The interactions between C=C and C=O double bonds in
several unsaturated ketones have been studied by comparing
MIND0/2 caloulations wiith ionisation potentials determined by
photoelectron spectroscopy (PES). With one exception (norbornadienone)
the direct through-space interactions in conjugated .ketones
appear to be negligible, the double bonds couple hyperoonjugatively
via the intervening a bonds. This kind of approach should prove
useful for studying other long range interactions

M. J. S. Dewar

Nicolae Bodor

Zvonimir B. Maksić

English

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CROATICA CHEMICA ACTA CCACAA 48 (1) 9-15 (1976) CCA-908 YU ISSN 0011-1643 539.19 Original Scientific Paper A Study of the Interactions Between the Double Bonds in Unsaturated Ketones* Nicolae Bodor**, M. J. S. Dewar and Zvonimir B. Maksic*** Department of Chemistry, The University of Texas at Austin, Austin, Texas, 78712, U.S.A. Received April 28, 1975 The interactions between C=C and C=O double bonds in several unsaturated ketones have been studied by comparing MIND0/2 caloulations wiith ionisation potentials determined by photoelectron spectroscopy (PES). With one exception (norborna-dienone) the direct through-space interactions in conjugated .ketones appear to be negligible, the double bonds couple hyperoonjugatively via the intervening a bonds. This kind of approach should prove useful for studying other long range interactions. The MINDOi2 method1 gives good estimates of the heats of atomisation and geometries for a wide variety of origanic molecules. It reproduces the ener-gies of the molecular orbitals quite satisfactorily as revealed by earlier cal-culations of ionisation potential,s2 , employing Koopmans' theorem3• The latter implicitly assumes that the orbitals in a molecule and the corresponding cation are the same i.e. they remain »frozen«. This assumption does nO't hold exactly since the orbitals adjust themselves to the increase in the positive charge. However, the reorganisation energy is canceled to the large extent by the ch:mge in the correlation energy so that Koopmans' theorem is in general fairly well obeyed. It 'provides invaluable tool for the interpretabon of photoelectron spectra in conjuction with the MO model and gives also useful pictorial insight into intramolecular interactions. Namely, the energies of the molecular orbitals descr~bing localised or semilocalised electrons depend on the chemical environment of the electronic group in question, .so that the corres:ponding ionisation potentials exhibit characteristic »chemical shifts« in the photoelectmn spectrum. The nature and magnitude of such shifts can than provide information concerning the kinds of interaction that take place between the localized group and its environment. Thus the n:-electrons of two isolated C= C double bonds can interact with one another either directly across space or hyperconjugatively via intermediate a bonds. Although the physical nature of both interactions is essentially the same, they often lead to differ~nt symmetries for higher MO formed by interaction of the CC n: M0s4 • * This work was supported by Air Force Office of Scientific Research through Contract F 44620-71-C-0119 and by Robert A. Welch Foundation through Grant F-126. ** Robert A. Welch Postdoctoral Fellow *** On leave of absence from the Institute »Ruder Boskovic«, 41001 Zagreb, Yugoslavia during the academic year 1971-72. 