Theoretical studies on the S—N interaction in sulfinamides

Bharatam, Prasad V.; Amita,; Kaur, Deepinder

doi:10.1002/poc.465

Cited by 27 publications

(12 citation statements)

References 61 publications

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“…Experimental or G 2 (MP 2 )‐calculated HOFs of references are listed in Table . G 2 (MP 2 )‐calculated HOF of NH 3 (−41.28 kJ/mol) is quite close to its experimental value (−45.90 kJ/mol), which well agrees with previous reports that G 2 (MP 2 ) theory can predict HOFs accurately …”

Section: Resultssupporting

confidence: 90%

“…G 2 (MP 2 )-calculated HOF of NH 3 (À41.28 kJ/mol) is quite close to its experimental value (À45.90 kJ/mol), [27] which well agrees with previous reports that G 2 (MP 2 ) theory can predict HOFs accurately. [31][32][33] Table 2 summarizes gas-phase HOFs, solid-phase HOFs and related parameters of these compounds. Obviously, both gasphase and solid-phase HOFs of these compounds are large and positive, which are favor for HEDMs.…”

Section: Methodsmentioning

confidence: 99%

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Computational study of pyrazine‐based derivatives and their N‐oxides as high energy materials

Lin

Chen

Zhu

et al. 2013

J of Physical Organic Chem

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Gas-phase heats of formation (HOF), solid-phase HOF, detonation properties, electronic structure and thermal stability for a series of polynitro pyrazine derivatives containing three heterocycles have been investigated using density functional theory. It is found that the nitro group is an efficient tool to improve HOF of pyrazine derivatives. Furthermore, detonation velocities and detonation pressures of these compounds are evaluated using empirical Kamlet-Jacobs equations. As a result, it indicates that the nitro group is useful to enhance detonation properties. Detonation velocities of five compounds are 9. 67, 9.20, 9.74, 9.76 and 9.87 km/s, respectively, which are significantly larger than that of HMX (9.10 km/s). Bond dissociation energy is also performed to investigate their thermal stability, showing that thermal stability of these compounds is little affected by nitro groups or the position of substituent groups. Considering solid-phase HOF, detonation properties and thermal stability, some of pyrazine derivatives can be potential high energy density materials.

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Section: Resultssupporting

confidence: 90%

Section: Methodsmentioning

confidence: 99%

Computational study of pyrazine‐based derivatives and their N‐oxides as high energy materials

Lin

Chen

Zhu

et al. 2013

J of Physical Organic Chem

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“…We find only very small electron density changes during rotation, suggesting that the nature of the bond is not affected, Table S1, and thus implying little to no π contributions in this bond. Taken together, our results support previous proposals that rotational barriers are dominated by electron repulsion. − We note that S L 2,3 -edge XAS might allow for direct evaluation of d–p π contributions and are currently exploring this avenue.…”

Section: Discussionsupporting

confidence: 90%

Nature of S–N Bonding in Sulfonamides and Related Compounds: Insights into π-Bonding Contributions from Sulfur K-Edge X-ray Absorption Spectroscopy

Okbinoglu

Kennepohl

2021

J. Phys. Chem. A

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Molecules containing sulfur−nitrogen bonds, like sulfonamides, have long been of interest because of their many uses and interesting chemical properties. Understanding the factors that cause sulfonamide reactivity is important, yet there continues to be controversy regarding the relevance of S−N π bonding in describing these species. In this paper, we use sulfur K-edge X-ray absorption spectroscopy (XAS) in conjunction with density functional theory (DFT) to investigate the role of S 3p contributions to π-bonding in sulfonamides, sulfinamides, and sulfenamides. We explore the nature of the electron distribution of the sulfur atom to its nearest neighbors and widen our scope to its effects on rotational barriers along the sulfur−nitrogen axis. The experimental XAS data together with time-dependent DFT calculations confirm that sulfonamidesand the other sulfinated amides in this serieshave essentially no S−N π bonding involving S 3p contributions and that electron repulsion is the dominant force affecting rotational barriers along the S−N axis.

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“…In this area a great leap forward has been taken since the works of Bharatam who studied the N-S bond rotational barrier, the E : Z isomerization pathway and the charge distribution in sulfinimines using ab initio and DFT methods at the B3LYP/6-31+G* (+ZPE) level. 13,14 Thus, Bharatam demonstrated that sulfinimine 1 exhibits a natural tendency to prefer the conformation C1, wherein the S-O bond and the lone pair of electrons on the nitrogen atom are antiperiplanar (Fig. 1).…”

Section: Structure and Conformation Of Tert-butanesulfiniminesmentioning

confidence: 99%

tert-Butanesulfinimines: structure, synthesis and synthetic applications

et al. 2009

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Since Ellman's seminal works, over the past ten years tert-butanesulfinimines have proved to be useful chiral amino intermediates for organic synthesis. Through highly stereoselective reactions, amongst which reductions, nucleophilic 1,2-additions and ylide condensations, a broad range of nitrogen-containing compounds has been synthesized. Although the stereoselectivity levels are high in most cases, the sense of the stereoinduction is generally not predictable. The object of this critical review is to present the models proposed to rationalize the stereochemical outcome of the reactions involving tert-butanesulfinimines and to point out an obvious lack of homogeneity amongst them (128 references).

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Theoretical studies on the S—N interaction in sulfinamides

Cited by 27 publications

References 61 publications

Computational study of pyrazine‐based derivatives and their N‐oxides as high energy materials

Computational study of pyrazine‐based derivatives and their N‐oxides as high energy materials

Nature of S–N Bonding in Sulfonamides and Related Compounds: Insights into π-Bonding Contributions from Sulfur K-Edge X-ray Absorption Spectroscopy

tert-Butanesulfinimines: structure, synthesis and synthetic applications

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