Physikalische eigenschaften und bindungszustände schwefelorganischer verbindungen—I

Goetz, Horst; Klabuhn, B.; Marschner, F.; Hohberg, H.; Skuballa, Werner

doi:10.1016/s0040-4020(01)92501-3

Cited by 11 publications

(2 citation statements)

References 30 publications

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“…On the basis of dipole moments (24), 19F n.m.r. (25) and pK, values (16)(17)(18)(19)(20)(21)(22)(23)(24)(25)(26)(27)(28) however, the d-orbital acceptance properties are considered to be predominant. Accordingly the observed deshielding at the paracarbon of 12 relative to benzene is reasonable.…”

Section: Methyl Pherzyl Sulfoxidesmentioning

confidence: 99%

A Carbon-13 Nuclear Magnetic Resonance Investigation of Some Substituted Methyl Phenyl Sulfides, Sulfoxides, and Sulfones

Buchanan¹,

Reyes-Zamora²,

Clarke³

1974

Can. J. Chem.

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Carbon-13 chemical shifts for 33 methyl phenyl sulfides, sulfoxides, and sulfones are reported. Observed trends are discussed in terms of the steric and electronic influences of the substituent groups. Additivity correlations for para-disubstituted materials are noted. In general, the shieldings of methyl carbons bonded to sulfur are rather insensitive to the nature of the aromatic substituents. By contrast to the proton shieldings, the CH3SO and CH3SO2 carbons exhibit nearly identical chemical shifts.

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Section: Methyl Pherzyl Sulfoxidesmentioning

confidence: 99%

A Carbon-13 Nuclear Magnetic Resonance Investigation of Some Substituted Methyl Phenyl Sulfides, Sulfoxides, and Sulfones

Buchanan¹,

Reyes-Zamora²,

Clarke³

1974

Can. J. Chem.

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“…); 0.67 [9, 10] (s I ); 0.13 [9,10] son with the corresponding s constants of other substituents, with the aim to explain or predict the reactivity of these compounds (see, e.g., [12314]). The compound C 6 H 5 S(O)CH 3 was studied by the methods of dipole moments [15], photoelectron spectroscopy [16 318], 1 H [19,20], 13 C [17,19322], and 17 O [19,20,23] NMR spectroscopy, X-ray emission spectroscopy [22], and Kerr constants [24]. The compound C 6 H 5 S(O)CF 3 was studied by the methods of dipole moments [25] and 19 F [26], 13 C [26,27], and 17 O [26] NMR spectroscopy.…”

mentioning

confidence: 99%

An ab initio Quantum-Chemical Study of C6H5S(O)CH3 and C6H5S(O)CF3

et al. 2005

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The potential functions of internal rotation around the C sp 23S bond in the C 6 H 5 S(O)CH 3 and C 6 H 5 S(O)CF 3 molecules were obtained by ab initio MP2(full)/6-31+G* calculations. The stationary points were identified by solving the vibrational problems. The structures in which the plane of the C sp 23S3C sp 3 bonds is approximately perpendicular to the benzene ring plane correspond to the energy minimum. The barriers to rotation around the C sp 23S bond, corrected for the zero-point vibration energy, are 21.29 [C 6 H 5 S(O)CH 3 ] and 28.98 [C 6 H 5 S(O)CF 3 ] kJ mol !1 . The bond angles (deg) are as follows: 95.7 (CSC), 107.1 (C sp 2SO), 106.3 (C sp 3SO) in C 6 H 5 S(O)CH 3 ; 93.5 (CSC), 108.2 (C sp 2SO), 105.2 (C sp 3SO) in C 6 H 5 S(O)CF 3 . The bond lengths are as follows (A): 1.520 (S=O), 1.804 (C sp 23S), 1.810 (C sp 33S) in C 6 H 5 S(O)CH 3 ; 1.507 (S=O), 1.799 (C sp 23S), 1.870 (C sp 33S) in C 6 H 5 S(O)CF 3 . According to the results of NBO calculations, the formally double S=O bond consists of a strongly polarized covalent s bond (S6O) and an almost ionic bond.An increase in the S=O bond multiplicity relative to a single bond is mainly due to hyperconjugation by the mechanism n(O)6s*(C sp 23S) and n(O)6s*(C sp 33S) and, to a lesser extent, by interaction of the oxygen lone electron pairs with the Rydberg orbitals of the S atoms, characterized by a large contribution of the d component.

