Intramolecular redox cyclization upon oxidation of a sulfur(II)-containing diazene: X-ray structures of (Ar = 4-CH3C6H4) and MeSO2N(4-CH3C6H4)CN=NC(C6H4CH3-4)NSO2Me

Chandrasekhar, Vadapalli; Chivers, Tristram; Ellis, Laura; Krouse, Ian H.; Parvez, Masood; Vargas‐Baca, Ignacio

doi:10.1139/v97-143

Cited by 9 publications

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“…The dominant part of the published examples deals with stabilization through CB of certain conformation either in starting compounds or in intermediates. These works include the application of the chiral isothiourea derivatives as organocatalysts that act via formation of intramolecular S···O CB in the intermediate, stabilization of an intermediate in Pummerer reaction by inter- and intramolecular S···O contacts, facilitation of the intramolecular redox cyclization of S-containing diazene, the photocyclization of 2,3-dithiazolylbenzothiophene, and the bond-switch rearrangement of substituted isothiadiazoles and isothiazoles by formation in both cases intramolecular S···N CBs in the starting compounds. The other reports disclose electronic effects of CB on the reaction center, viz.…”

Section: Introductionmentioning

confidence: 99%

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

et al. 2016

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The reaction of cis-[PdCl(CNXyl)] (Xyl = 2,6-MeCH) with various 1,3-thiazol- and 1,3,4-thiadiazol-2-amines in chloroform gives a mixture of two regioisomeric binuclear diaminocarbene complexes. For 1,3-thiazol-2-amines the isomeric ratio depends on the reaction conditions and kinetically (KRs) or thermodynamically (TRs) controlled regioisomers were obtained at room temperature and on heating, respectively. In CHCl solutions, the isomers are subject to reversible isomerization accompanied with the cleavage of Pd-N and С-N bonds in the carbene fragment XylNCN(R)Xyl. Results of DFT calculations followed by the topological analysis of the electron density distribution within the formalism of Bader's theory (AIM method) reveal that in CHCl solution the relative stability of the regioisomers (∆G = 1.2 kcal/mol; ∆G = 3.2 kcal/mol) is determined by the energy difference between two types of the intramolecular chalcogen bonds, viz. S•••Cl in KRs (2.8-3.0 kcal/mol) and S•••N in TRs (4.6-5.3 kcal/mol). In the case of the 1,3,4-thiadiazol-2-amines, the regioisomers are formed in approximately equal amounts and, accordingly, the energy difference between these species is only 0.1 kcal/mol in terms of ∆G (∆G = 2.1 kcal/mol). The regioisomers were characterized by elemental analyses (C, H, N), HRESI-MS and FTIR, 1D (H, C) and 2D (H,H-COSY, H,H-NOESY, H,C-HSQC, H,C-HMBC) NMR spectroscopies, and structures of six complexes (three KRs and three TRs) were elucidated by single-crystal X-ray diffraction.

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Section: Introductionmentioning

confidence: 99%

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

et al. 2016

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“…On the other hand, the reaction of diazene 63c with MCPBA resulted in ring closure via an intramolecular redox process to give the 1,2,3,5-thiatriazole derivative 64 [41].…”

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confidence: 99%

Poly-sulfur-nitrogen heterocycles via sulfur chlorides and nitrogen reagents

Torroba

1999

J. prakt. Chem.

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Nitrogen and sulfur organic aromatic heterocycles are formally derived from aromatic carbon cycles by a heteroatom taking the place of a ring carbon atom or a complete CH=CH group. The presence of heteroatoms results in significant changes in the cyclic molecular structure due to the availability of unshared pairs of electrons and the difference in electronegativity between heteroatoms and carbon. Therefore, nitrogen and sulfur heterocyclic compounds display physicochemical characteristics and reactivity far from the parent aromatic hydrocarbons. On the other hand, the presence of many nitrogen and sulfur atoms in a ring is normally associated with instability and difficulties in the synthesis but, in fact, surprisingly stable heterocycles with unusual properties can be frequently obtained from simple or- Poly-Sulfur-Nitrogen Heterocycles via Sulfur Chlorides and Nitrogen ReagentsTomás Torroba* Burgos/Spain, Departamento de Química, Facultad de Ciencias, Universidad Received October 28th, 1998, respectively January 4th, 1999Keywords: Conducting materials, Nitrogen heterocycles, Phosphorus heterocycles, Selenium, Sulfur heterocycles Abstract: The family of poly-sulfur-nitrogen heterocycles includes highly stable aromatic compounds that display physicochemical properties with relevance in the design of new materials, especially those relating to molecular conductors and magnets. The interesting characteristics found in many of these heterocycles have led to the development of modern synthetic methods that are the subject of this review. Heterocycles such as 1,2,3-and 1,2,5-thiadiazoles, 1,2,3-and 1,3,2-dithiazoles, 1,2,3,5-dithiadiazoles, thiatriazines, trithiadiganic substrates and the appropriate inorganic reagent. This paper reviews the most common synthetic methods to obtain poly-sulfur-nitrogen heterocyclic systems that lie in the middle way between organic and inorganic chemistry. Carbon atoms confer high stability to such rings, according to the aromaticity and antiaromaticity rules, and the nitrogen-sulfur core gives unusual properties to the compounds, in accordance with their electron rich π-excessive nature. The physicochemical properties of this family of compounds have relevance in the design of new materials, specially concerning organic conductors. In contrast with the number and variety of such heterocycles, the number of synthetic methods to afford them is, in practice, restricted to the availability of the appropriate sulfur reagent. The classification of synthetic methods follows the applications of the most common sulfur reagents to the synthesis of heteroaromatic carbon-nitrogen-sulfur rings and sometimes extends to selenium or phosphorus related heterocycles. Binary inorganic sulfur-nitrogen cycles are covered by some reports from Chivers and Oakley [1]. Some binary S-N rings, as B-F in figure 1, constitute the models and sometimes precursors of the organic members of the series.azines, dithia(and trithia)diazepines, trithiatriazepines, dithia(and trithia)tetrazozines, and fused systems are mo...

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Benzeneselenenyl Chloride

Iwaoka¹,

Tomoda²,

Rayner³

et al. 2004

Encyclopedia of Reagents for Organic Synthesis

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Intramolecular redox cyclization upon oxidation of a sulfur(II)-containing diazene: X-ray structures of (Ar = 4-CH₃C₆H₄) and MeSO₂N(4-CH₃C₆H₄)CN=NC(C₆H₄CH₃-4)NSO₂Me

Cited by 9 publications

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Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

Poly-sulfur-nitrogen heterocycles via sulfur chlorides and nitrogen reagents

Benzeneselenenyl Chloride

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Intramolecular redox cyclization upon oxidation of a sulfur(II)-containing diazene: X-ray structures of (Ar = 4-CH3C6H4) and MeSO2N(4-CH3C6H4)CN=NC(C6H4CH3-4)NSO2Me

Cited by 9 publications

References 0 publications

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)PdII Complexes

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)PdII Complexes

Poly-sulfur-nitrogen heterocycles via sulfur chlorides and nitrogen reagents

Benzeneselenenyl Chloride

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Intramolecular redox cyclization upon oxidation of a sulfur(II)-containing diazene: X-ray structures of (Ar = 4-CH₃C₆H₄) and MeSO₂N(4-CH₃C₆H₄)CN=NC(C₆H₄CH₃-4)NSO₂Me

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes

Difference in Energy between Two Distinct Types of Chalcogen Bonds Drives Regioisomerization of Binuclear (Diaminocarbene)Pd^II Complexes