JOURNAL OF T H E AMERICAN CHEMICAL SOCIETY Registered in the U. S. Palent Ofice.
@ Copyripht,
VOLUME88, NUMBER 2
1966, b y the A m e r i c a n Chemical Society
JANUARY 20, 1966
Physical and Inorganic Chemistry Molecular Orbital Calculations of Spin-Spin Coupling Constants for Hydrocarbons Robert C. Fahey, Gary C. Graham, and Robert L. Piccioni Contributionf r o m the Department of Chemistry, University of California at San Diego, La Jolla, California. Received August 13, 1965 Abstract: Contact contributions to H-H and W-H coupling constants in a selection of hydrocarbons are calculated according to the molecular orbital theory developed by Pople and Santry using one-electron wave functions and energies generated according to the extended Hiickel theory. Results are shown to be in semiquantitativeagreement with experiment for most types of coupling. Calculated values of directly bonded JHCHcorrelate with the observed values but are uniformly lower by a factor of about 1.5. For coupling through two bonds, both J H H and J H C Hare calculated to be negative in all the examples studied. This is in agreement with experiments for most saturated hydrocarbons but is in serious error for ethylene and acetylene. Calculated vicinal H-H couplings follow observed values in most of the cases studied.
ost of the recent theoretical studies of spin-spin coupling have utilized the valence-bond (VB) A molecular orbital (MO) theory has also been developed, but has, until recently, received less attention. In both the VB and MO methods, use has been made of the “average excitation energy approximation.” 6 ~ 7 This leads, in the case of the MO method as developed by McConnell,* to the prediction that all coupling constants between protons are positive. This is in contradiction to experiment. Recently, Pople and SantryYhave developed the MO method without invoking the “average excitation energy approximation.” In this more general form, couplings of either sign can arise. Pople has applied the theory to evaluate a number of couplings over one bond and found reason-
M
(1) M. Karplus, D. H. Anderson, T. C. Farrar, and H. S. Gutowsky, J. Chem. Phys., 27, 597 (1957). (2) M. Karplus and D. H. Anderson, ibid., 30, 6 (1959). (3) H. S. Gutowsky, M. Karplus, and D. M. Grant, ibid., 31, 1278 (1959). (4) M. Karplus, ibid., 30, 11 (1959). (5) M. Barfield and D. M. Grant, ibid., 36, 2054 (1962); J . Am. Chem. Soc., 83, 4726 (1961); 85, 1899 (1963). (6) N. F. Ramsey, Phys. Rev., 91, 303 (1953). (7) A. D. McLachlan, J . Chem. Phys., 32, 1263 (1960); M. Karplus, ibid., 33, 941 (1960). (8) H. M. McConnell, ibid., 24, 460 (1956). (9) J. A. Pople and D. P. Santry, Mol. Phys., 8, 1 (1964).
able agreement with experiment. The theory accounts qualitatively for the variation in geminal couplings with structure,I0 but numerical calculations according to a one-electron MO theory with neglect of overlap give the wrong sign for the coupling in methane,” as do the earlier VB calculations. l z 3 The MO method clearly shows promise and deserves to be tested further In the present paper, we employ the extended Huckel theory, l 2 which includes overlap, to calculate coupling constants in a number of hydrocarbons. Method According to Ramsey’s general theoryY5 nuclear spin-spin interactions occur by four distinct mechanisms. The direct dipolar interactions, which lead to a line broadening in solids, average to zero under rapid rotation in liquids. l 3 The nuclear spin-electron spin (10) J. A. Pople and A. A. Bothner-By, J. Chem. Phys., 42, 1339 (1965). (11) J. A. Pople and C. P. Santry, Mol. Phys., 9, 301, 311 (1965). (12) R. Hoffmann, J . Chem. Phys., 39, 1397 (1963), and references
therein . (13) In the liquid crystal nematic phase, direct dipolar interactions often do not average to zero and give rise to large splittinqs in the observed n.m.r. spectrum. For examples and references see L. C. Snyder and E. W. Anderson, J . Am. Chem. Soc., 86,5023 (1964); W. D. Phillips, J. C. Powell, and L.R. Melby, J . Chem. Phys., 41, 2551 (1964).