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Spektroskopische Substituentenkonstanten, V. Zum Konzept variabler Effekte von 3d‐Substituenten²⁾

Schiemenz

1971

Justus Liebigs Ann. Chem.

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Die UV-Spektren von p-Methoxy-phenyl-phosphor(V)-Verbindungen sprechen nicht dafur, daR das Phosphor-Atom einen je nach Art von Zweitsubstituenten unterschiedlichen elektronischen Effekt auf den Ring ausubt. Auch die Hammett-Konstanten liefern keinen Hinweis auf ein solches Phanomen. Spectroscopic Substituent Constants, V l ) . The Concept of Variable Electronic Effects of 3d-Substituentsz)The UV spectra of p-methoxyphenyl-phosphorus(V) compounds do not reveal a dependence of the electronic effect of phosphorus on the nature of a second substituent. The Hammett constants also do not indicate such a phenomenon.Voraussetzung fur eine schlussige theoretische Interpretation der Bindungsverhaltnisse in Phosphor-substituierten Aromaten ist die experinientelle Klarung der Effekte, die der Phosphor als Substituent am aromatischen Ring ausubt. Die hierzu bisher herangezogenen Verfahren liefern MeBgroBen, die von mehreren Parametern abhangen und dadurch wiederholt zu unterschiedlichen Deutungen AnlaB gaben. Zum Beispiel besitzt der Phosphor auf Grund verschiedener Kriterien -M-Qualitaten, jedoch ist ungeklart, ob er in p-disubstituierten Aromaten dieselben Eigenschaften wie gangige -M-Gruppen hat oder eine Sonderrolle spielt.1964 glaubten wir eine solche Sonderrolle des Phosphors in den UV-Spektren zu erkennen3) : Einerseits hatten wir gefunden, daB P-haltige Substituenten die Dimethylanilin-Hauptbande in einer fur mittelstarke -M-Gruppen typischen Weise bathochrom verschieben. Dagegen hatten Jaf& und Freedman4) aus dem Fehlen eines nennenswerten Effekts dieser Art bei 1 C1, NO21 und C6H5P02H2 nebst ihren Anionen gefolgert, daR es zwischen den Substituenten und dem Ring keine4) (bzw. nur eine geringes)) derartige Konjugation gebe.(X = H) sowie den Sauren X -C C~H~-P O~H~, X -C C~H~( Y -C &~) P~~H [X und Y = H,

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Physikalische eigenschaften und bindungszustände schwefelorganischer verbindungen—I

Cited by 11 publications

References 30 publications

A Carbon-13 Nuclear Magnetic Resonance Investigation of Some Substituted Methyl Phenyl Sulfides, Sulfoxides, and Sulfones

A Carbon-13 Nuclear Magnetic Resonance Investigation of Some Substituted Methyl Phenyl Sulfides, Sulfoxides, and Sulfones

An ab initio Quantum-Chemical Study of C6H5S(O)CH3 and C6H5S(O)CF3

Spektroskopische Substituentenkonstanten, V. Zum Konzept variabler Effekte von 3d‐Substituenten²⁾

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Physikalische eigenschaften und bindungszustände schwefelorganischer verbindungen—I

Cited by 11 publications

References 30 publications

A Carbon-13 Nuclear Magnetic Resonance Investigation of Some Substituted Methyl Phenyl Sulfides, Sulfoxides, and Sulfones

A Carbon-13 Nuclear Magnetic Resonance Investigation of Some Substituted Methyl Phenyl Sulfides, Sulfoxides, and Sulfones

An ab initio Quantum-Chemical Study of C6H5S(O)CH3 and C6H5S(O)CF3

Spektroskopische Substituentenkonstanten, V. Zum Konzept variabler Effekte von 3d‐Substituenten2)

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Spektroskopische Substituentenkonstanten, V. Zum Konzept variabler Effekte von 3d‐Substituenten²⁾