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    Bathochromic Displacements and Other Steric Effects in Electronic Spectra

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    hernando guerrero
    This document summarizes and critiques a recent paper by Heilbronner and Gerdi regarding their proposed unified theory of steric effects in electronic spectra of organic compounds. The author argues that Braude's original classification of steric effects into two distinct types - those that only change absorption intensity and those that change both intensity and wavelength - is valid based on experimental evidence. While Heilbronner and Gerdi claim Braude's theory cannot account for bathochromic shifts observed in some compounds, the author shows this possibility was not excluded in Braude's original paper. In conclusion, the author believes steric effects are better understood by treating the two types independently rather than with a single unified theory.

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    Bathochromic Displacements and Other Steric Effects in Electronic Spectra

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    hernando guerrero
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    This document summarizes and critiques a recent paper by Heilbronner and Gerdi regarding their proposed unified theory of steric effects in electronic spectra of organic compounds. The author argues that Braude's original classification of steric effects into two distinct types - those that only change absorption intensity and those that change both intensity and wavelength - is valid based on experimental evidence. While Heilbronner and Gerdi claim Braude's theory cannot account for bathochromic shifts observed in some compounds, the author shows this possibility was not excluded in Braude's original paper. In conclusion, the author believes steric effects are better understood by treating the two types independently rather than with a single unified theory.

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    forbes1958

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    This document summarizes and critiques a recent paper by Heilbronner and Gerdi regarding their proposed unified theory of steric effects in electronic spectra of organic compounds. The author argues that Braude's original classification of steric effects into two distinct types - those that only change absorption intensity and those that change both intensity and wavelength - is valid based on experimental evidence. While Heilbronner and Gerdi claim Braude's theory cannot account for bathochromic shifts observed in some compounds, the author shows this possibility was not excluded in Braude's original paper. In conclusion, the author believes steric effects are better understood by treating the two types independently rather than with a single unified theory.

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    © All Rights Reserved
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    20 views3 pages

    Bathochromic Displacements and Other Steric Effects in Electronic Spectra

    Uploaded by

    hernando guerrero
    This document summarizes and critiques a recent paper by Heilbronner and Gerdi regarding their proposed unified theory of steric effects in electronic spectra of organic compounds. The author argues that Braude's original classification of steric effects into two distinct types - those that only change absorption intensity and those that change both intensity and wavelength - is valid based on experimental evidence. While Heilbronner and Gerdi claim Braude's theory cannot account for bathochromic shifts observed in some compounds, the author shows this possibility was not excluded in Braude's original paper. In conclusion, the author believes steric effects are better understood by treating the two types independently rather than with a single unified theory.

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    310 H E L V E T I C A C H I M I C A ACTA.

    38. Bathochromic Displacements and Other Steric Effects


    in Electronic Spectra
    by W. F. Forbes.
    (25. VI. 57.)

    In a recent paper, Heilbronner G Gerdi12) discuss the electronic spectra of


    azulene aldehydes and azulene ketones with particular reference to classifica-
    tion of steric effects in electronic spectra, and conclude from their observations
    that some of the assumptions implied in a previous classification of steric
    effects into two types3) are unwarranted. In particular it is deduced that the
    occurrence of bathochromic shifts in substituted azulenes, due to steric effects,
    invalidates the proposed mechanism of the classification due to Braude3) and
    his colleagues, since Braude’s classification is interpreted to mean that if a
    wavelength shift occurs because of steric inhibition of resonance, the correspond-
    ing energy change must always be positive.
    Now although in some of the review references cited, particularly those
    where reference is made to special examples such as diphenyls or aceto-
    phenones3), the wording may be interpreted in the sense as proposed by
    Heilbroianer C Gerdi12), examination of the original paper shows that the
    general classification of steric effects proposed by Braude ef aL3) is as follows:
    (1)Steric effects which only cause a change in the absorption intensity of the
    band characteristic of the whole chromophoric system, with no unusual
    change in wavelength; and (2) Steric effects which cause a change4) in both
    wavelength and absorption intensity. It is added that ‘steric inhibition of
    electronic interaction normally4) raises the energy level of the excited state
    more than that of the ground state’, which however is surely not the same as
    proposing an inevitable hypsochromic shift.
    Braude’s ad hoc hypotheses concern two generalisations, both of them well
    borne out by the experimental data. The first of these is that steric interactions
    sometimes give rise to changes in the absorption intensity only, and that this is a
    different type of steric effect from the second type, which causes also wavelength
    changes. This follows, partly because one substituent may in one series of
    compounds cause only an intensity change, whereas in another series of com-
    l)Laut besonderem Beschluss des Redaktionskomitees veroffentlicht.
    2,E. HeiZbronner G. R . Gerdil, Helv. 39, 1996 (1956).
    8 ) E. A . Braude, F . Sondheilner & W . F . Forbes, Nature 173, 117 (1954); cf. also
    E. A . Braude, Experientia 11, 457 (1955); E . A . Bvaude G. E . S . Waight, ,The Relation-
    ship Between the Sterochemistry and Spectroscopic Properties of Organic Compounds‘
    in: W . KZyne, Progress in Stereochemistry, Vol. I, p. 148, London 1954; B. A . Braude,
    Ultraviolet and Visible Light Absorption in: E . A . Braude & F . C. Nachod, Determination
    of Organic Structures by Physical Methods, p . 131, New York 1955.
    4, Our italics.
    Volumen XLI, Fasciculus I (1958) - No. 38. 311

    pounds a wavelength shift also occurs. Further, the frequent occurrence of the
    first type of steric effect points against this being merely a special case of the
    second type. Some examples are listed in the Table. The mechanism underlying
    the two types of steric effects is believed to be different, and it should therefore
    frequently prove possible to predict the type of steric effect which will occur in
    a particular example.
    Steric Effects of Type I.