10 N. BODOR ET AL. It is possible to distinguish between them on this basis by comparison of the observed ionisation potentials with those calculated by MIND0/24b. In this paper we examine the magnitude and mode of the interactions between a carbonyl group and one or more C=C double bonds in some five membered cyclic unsaturated ketones and related compounds. The geometries of the molecules were minimized with respect to the parameter·s determining the molecular skeletons by using the program written by Dr. A. Brown a.nd modified by Dr. J. S. Wasson5 based on the simplex algorithm6• The complete optimization of the molecular geometries was necessary because we found that the orbital energies, in particular the separations between the highest levels, are strongly dependent on the geometry. For instance, the highest molecular orbitals in norbornenone are very sensitive to changes 'in the angle between the »wings« of the molecule. By optimizing the geometry of each molecule we ensure that the results are compatible and comparable among themselves. The parameters for MIND0/2 method used in this paper were those of ref. (1). RESULTS AND DISCUSSION Experimental geometries are available only for cyclopentene, cyclopen-tadiene and norbornadiene. The calculated bond lengths and bond angles are compared with experiment in Table I. The agreement is only fair, the C- C and C- H bonds being consistently too short and too long respectively. However the qualitative features are very well reproduced, for example the variation in C-C bond lengths with the hybridizat ion of the particip ating carbon atoms. The C-C single bond lengths in cyclopentene are not known unambiguously7• Our calculation supports the suggested assignment7 in which the shorter C- C bond is adjacent to a double bond, as one would expect in view of the different hybridi·zation of the carbon atoms. Norbornadiene is a very interesting molecule since it has three different kinds of C-C bonds and a somewhat unusual bridge angle. The calculated geometry of norbor-nadiene is in good overall agreement with experiment although the C1- C1 bond length is somewhat too short. The bridge angle in norbornadiene is not uniquely determined by the gas electron diffraction measurements8 and one has to make a choice between values of 92.2° and 96.0°. Our calculated angle (94.4°) sli:ghtly favours the latter value but not significantly since the possible error in bond angles calculated by the MIND0/2 method is about 2°. The calculated dihedral angle of norbornadiene is in good agreement with ex-periment. Our calculations lead to a planar arrangement of the heavy atoms in cyclopentene-2-one and cyclopentene-3-one, in full accord with recent micro--wave measurements9• The calculated first ionisation potentials are compared with experiment in Table II. The agreement is very .good except that the calculated values a·re uniformly too hLgh. This is not of great significance because the difference is practicaly constant and could be removed by changing the origin of the energy scale. The MOs representing the C=C and C=O :n: bonds can be quite clearly recognised, being only slightly perturbed by their mutual interaction. The observed and calculated changes in the corresponding ionisation potentials therefore provide a useful guide in studying long range interactions. TABLE I Calculated and experimental geometries for cyclopentene, cyclopentadiene, and norbornadiene Compound I Bond lengths Bond angles calcd. I eX'P· calcd. I ex1p, 4 C1-C2 = 1.328 (1.343)" C1C2H = 123.2° sQ C2-C3 = 1.454 (1.519) HC3H = 104.70 C3-C4 = 1.526 (1.546) HC4H = 102.20 C1-H = 1.100 C1C2C3 = 113.5° (111°)• C3-H = 1.105 C2C3C4 = 101.9° (103°) C4-H = 1.118 C3C4C5 = 109.2° (104°) 4 C1-C2 = 1.412 (1.469)b C1 C2H = 126.90 503 C2-C3 = 1.344 (1.342) C2C3H = 127.30 C3-C4 = 1.464 (1.509) HC4H = 95.2P C1-H = 1.105 C3C4Cs = 99.6° (102.8o)b 1 2 C4-H = 1.108 C1C2C3 = 106.5° (109.4°) C2C3C4 = 113.7° (109.4°) 7 C1-C2 = 1.338 (l.343f C1C2H = 128.3° C1-C3 = 1.495 (1.535) C1C3H = 119.8° C3-C1 = 1.546 (1.573) HC1H = 97.6° C1-H = 1.084 C3C1C4 = 94.4° C3-H = 1.090 (94 ± 3)c 1 ~ I C1-H = 1.093 • M. I. Davis and T. W. 