193
194
(spin dipolar), nuclear spin-electron orbital (spin orbital), and Fermi contact interactions are in general nonzero for liquids. However, the spin-dipolar and spin-orbital contributions are, in the first approximation, negligible if either of the nuclei involved in the coupling is a p r ~ t o n . ~We will here restrict our attention to couplings involving protons and need, therefore, consider only the contact contributions to the spin-coupling constant. In the one-electron MO approximation, the contact contribution, J(3).4B, to the coupling of nuclei A and B is given by
culations are as follows: cyclohexane, chair form; cyclopentane, planarB L ccc = 108'; cyclobutane, planar, DCH 7 1.09 A., L HCH 112'; cyclopropane, DCC = 1.53 A., D C H = 1.09 A., LHCH = 114'; ethylene, DCC = 1.34 @H = 1.09 < H C H = 120'; benzene, Dcc = 1.395 A., DCH = 1.09 A.; acetylene, DCC = 1.21 D C H = 1.06 A. Unless determined by symmetry or otherwise stated, bond angles are taktn as 109" 28' and bond distances of 1.10 and 1.54 A. are used for C-H and C-C bonds, respectively. o=
A.,
A.,
A.,
Results The calculated and observed coupling constants are compared in Tables I, 11, and 111. The signs for these
YPVU
The derivation of eq. 1 is given by Pople and S a n t r ~ . ~ Table I. Coupling through One Bond, J I l C H They further simplified eq. 1 by retaining only one-center Compound J(3)cn~cda Jobsda integrals involving valence-shell S orbitals on nuclei A and B. However, not all terms involving the product hlethane 83 125 Ethane 84 of a one-center integral with a two-center integral are 125 Cyclohexane 856 123, 124 truly negligible. In the present work we retain the Cyclopentane 85 128 more important terms of this type. Specifically we Cyclobutane 93 134 include all terms for which Cyclopropane 107 161 Ethylene Benzene Acetylene
X = p = Aandv = u = B X'#p=Aandv=u=B p'#X=Aandv=u=B X = p = Aandv' # u = B X = p = Aandu' # v = B
where X and p are valence-shell S orbitals on A, v and u are valence-shell S orbitals on B, A ' and p' are any vz$ence-shell orbital on an atom located less than 2.0 A. from A, and Y' and G' are any valenceshell orbital on an atom located less than 2.0 from B. One-electron wave functions and energies are computed according to the extended Huckel theory, using the following valence-state ionization potentials (e.v.) for the diagonal matrix elements: H,,(HlS) = - 13.6, H,,(C2P) = -11.4, and H,,(C2S) = -21.4. All overlaps are included and the off-diagonal matrix elements are approximated by
107 100 169
Jobsdl
Ref.
J(3)cs~cd
1.51 1.50 1.45 1.51 1.44 1.50 1.46 1.59 1.47
C
d, e c,f c,f' j' C
d, e c d, e
156 159 249
a Values are given to the nearest C.P.S. * Average of the coupling to H, (86c.p.s.)andH,(84c.p.s.). N. Muller a n d D . E. Pritchard, J . Clieni. Pliys., 31, 768 (1950). R. M. Lynden-Bell and N. Sheppard, Proc. Roy. Soc. (London), A269, 385 (1962). e D. M. Graham and C. E. Holloway, Caii. J . Clzem., 41, 2114 (1963). C. S. Foote, Tetrahedron Letters, 579 (1963).
A.
HIIY= 0.5K(H,,
Table 11. Coupling through Two Bonds
(14) See ref. 9 for the definition of terms used in eq. l . (15) J. R. Morton, J. R. Rowlands, and D. H. Whiffan, National Physical Laboratory Report BPR 13, 1962.
Journal of the American Cheniical Society
Coupling
C.P.S.
C.P.S.
Ref.
