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Hydrogen isotope effects in electron donor-acceptor systems
TetrahedronLettersNo. 71, pp 2919 - 2920. @Perga.m,n Press Ltd. 1979.Printedln Great Britain.
HYDROGEN
OO<$O-4039/79/0729-2919$02.00/O
ISOTOPE EFFECTS IN ELECTRON DONOR-ACCEPTOR
SYSTEMS
F.M. Martens, J.W. Verhoeven* and Th.J. de Boer Laboratory for Organic Chemistry, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands. Abstract: The charge-transfer (CT) transition of complexes involving alkylated aromatic electron donors shifts hypsochromically upon benzylic deuteration. This is attributed to hyperconjugative effects. The study of hydrogen
isotope effects on the properties of electron donor-acn I, ceptor (EDA) complexes has received little attention'-+. Our data compiled in
Table 1 now show, that small but significant hypsochromic -transition occur upon deuteration
aromatic donors and strong pi-electron Table 1
Donor
acceptors.
Solvent (20°C)
Acceptor
shifts of the CT-
in the donor for various complexes between
+T
(nm)
benzene
TCNEb
CH2C12
388.2~0.2
benzene-d6
TCNE
CH2C12
588.2
toluene
TCNE
CH2C12
412.6
toluene-d8
TCNE
CH2C12
411.9
Q-xylene
TCNE
cyclohexane
40 5/465.5
&-xylene-d10 HMBc
TCNE
cyclohexane
405/462.5
TCNE
CH2C12
539.6
HMB-d?8
TCNE
CH2C12
537,5
CH2C12
518.8
CH2C12
516.5
HMB
chloranil
HMB-d18
chloranil
d
a Shift of CT maximum upon deuteration. hexamethylbenzene.
d
AhvgT (cm
-1
0 2 10 41 141 72 86
b TCNE = tetracyanoethylene.
' HMB =
Chloranil = tetrachloro-p-benzoquinone.
The shift does not occur upon exclusive substitution of aromatic hydrogens but only upon substitution
of benzylic hydrogens
(cf. Fig. I), which excludes an
inductive mechanism. An explanation based upon steric effects would require a larger complex separation5 for the deuterated donors but the steric requirements of -C-2H are actually known 677 to be less than those of -C-'H. Therefore the increase in CT transition
energy IS tentatively
attributed to a slight in-
crease of the donor ionization potential (ID) due to less effective hyperconjugative interaction of -C-2H than -C-'H with the donor pi-system 8-10 . A
unique confirmation
of the hyperconjugative
comes from the behaviour CT-transitions
of the E-xylene/TCNE
nature of the present effects complex. The two closely spaced
shown by this system (cf. Fig. 2)
can be attributed5 to excita-
tions znoolving the highest occupied level (HOMO) and the penultimate
level
(HOMO-l) of the donor respectively. Only HOMO can be influenced by conjugative substituent effects since HOMO-l contains a nodal plane in which the substi2919
)
2920
No. 31
tuents lie (cf. Fig. 3). -_D-xybzno ---p-xykno-d,
Fig. 1 CT absorption of benzene/TCNE and of Fig. 2 CT absorption of E-xylene/ TCBE. IR'IB/TCNE. I The effect of perdeuteration of E-xylene (cf. ___
Table 1 and Fig. 2) thus corroborates our in-
___
terpretation ly
I HOMO
of the isotope effects since on-
a hypsochromic
shift of the longest wave-
length CT transition
HOMO-l
Fig. 5 Nodal properties of the two highest occupied MO's of e-xylene.
is observed while the
second transition remains unaffected! It seems important to note, that the changes in I D due to benzylic deuteration
as detected
by the present work are in principle sufficiently large (i.e. up to about 0.4 kcal/mol) to account for a significant kinetic isotope effect on one electron transfer reactions. This contrasts with the general (tacit) assumption, that in reactions involving one electron abstraction as a primary step -such as many 11-14 of alkylaromatics- the electron transoxidative side chain substitutions fer step is devoid of any isotope effect. Acknowledgement:
We are very grateful to Prof. L.E. Eberson
for a gift of z-xylene-dlO,
(University of Lund)
and for a stimulating discussion of our results.
