Relation between the Electronegativities of Adjacent Substitutents and the Stretching Frequency of the Carbonyl Group

Kagarise, R. E.

doi:10.1021/ja01610a093

Cited by 179 publications

(71 citation statements)

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“…Thus the following is probably the order of the strengths of these sulphonic acids, similar effect of electronegative substituents on the characteristic frequency of a group has been observed in other cases, e.g. for phosphoryl co~llpoullds (13) and for carbonyl colnpoullds (14), and attempts have been lllade to devise quantitative relationships between the vibrational frequency of a group and the effective electronegativities of the attached substituents.…”

mentioning

confidence: 57%

Characteristic Vibrations of the Sulphuryl Group

Robinson¹

1961

Can. J. Chem.

115

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ABSTRACT'Mant~script received September 16, 1960. Contribution from the Department of Chemistry, McMaster Uniuersity, Hamilton, Ontario. A compilation of the S--0 symmetric and asynlnletric stretching frequencies is given for a large number of compounds containing a n -SO,-group. I t is shown that a linear relationship between vso,(,,,) and vso, (,,,) is valid for a large number of sulphuryl and polysulphuryl compounds and that the actual frequencies depend in a systematic manner on the electronegativities of the attached groups. These relationships have proved very useful in assigning and in some cases reassigning the S-0 bands in the infrared and Raman spectra of a number of sulphuryl compounds. I t is pointed out that there is a relationship between the SO2 frequencies of some sulphonic acids and their acid strengths.The calculation of values for group electronegativities from the vibration frequencies of the P=O and SOX groups is discussed.For a variety of organic con~pouncls including sulphones, sulphoilyl chlorides, covaleilt sulphates, sulphonamides, sulphonic acid esters, and sulphonates, the sulphur-oxygen symmetrical and ai~tisyinmetrical stretching frequencies obtained from infrared and Raman spectra have been characterized. A compilation of these frequeilcies has been given by Bellamy (1).In 1957 Bellamy and Williams (2) pointed out that any change in the symmetric frequency, v~~,~,~~) , is accompanied by a proportioilal change in the asymmetric frequency, vso,(naym). They plotted vso2(,,,) against vs0, (,,,,) for 29 coinpouilds taken from the work of Haszeldine and Kidd (3, 4), Barnard, Fabian, and I

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mentioning

confidence: 57%

Characteristic Vibrations of the Sulphuryl Group

Robinson¹

1961

Can. J. Chem.

115

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“…The same trend is observed for the reduction potential of the reduction of the carbene ligand (more negative). This trend is not in the order of the electronegativity of the O (3.44) > N (3.04) > S (2.58), although it is possible that the CH 3 group ( CH3 = 2.34 [37]) donates electron density to N, rendering (NCH 3 ) less electronegative than N and possibly than S. Connor and Jones [38] studied a number of heteroaromatic chromium carbene complexes (CO) 5 CrC(Y)X to determine the extent to which the electron-donating ability of the heteroaromatic ring aids in stabilizing the empty p-orbital on the carbene carbon atom. The order of increasing electron-donating ability was found to be Y = 2-furyl < 2-thienyl < 2-(N-methylpyrrolyl).…”

Section: Tungsten Monocarbene Complexes With Monomeric Heteroaromaticmentioning

confidence: 91%

Fischer mono- and biscarbene complexes of tungsten with mono- and dimeric heteroaromatic substituents

Landman

Buitendach

Conradie

et al. 2015

Journal of Electroanalytical Chemistry

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An electrochemical study of a series of mono and biscarbene complexes of tungsten pentacarbonyl with mono-and dimeric heteroarene substituents are reported and compared in CH 3 CN and DCM.Results revealed that the order of oxidation (reduction) depends largely on the aryl substituent attached to the carbene carbon (2-thienyl, 2-furyl or 2-(N-methylpyrrolyl)). The order of oxidation (reduction) for monocarbene complexes containing a monomeric heteroarene substituent ((1) -(3)), a dimeric heteroarene substituent ((4) -(6)) or biscarbene complexes connected with a heteroarene substituent ( (7) - (9)) is the same, namely 2-thienyl > 2-furyl > 2-(N-methylpyrrolyl). Carbene complexes containing a larger conjugated heteroarene substituent attached to the carbene carbon reduce more easily than the monomeric analogues. Tungsten biscarbene complexes exhibit two separate oxidation potentials for the two metal centres or one large oxidation peak, consistent with the simultaneous oxidation of the two W metal centres.

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“…More marked are the variations in the C-Cl lengths; essentially identical bond distances have been determined for formyl chloride and propiolyl chloride while that found for acetyl chloride is somewhat longer. Kagarise (51) suggested that electronegative substituents should lower the contribution of nonbonded resonance structures such as RCO+Cl-; therefore the longest C-CI bond would be expected for acetyl chloride because of the presence of the "electron-donating" methyl group. "The HCOCl structure is an r structure.…”

Section: Comments On the Structure Ofpropiolyl Chloridementioning

confidence: 99%

The microwave spectrum, harmonic force field, structure, and dipole moment of propiolyl chloride

Davis¹,

Gerry²

1982

Can. J. Chem.

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The microwave spectra of four isotopic species of propiolyl chloride, HCCCOCl, have been measured for their ground and υ9 = 1 excited vibrational states. Values for the rotational constants, quartic centrifugal distortion constants, chlorine nuclear quadrupole coupling constants, and the molecular dipole moment have been obtained. The centrifugal distortion constants have been combined with vibrational wavenumbers from the literature to calculate an approximate harmonic force field. Effective and ground state average structures of the most abundant isotopic species, H12C12C12C16O35Cl, are presented.

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Relation between the Electronegativities of Adjacent Substitutents and the Stretching Frequency of the Carbonyl Group

Cited by 179 publications

References 0 publications

Characteristic Vibrations of the Sulphuryl Group

Characteristic Vibrations of the Sulphuryl Group

Fischer mono- and biscarbene complexes of tungsten with mono- and dimeric heteroaromatic substituents

The microwave spectrum, harmonic force field, structure, and dipole moment of propiolyl chloride

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