'Muecke, J. Phys. Chem., 14 (1970) 1104. b L. H. Scharpen and v. w. Laurie, J. Chem. Phys., 43 (1965) 2765. c A. Yokozeki and K. Kuchitsu, BuU. Chem. Soc. Jap. 44 (1971) 2356. Dihedral angles C1C2C3--C3C4Cs = 167.1° (151°) C1C2C3--C4C5Cs = 112.80 (115.6° ± 2.2°) z ..., l:"J ::0 > () ..., 0 z (fJ bj l:"J ..., :;: l:"J l:"J z ..., ~ t:l 0 c:: bj t"' l:"J bj 0 z t:l (fJ ...... ...... 12 N. BODOR ET AL. TABLE II Calculated and observed first ionisation potentials First Ionisation Potential Compound Calcd. Observed ------·------~-- --~------cyclopentene cyclopentadiene norbornane norbornene norbornadiene cyclopentanone cyclopentene-2-one cyclopentene-3-one cyclopentadienone norbornane-7-one norbornene-7-one norbornadiene-7-one 9.30 9.08 9.87 9.39 9.26 9.78 9.73 9.76 9.84h 9.48 9.47 9.74 a M. J. S. Dewar and S . D. Worley, J . Chem. Phys., 50 (1969) 654. b P. Bischof and E . Heilbronner, Heiv. Chim. Acta, 53 (1970) 1677. e D. A. Demeo and A. J. Yencha, J. Chem. Phys., 53 (1970) 4536. d adiabatic Iv given in ref. c) 9.ooa; 9.18b 8.55" 9.74c,d 8.97° {9.20') 8.95' 9.25''" 9.34' 9.44' 9.01' 9.19' e P. Bischof, J. A. Hashmall, E . Heilbronner and V. Hornung, HeLv . Chim. Acta, 52 (1959) 1745. ' D. Chadwick, D. C. Frost, and L. Weiler, J. Amer. Chem. Soc., 93 (1_971) 4320. g D. Chadwick, D. C. Frost, and L. Weiler, Tetrahedron Letters, (1971) 4543. h assigned to ionisation from n-level. ' D . Chadwick, D. C. Frost and L . Weiler, J. Amer. Chem. Soc., 93 (1971) 4962. We first examined the interactions between a carbonyl group and a C=C bond B, y to it. In order to assess the importance of through-space interactions, we carried out the MIND0/2 calculations omitting the integrals representing these. The results (Table III) show that ommission of these integrals usually has little or no effect on the calculated Jtcc and Jtco ionisation potentials, iim-plying that any Jtcc-Jtco interactions in these, compounds must be of hyper-conjugative (thraugh-bond) type. This conclusion is supported by the comparisons in Table IV. Introduction of a carbonyl group into an olefine raises the nee ionisation potential, implying a lowering of the energy of the Jtcc MO. If the Jtcclnco interaction were of through-space type the opposite would be the case; for the Jtco MO lies befow nee in energy and a direct interaction between them should therefore raise nee and lower Jtco. Furthermore, s1nce through-space interactions depend on overlap of the interacting orbitals, they should die away very rapidly with distance. This is not the case for the ncclnco interactions in Table IV, the interactions remainig large in the y () unsaturated ketones I and II, which are shematically shown in Figure 1. Norbornadienone is particularly interesting in this connection being the only case studied in which the first ionisation potential is predicted to co·r-respond to ionisation from nee rather than n0 • This is because it was the only compound for which the direct through-space ncclnco interaction was predicted INTERACTIONS BETWEEN THE DOUBLE BONDS 13 0 I II Figure 1. TABLE III Comparison of ionisation potentials (eV) obtained by the full MIND0/2 method with those calculated when integrals corresponding to through-space interactions were set equal to zero Compound 0 11 cb 0 11 0 II full MIND0/2 through space interaction excLuded :n:c =c vs. lone pair I 9.76 (n0) 9.84 (:rtC =C) 9.73 (n0) 9.81 (:rtC =C) to be appreaciahle. The direct interaction is large ( ~ 0.3 eV) and, as