REFERENCES 1. E.A. Halevi and M. Nussim, J. Chem. Sot. 876 (1963). 2. P.H. Emslie and R. Foster, Tetrahedron 2l, 2851 (1965). 3. F. Shahidi and P.G. Farrell, J. Chem. Sot., Chem. Commun. 455 (1978). 4. J.A. Chudek and R. Foster, Tetrahedron 2, 2209 (1978). "Organic Charge Transfer Complexes", Academic Press, London 6. R.E. Carter and L. Melander in "Advances in Physical Organic Chemistry" , Vol. 10, l-27, V. Gold Ed., Academic Press, London (1973). 7. S.F. Lee, G. Barth and C. Djerassi, J. Amer. Chem. Sot. 100, 8011 (1978 8. E.A. Halevi in "Progress in Physical Organic Chemistry"? Vol. 1, 109-22 :- 9 S.G. Cohen, A. Streitwieser and R.W. Taft Eds., Interscience, New York (1963). ’ 2416 (1963). 9. V.J. Shiner Jr and J.S. Humphrey Jr, J. Amer. Chem. Sot. (1965). 10. D.D. Traficante and G.E. Maciel, J. Amer. Chem. Sot. g, 11. L. Jonsson and L.G. Wistrand, J. Chem. Sot., Perkin Trans. I, 1 (1979). 12. K. Nyberg and L.5. Wistrand, J. Org. Chem. 43, 2613 (1978). 13. L. Eberson, L. Jonsson and L.G. Wistrand, Acta Chem. Stand. m, 520 (1978). 14. P.J. Andrulis, M.J.S. Dewar, R. Dietz and R.L. Hunt, J. Amer. Chem- Sot- 88, 5473 (1966).
(Receivedin UK 23 May 1979)
HYDROGEN
OO<$O-4039/79/0729-2919$02.00/O
ISOTOPE EFFECTS IN ELECTRON DONOR-ACCEPTOR
SYSTEMS
F.M. Martens, J.W. Verhoeven* and Th.J. de Boer Laboratory for Organic Chemistry, University of Amsterdam, Nieuwe Achtergracht 129, 1018 WS Amsterdam, The Netherlands. Abstract: The charge-transfer (CT) transition of complexes involving alkylated aromatic electron donors shifts hypsochromically upon benzylic deuteration. This is attributed to hyperconjugative effects. The study of hydrogen
isotope effects on the properties of electron donor-acn I, ceptor (EDA) complexes has received little attention'-+. Our data compiled in
Table 1 now show, that small but significant hypsochromic -transition occur upon deuteration
aromatic donors and strong pi-electron Table 1
Donor
acceptors.
Solvent (20°C)
Acceptor
shifts of the CT-
in the donor for various complexes between
+T
(nm)
benzene
TCNEb
CH2C12
388.2~0.2
benzene-d6
TCNE
CH2C12
588.2
toluene
TCNE
CH2C12
412.6
toluene-d8
TCNE
CH2C12
411.9
Q-xylene
TCNE
cyclohexane
40 5/465.5
&-xylene-d10 HMBc
TCNE
cyclohexane
405/462.5
TCNE
CH2C12
539.6
HMB-d?8
TCNE
CH2C12
537,5
CH2C12
518.8
CH2C12
516.5
HMB
chloranil
HMB-d18
chloranil
d
a Shift of CT maximum upon deuteration. hexamethylbenzene.
d
AhvgT (cm
-1
0 2 10 41 141 72 86
b TCNE = tetracyanoethylene.
' HMB =
Chloranil = tetrachloro-p-benzoquinone.
