Rotation about Single Bonds in Organic Molecules

Sternhell, S.

doi:10.1016/b978-0-12-378850-4.50052-3

Cited by 16 publications

(3 citation statements)

References 184 publications

(52 reference statements)

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“…Indeed, the degree of this electronic effect manifests itself through electron-withdrawing elements immediately adjacent to the S−S bond (Table ). Restricted rotation about single bonds is not usually influenced solely through stereoelectronic interactions. For instance, well-documented high torsional barriers in amides, − thioamides, ,, sulfenamides, acrylonitriles (DMAAN), and carbamates , are due in part to resonance-induced double-bond character in these systems .…”

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confidence: 99%

Generalized Synthesis and Physical Properties of Dialkoxy Disulfides

Zysman‐Colman

Harpp

2005

J. Org. Chem.

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A substrate study was undertaken in order to probe the scope of S(2)Cl(2) coupling of alcohols to form dialkoxy disulfides. Compounds 1b and 1f are new; along with 1a, 1c, 1h, and 1j, all of the title compounds are fully characterized, and the yields of 1a and 1c have been optimized from previously reported syntheses. The effect of the R-substituent about the OSSO moiety has been carefully probed as yields vary. A substrate and a solvent study of the coalescence behavior of this class was carried out. The origin of the inherently large barrier to rotation and the resultant thermal decomposition pathway is discussed. Both phenomena are shown to be solvent independent; hindered rotation is substrate independent. The decomposition of 1a is ca. 7 kcal/mol higher than the barrier to rotation about the S-S bond. The combined evidence suggests acyclic unsymmetric homolytic cleavage of the dialkoxy disulfide.

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confidence: 99%

Generalized Synthesis and Physical Properties of Dialkoxy Disulfides

Zysman‐Colman

Harpp

2005

J. Org. Chem.

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“…In particular, NMR is used to measure quantum yields for irreversible photochemical reactions (1) and, in addition, NMR branch of photochemically induced polarization of nuclei provides detection of short-lived radicals arising in flash photolysis of substances (2). Being a well-developed NMR tool, dynamic NMR spectroscopy (DNMR) is commonly used to obtain kinetic parameters of dark reversible chemical reactions in solutions (5,6). In addition to the classical (narrow) understanding of DNMR (5), there is an expanded general framework (7).…”

Section: Introductionmentioning

confidence: 99%

NMR application for a study of reversible photochemical kinetics: A multisite case

Babailov

Mainichev

Purtov

2007

Concepts Magnetic Resonance

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“…In particular, NMR is used to measure quantum yields for irreversible photochemical reactions (1), and the NMR branch (photochemically induced polarization of nuclei) provides detection of shortlived radicals arising in flash photolysis of substances (2). Being a well-developed NMR tool, dynamic NMR spectroscopy (DNMR) is commonly used to obtain kinetic parameters of dark reversible chemical reactions in solutions (5)(6)(7). DNMR is rarely used for experimental study of reversible photochemical reactions in solution (8,9).…”

Section: Introductionmentioning

confidence: 99%

NMR in photoinduced chemical exchange systems: Theoretical basis of double-resonance inverse fractional population transfer

Babailov

Mainichev

2006

Concepts Magn. Reson.

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ABSTRACT:The analytical expression describing dynamics of the nuclear magnetization with the use of double-resonance NMR in the transfer of inverse fractional population under photoinduced chemical exchange is obtained. An experimental procedure for the definition of effective rate constants and quantum yield of responses is considered. The technical approach created allows for planning experimental strategies for the study of photoinduced chemical exchange in any solvable substances.

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Rotation about Single Bonds in Organic Molecules

Cited by 16 publications

References 184 publications

Generalized Synthesis and Physical Properties of Dialkoxy Disulfides

Generalized Synthesis and Physical Properties of Dialkoxy Disulfides

NMR application for a study of reversible photochemical kinetics: A multisite case

NMR in photoinduced chemical exchange systems: Theoretical basis of double-resonance inverse fractional population transfer

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