    Hindered Compound

    .
    I I
    lmax’F
    mP
    Reference Compound &
    Solvent
    and
    __ 3eferencs
    Pivalophenone . . 236 8100 Acetophenone . . . 238 13,040 n-Hep-
    tama)
    2-Hydroxy-4-toluic
    acid . . . . . . . 242 9600 p-Toluic acid . . . . 241, 14,400 PH 3b)
    3 :4-Dihydroxybenzoic
    acid. . . . . . . 251 7800 p-Hydroxybenzoic acic 251 12,500 pH 7b3c
    2 :4-Dimethoxy-
    benzoic acid . . . 246 8500 p-Anisic acid . . . . 247 14,000 p H llb)
    3-Amino-4-hydroxy- p-Hydroxybenzoic
    benzoic acid . . . 280 9200 acid . . . . . . . 280 16,300 p H llb)
    3 :4-Dihydroxyaceto- p-Hydroxyaceto-
    phenone . . . . . 274 9900 phenone . . . . . 275 14,300 ).lNHCI
    2 :4-Dihydroxyhenzal- p-Hydroxybenzal-
    dehyde . . . . . 331 20,301 dehyde . . . . . 330 27,900 p H llb)
    2-Methoxy-5-chloro-
    nitrobenzene . . . 265 3900 m-Chloronitrobenzene 264 7100 Waterb)
    2 : 5-Dimethoxynitro-
    benzene . . . . . 273 3300 m-Nitroanisole . 27 3, 6000 Waterb)
    2 :4 :6 -Trimethylsty-
    rene. . . . . . . 245 7000 Styrene . . . . . 244 14,000 Ethanol
    octaned)
    ~ __ __
    a) G. D. Hedden 6 W . G. Bxown, 1. Amer. chem. SOC.75. 3 14 (1‘ 3).
    b, L. Doub & J . M . Vandenbelt, -J. Amer. chem. SOC.77; 4535 (1955); 71, 2414
    (1949); 69, 2714 (1947).
    c, Value for p-Hydroxybenzoic acid in 95% ethanol, C. Moser 15A . I . Koh-
    Zenberg, J. chem. SOC.1951, 804.
    d, K . C. Bryant, G. T. Kennedy 6 E. M . Tanner, J . chem. SOC.1949, 2389,
    and E. A . Braude, Experientia 11, 457 (1955).

    I t may be noted that the Table includes the value of 2:4:6-trimethylstyrene


    which on the basis of Heilbronner G Gerdil’s unified theory2) is predicted to
    show a large hypsochromic shift compared to styrene. Although a number of
    differing data are found in the literature5), it appears that together with other
    bands, a band a t 244.5 & 0.5 mp occurs for both the above-mentioned com-
    pounds. Further, Braude’s hypotheses, like other similar hypotheses, are of
    course not intended to provide a rigid theoretical interpretation, but rather
    serve as a starting point for further work. This may be illustrated by one

    5) Cf. E . A . Braude & F . Sondheimer, J. chem. SOC.1955, 3773.


    312 HELVETICA C H I M I C A A C T A ,

    development which discusses the relative contributions of s-cis and s-trans


    conformations to the observed absorption intensitiess).
    Apart from questioning the existence of a special type of steric effect in
    the electronic spectra of organic compounds (which gives rise to intensity
    changes only), Heilbronner & Gerdi12) also criticise Braude's hypotheses for
    their supposed failure to account for the occurrence of bathochromic shifts
    because of steric interactions. This possibility, however, as has already been
    pointed out, is not excluded in the paper criticised by Heilbronner C Gerdil'),
    and has in fact also been more fully discussed in a recent papers), which itself
    is based on a number of well known experimental datas).
    Finally, the following point may be briefly mentioned:- Braude and his
    colleagueslo) do not propose the use of the usual van der Waals radii as a
    measure of interference. The values suggested by them-but perhaps mis-
    leadingly named van der Waals radii by Heilbronner & Gerdi12)-are about
    half the usual van der Waals radii. Although slightly larger values have been
    suggested in a more recent paperll), this does not invalidate the basic argument
    of Braude that the usual van der Waals radii are generally not satisfactory for
    relating steric interactions in ultraviolet absorption spectra.

    SUMMARY.
    A recently proposed unified theory of steric effects in the electronic spectra
    of organic compounds is criticised on the grounds that steric effects of that
    type normally fall into at least two distinct patterns. It is proposed that these
    two types of steric effects can be better understood by being treated in-
    dependently. A brief survey of the relevant data is given.
    Memorial University of Newfoundland, St. John's,
    Newfoundland, Canada.

    6)W . F . Forbes & W . A . Muellev, Canad. J. Chemistry 34, 1347 (1956).


    7)E. Heilbronner & R. Gerdil, loc. cit. and particularly the SUMMARY of that paper.
    8 ) W . F . Forbes & W . A . Mueller, Canad. J. Chemistry 35, 488 (1957).
    9) See for example W . M . Schubert & W . A . Sweeney, J. Amer. chem. SOC.77, 2297
    (1955); 0. H . Wheeler, ibid. 78, 3216 (1956).
    lo) I?. A . Braude & F . Sondheimer, J. chem. SOC.1955, 3754.
    11) W . F . Forbes G. W . A . Mueller, Canad. J. Chemistry 34, 1542 (1956).

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