expected, raises the energy of the n:cc MO. As a result, for this compound alone n:cc lies above n 0 • This difference is very small indeed (0 .02 eV) and consequently may 14 N. BODOR ET AL. TABLE IV Stabilization effect of the carbonyl group on the itc~c levels (in eV) Compounds ~it· "c~ c calc. (obs.) no ---cyclopentene 9.30 0 cyclopentene-3-one 9.84 0.54 (0.80)" 9.76 cyclopentene-2-one 10.26 0.96 (0.92)" 9.73 cyclopentadiene 9.08 0 cyclopen tadienone 10.12 1.04 9.84 norbornene 9.53 0 norbornene-7-one 9.93 0.40 (0.65)e 9.47 exo-ketone (I) 9.67 0.14d (0.22)e 9.44 endo-ketone (II) 9.73 0.20d (0.23)" 9.42 norbornadiene 9.26 0 norbornadiene-7-o.ne 9.74 0.48 9.76 cyclopentanone 9.78 norbornane-7-one 9.48 • the difference a " is calculated relative to the parent cycloalkene if it is not stated otherwise. b Reference i) Table II. e Reference f) Table II. '' Relative to the norbornene. e M. D. Brown, J. Hudec, and J . M. Mellor, Chem. Comm., (1971) 1640. not be significant at all in view of the large number of approximations involved in the theoretical model. In any case, one can expect that rrcc and n 0 levels are very c1ose. It is curious that the direct rrccfrrco interaction in 7-norbornenone (- 0.4 eV) is so much smaller. This again shows how sensitive direct inter-actions are to small changes in geometry. REFERENCES 1. (a) M. J . S. Dewar and E. Hase 1 b a ch, J. Amer. Chem. Soc. 92 (1970) 590; (b) N. B o do r, M. J. S. Dewar, A. Ha r get, and E. Hase 1 b a ch, J . Amer. Chem. Soc. 92 (1970) 3854. For a review see (c) M. J. S. Dewar, Fortschr. Chem. Forsch. 23 (1972) 1. 2. N. Bodor, M. J . S. Dewar and S. D. Worley, J . Amer. Chem. Soc. 92 (1970) 19; N. Bodor, M. J . S. Dewar, W. B. Jennings, and S. D. W or 1 e y, Tetrahedron 26 (1970) 4109. 3. T . Koopmans, Physica 1 (1934) 104. 4. (a) R. Hoff m an, E. He i 1 bro n n er, and R. G 1 e it er, J . Amer. Chem. Soc. 92 (1970) 706; (b) M. J . S. Dewar and J. S. Wasson, J . Amer. Chem. Soc. 92 (1970) 3506; (c) E. He i 1 bro n n er and H. D. Martin, Helv. Chim. Acta 55 (1972) 1490; (d) F . Brog li, E. He i 1 bro n n er, a1nd J . Ip a kt sch i, Helv. Chim. Acta 55 (1972) 2447; (e) C. Mi.iller, A. Schweig, and H. Vermeer, J. Amer. Chem. Soc. 97 (1975) 982 and the references cited therein. 5. M. J . S. D e war and J . S. Wasson (unpublished) ; N. B o do r, M. J . S. D e war, and J . S. Wass o n, J. Amer. Chem. Soc. 94 (1972) 9095. INTERACTIONS BETWEEN THE DOUBLE BONDS 15 6. J . A . Ne Ider and R. Mead, Computer J . 7 (1964) 308. M. I. Davis and T . W. Muecke, J. Phys. Chem. 14 (1970) 1104. 8. A . Yoko z e k i and K. Ku chits u , Bull. Chem. Soc. J ap., 44 (1971) 2356. 9. C. L. Norris, R. C. B ens on, and W. H . FI y gar e, Chem. Phys. Lett. 10 (1971) 75. SAZETAK Studij interakcija dvostrukih veza u nekim nezasicenim ketonima N . Bodor, M. J. S. Dewar i Z. B. Maksic Studirana je interakcija izmedu dvostrukih C=C i C=O veza u nekim konjugi-ranim ketonima u sporedbom izracunatih donizacij.skih potencijala s eksperimentalnim vrijednostima. Pri tome je koristena MIND0/2 semiempirijska metoda. Ustanovljeno je da je direktna interakcija »ikroz prostor« vrlo mala. Izuzetak je jedino 7-norbor-nadienon. Kod ostalih molekula se interakcija dvostrukih veza prenosi preko kemij skih veza. Izraeunani ionizacijski potencijaH su u dobrom slaganju s eksperi-mentalnim vrijednostima. DEPARTM E N T OF CHEMISTRY THE U N IVERSITY OF TEXA S AT A U STIN A USTIN, TEXA S , 78712, U .S .A. I GRUPA ZA TEORIJSKU KEMIJU INSTITUT »RUDER BOSKOVIC« 41001 ZAGREB, J UGOSLA VIJA Prispjelo 28. travnja 1975. 

A Study of the Interactions Between the Double Bonds in Unsaturated Ketones

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