~
Methane Ethane
H-H H-H 3C-H Cyclohexane H-H '3C-H, l3C-He Cyclopentane H-H '3C-H Cyclobutane H-H
+ Hvu)Spv
(2) with K = 1.75.l 2 Slater atomic orbitals with exponents of 1.2 for hydrogen and 1.625 for carbon are used as the basis set. Slater orbitals cannot be used in the evaluation of the contact integrals (4h\?j(r)(+X) owing to the improper behavior at the nucleus for 2s orbitals. For this part of the calculation, hydrogen-like orbitals are adopted. The effective nuclear charge, Z e ~ is , taken as 1.2 for hydrogen. For carbon, 2,s is chosen so that the integral (2S;6(rc)12S) has the same value (2.767 a.u.) as that obtained from self-consistent field calculations.15 This requires a value of 4.11 for carbon. A version of the extended Huckel theory computer program developed by Hoffman1* was modified to include the calculation of J(3'an.Input consists of the appropriate H,,, Slater exponent, and atom coordinates for each atomic orbital and the effective nuclear charges for the nuclei whose coupling is to be computed. Pertinent data on the structures assumed for the cal-
Jabsd,
J(3)cn~cd,
Compound ~~~~
'3C-H Cyclopropane H-H '3C-H Ethylene H-H 13C-H I3C-H Benzene 13C-H Acetylene
-16.5 -16.7 -4.0 -17.0 -4.1 -4.2 -17.5
-12.4
J'
-4.5, -4.8 -12 to -13O
g, h
i,j
-8 to -13b
k
-4.2 -18.1 -3.3 -19.3 -2.8 -15.2 -8.0 -6.9 -5.9
- 4 . 3 to -9.lC - 1 3 . 1 , ~ -15.3d -10.9d
1
m, n
-5.66
0
2.5,2.3,2.0 -2.4
g, 11
49.3, 49.7
g,li,p g, h
~
For norbornene For derivatives of the parent hydrocarbon. and norbornane derivatives. For bicyclo[2.l.l]hexane derivatives. For cyclobutanone derivatives. e Predicted for cyclopropane from studies on cyclopropane derivatives: T. Schaefer, F. Hruska, and G . Kotowycz, Can. J . Chem., 43,75 (1965). Reference 1. 0 Footnote d, Table I. h Footnote e , Table I. ' J. I. Musher, J . Chem. Phys., 34, 594 (1961). 7 F. A. L. Anet, J. A m . Cliem. Soc., 84, 1053 (1962). k P. Lazlo and P. von R . Schleyer, ibid.,86, 1171 (1964), and references therein. 1 K. B. Wiberg, B. R. Lowry, and B. J. Nist, ibid.,84, 1594 (1962). m M. Takahashi, D. R . Davies, and J. D. Roberts, ibid., 84, 2935 (1962). n K. L. Servis and J. D . Roberts, J . Phys. Chem., 67, 2885 (1963). T. Schaefer, et al., footnote e above. p G. S. Reddy and J. H. Goldstein, J . Mol. Spectry., 8, 475 (1962).
88:2 1 January 20, I966
O-
0
195 Table HI.
Coupling through Three Bonds
~~
Compound
Coupling
J(')oalod,
Jobad,
C.P.S.
C.P.S.
Ref.
H - H , + = 0" 7 . 8 = 30" 5 . 7 = 60' 1 . 8 = 90' 0 . 2 = 120' 3 . 4 = 150' 9 . 2 = 180'11.9 Cyclohexane H,-H, 1 1 . 0 9-13O Ha-He 1 . 8 2-6a He-& 1 . 9 2-4" Cyclopentane H-H, cis 7 . 8 5.8-11.4b trans 3 . 8 2.1-5.8* Cyclobutane H-H, cis 5.4 trans 5.1 Cyclopropane H-H, cis 3.7 9.20 trans 5.6 6.2c Ethylene H-H, cis 5 . 9 11.6, 11.5, 1 1 . 4 trans 16.8 19.1, 18.8 Acetylene H-H 8.5 9.6,9.8,9.1 Ethane
d, e d, e , f
E
f,g h h
(e.v.1
O t -10
E3
i I
j,k,I j , k, 1 j,k,I
b For norbornane and norbora For cyclohexane derivatives. nene derivatives. c Predicted for cyclopropane from results on substituted cyclopropanes: Schaefer, et al., footnote e, Table 11. d Footnote i , Table 11. e A. C. Huitric, J. B. Carr, W. F. Trager, and B. J. Nist, Tetrahedron, 19, 2145 (1963), and references therein. f D. H . Williams and N. S. Bhaca, J . Am. Chem. Soc., 86, 2742 (1964). 0 Footnote j , Table 11. h Footnote k , Table 11. i Schaefer, Footnote et al., footnote e, Table 11. j Footnote d, Table I. e, Table I. 1 Reference 1.
couplings are now established with reasonable certainty, based on the absolute sign of the ortho coupling in p-nitrotoluene. This coupling has been shownlo to be positive, and it may be reasonably assumed that all other large H-H couplings through three bonds are also positive. Relative sign determinations, either by spectral analysis l7 or spin-decoupling experiments, l8 allow other couplings to be related to H-H couplings over three bonds and thereby indirectly fix their absolute signs. The theoretical coupling constants reported here include the contributions from the terms involving products of one- and two-center integrals as described above. In most cases, the calculations have also been carried out with the neglect of these terms so that their effect is easily evaluated. The additional terms contribute from 11 to +27 C.P.S. to the 13C-H couplings in Table I, from +1.5 to +8.5 C.P.S. to the H-H couplings in Table I1 (making the total coupling less negative), from -0.4 to +1.6 C.P.S. to the 13C-C-H couplings in Table 11, and from 0.5 to f1.0 C.P.S. to the couplings in Table 111.
+
(16) A. D. Buckingham and I
