediamine (PPD) and N,N,N',N-tetramethyl-p-phenylenediamine (TPD) were obtained. With NMA, DMA and DEA only minor changes were observed in the vibrational frequencies of the amines and the SO, vibrational shifts show that the complexes are considerably weaker than the well known trimethylaminesulphur dioxide complex. On the other hand, with PPD and TPD there are significant variations in the spectra of the amines on complexation and the shifts of the SOz vibrational frequencies show that the interaction is comparable in strength to that existing in the trimethylaminesulphur dioxide complex. In the anilin-ulphur dioxide complex the spectral data reveal strong intermolecular hydrogen bonding interactions.The pre-resonance enhancement observed for the DMA and TPD complexes confirms the participation of the SO, moiety in the chromophoric group and adds evidence for the change-transfer nature of the interaction.

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Amine-sulfur dioxide complexes. Structure of N,N,N',N'-tetramethyl-p-phenylenediamine-bis(sulfur dioxide)

Cited by 26 publications

References 1 publication

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

Crown Ether Complexes of Alkali‐Metal Chlorides from SO₂

Raman and infrared spectra of some aromatic amine–sulphur dioxide molecular complexes

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Amine-sulfur dioxide complexes. Structure of N,N,N',N'-tetramethyl-p-phenylenediamine-bis(sulfur dioxide)

Cited by 26 publications

References 1 publication

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO3 Molecule

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO3 Molecule

Crown Ether Complexes of Alkali‐Metal Chlorides from SO2

Raman and infrared spectra of some aromatic amine–sulphur dioxide molecular complexes

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Product

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Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

Nature and Strength of the π‐Hole Chalcogen Bonded Complexes between Substituted Pyridines and SO₃ Molecule

Crown Ether Complexes of Alkali‐Metal Chlorides from SO₂