The shift does not occur upon exclusive substitution of aromatic hydrogens but only upon substitution
of benzylic hydrogens
(cf. Fig. I), which excludes an
inductive mechanism. An explanation based upon steric effects would require a larger complex separation5 for the deuterated donors but the steric requirements of -C-2H are actually known 677 to be less than those of -C-'H. Therefore the increase in CT transition
energy IS tentatively
attributed to a slight in-
crease of the donor ionization potential (ID) due to less effective hyperconjugative interaction of -C-2H than -C-'H with the donor pi-system 8-10 . A
unique confirmation
of the hyperconjugative
comes from the behaviour CT-transitions
of the E-xylene/TCNE
nature of the present effects complex. The two closely spaced
shown by this system (cf. Fig. 2)
can be attributed5 to excita-
tions znoolving the highest occupied level (HOMO) and the penultimate
level
(HOMO-l) of the donor respectively. Only HOMO can be influenced by conjugative substituent effects since HOMO-l contains a nodal plane in which the substi2919
)
2920
No. 31
tuents lie (cf. Fig. 3). -_D-xybzno ---p-xykno-d,
Fig. 1 CT absorption of benzene/TCNE and of Fig. 2 CT absorption of E-xylene/ TCBE. IR'IB/TCNE. I The effect of perdeuteration of E-xylene (cf. ___
Table 1 and Fig. 2) thus corroborates our in-
___
terpretation ly
I HOMO
of the isotope effects since on-
a hypsochromic
shift of the longest wave-
length CT transition
HOMO-l
Fig. 5 Nodal properties of the two highest occupied MO's of e-xylene.
is observed while the
second transition remains unaffected! It seems important to note, that the changes in I D due to benzylic deuteration
as detected
by the present work are in principle sufficiently large (i.e. up to about 0.4 kcal/mol) to account for a significant kinetic isotope effect on one electron transfer reactions. This contrasts with the general (tacit) assumption, that in reactions involving one electron abstraction as a primary step -such as many 11-14 of alkylaromatics- the electron transoxidative side chain substitutions fer step is devoid of any isotope effect. Acknowledgement:
We are very grateful to Prof. L.E. Eberson
for a gift of z-xylene-dlO,
(University of Lund)
and for a stimulating discussion of our results.
REFERENCES 1. E.A. Halevi and M. Nussim, J. Chem. Sot. 876 (1963). 2. P.H. Emslie and R. Foster, Tetrahedron 2l, 2851 (1965). 3. F. Shahidi and P.G. Farrell, J. Chem. Sot., Chem. Commun. 455 (1978). 4. J.A. Chudek and R. Foster, Tetrahedron 2, 2209 (1978). "Organic Charge Transfer Complexes", Academic Press, London 6. R.E. Carter and L. Melander in "Advances in Physical Organic Chemistry" , Vol. 10, l-27, V. Gold Ed., Academic Press, London (1973). 7. S.F. Lee, G. Barth and C. Djerassi, J. Amer. Chem. Sot. 100, 8011 (1978 8. E.A. Halevi in "Progress in Physical Organic Chemistry"? Vol. 1, 109-22 :- 9 S.G. Cohen, A. Streitwieser and R.W. Taft Eds., Interscience, New York (1963). ’ 2416 (1963). 9. V.J. Shiner Jr and J.S. Humphrey Jr, J. Amer. Chem. Sot. (1965). 10. D.D. Traficante and G.E. Maciel, J. Amer. Chem. Sot. g, 11. L. Jonsson and L.G. Wistrand, J. Chem. Sot., Perkin Trans. I, 1 (1979). 12. K. Nyberg and L.5. Wistrand, J. Org. Chem. 43, 2613 (1978). 13. L. Eberson, L. Jonsson and L.G. Wistrand, Acta Chem. Stand. m, 520 (1978). 14. P.J. Andrulis, M.J.S. Dewar, R. Dietz and R.L. Hunt, J. Amer. Chem- Sot- 88, 5473 (1966).
(Receivedin UK 23 May 1979)