Notes 433
2 shows the spectrum, which is attributed to the Experimental Section
CDS radical on the basis of the line intensities and
splitting constant. Comparison of Figures 1 and 2
shows that CD3 formation by solvent cleavage cannot
·
account for any significant portion of the central line
of Figure 1.
4. Summary and Discussion. The esr spectrum of
protonated methyl radical in a glass of TMPD and
perdeuterated 3MP at 77°K is shown to arise from the
ß scission of TMPD, with a biphotonic mechanism in-
dicated. It is of interest to note that the CH3 signal ap-
·
pears only after prolonged irradiation, but the trapped
electron (seen at a much lower microwave power)
appears after only a few minutes. Since ß scission does
occur in this perdeuterated glass, this pathway should
also be viable in the protonated systems. Whether or
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not it is the dominant mechanism for producing the
methyl radical fragment in the protonated systems re-
mains to be established. A similar study of perdeu-
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terated TMPD in protonated 3-MP could greatly
clarify this question.
Acknowledgments. The authors wish to acknowledge
the assistance of Richard Kornfield in obtaining the
mass spectrum of the perdeuterated 3-MP.
Keto-Enol Equilibria in 2,4-Pentanedione and
3,3-Dideuterio-2,4-pentanedione
by David W. Thompson and A. L. Allred*
Department of Chemistry and Materials Research Center,
Northwestern University, Evanston, Illinois 80301
(Received April 8, 1989)
Publication costs borne completely by The Journal of Physical Chemistry
The goal of this research was to investigate hydrogen
isotope effects on intramolecular hydrogen bonds. The
per cent of each enol tautomer, apparently containing
intramolecular hydrogen bonds, in D20 solutions of 3-
deuterio-3-methyl-2,4-pentanedione1 ·2 and 1-deuterio-
2-acetylcyclohexanone8 is less than the per cent enol
tautomer present in the corresponding completely pro-
tonated compound in H20. Values of acid ionization
constants show that there is less intramolecular hydro-
gen bonding for the deuterio maléate ion in D20 than for
the hydrogen maléate ion in Hs0.4 Interpretation of
the above results is difficult owing to the possibility of
different solvent effects from H20 and D20. Deute-
rium, in several systems,6-7 forms stronger intermolecular
hydrogen bonds than protium. In this research, keto-
enol equilibria were measured by nmr for pure /3-dike-
tones and 0.5 mole fraction solutions in cyclohexane and
by uv spectroscopy for dilute solutions in cyclohexane.
Preparation of S,S-Dideuterio-^,4-pentanedione, 3,3-
Dideuterio-2,4-pentanedione was prepared by stirring
2,4-pentanedione (Eastman Organic Chemicals) with
excess deuterium oxide (99.7 mol % D20), extracting
with methylene chloride, and finally fractionally dis-
tilling the deuterated product. This exchange process
was repeated three times.
Anal. Caled for CsH«D202: C, 58.80; total hydro-
gen, 9.87. Found: C, 58.60, 58.64; total hydrogen
assuming H:D =
3:1, 9.75, 10.1. Analysis was by
Micro-Tech Laboratories, Inc., Skokie, III.
The purity of the product was confirmed by nmr,
uv, ir,3 and mass spectra.9 Substitution of deuterium
at the 3 position of 2,4-pentanedione was ~93% as
shown by peak height measurements of the nmr signals
from the methylene protons of 2,4-pentanedione and
3,3-dideuterio-2,4-pentanedione, under similar instru-
ment settings. The hydroxyl group and the vinyl
carbon have the same per cent of protium within the
experimental error of nmr measurements.
No attempt was made to increase the methylene
deuterium content to the theoretical limit since approxi-
mately 2% deuterium substitution into the terminal
methyl groups was observed by nmr after the last ex-
change reported above.
Spectra. The keto-enol equilibrium constants were
determined by electronically integrating, with a Varían
Associates, Inc., A-60 spectrometer, the nmr signals of
the terminal methyl groups of the two tautomers.
Integrations were optimized according to the guidelines
of Jungnickel and Forbes.10 Uv data were obtained
with a Cary Model 14 spectrophotometer.
Results
The equilibrium and thermodynamic constants
derived from nmr data fot 2,4-pentanedione and 3,3-
dideuterio-2,4-pentanedione are summarized in
Table I.
The ultraviolet spectrum of 2,4-pentanedione exhibits
a maximum at 271 µ due to the enol tautomer. Sub-
stitution of deuterium into the 3 position does not alter
noticeably either the position or the shape of the enol
F. C. Nachod, Z. Phys. Chem., Abt. A, 182, 193 (1938).
(1)
(2) F. A. Long and D. Watson, J. Chem. Soc., 2019 (1958).
(3) T. Riley and F. A. Long, J. Amer. Chem. Soc., 84, 522 (1962).
(4) G. Dahlgren, Jr., and F. A. Long, ibid., 82, 1303 (1960).
(5) C. J. Creswell and A. L. Allred, ibid., 84, 3966 (1962), and
references therein.
(6) (a) G. R. Plourde, Dies. Abstr., 22, 1400 (1961); (b) R. West,
personal communication.
(7) D. W. Thompson, Ph.D. Thesis, Northwestern University,
1968.
(8) H. Ogoshi and K. Nakamoto, J. Chem. Phys., 45, 3113 (1966).
(9) “Catalog of Mass Spectral Data,” American Petroleum Insti-
tute, Project No. 44, Carnegie Institute of Technology, Pittsburgh,
Pa.
(10) J. L. Jungnickel and J. W. Forbes, Anal. Chem., 35, 938 (1963).
The Journal of Physical Chemistry, Vol. 75, No. 3, 1971
434 Notes

Table I: Equilibrium and Thermodynamic Constants for Enolization of

2,4-Pentanedione and 3,3-Dideuterio-2,4-pentanedione from Nmr Measurements

AS,
AH, cal mol”1
% keto K T, °c koal mol-1 deg”1

O 0

ch8cch2cch8 21.8 ± 0.3“ 3.59 37.3 -2.4 ± 0.2s -5.2 ± 0.6s

(pure) 13.6 ± 0.5 6.35 2.5
10.5 ±0.3 8.52 -19.0
O 0

ch8ccd>cch, 19.1 ±0.4 4.24 37.3 -0.10 ±0.04 2.6 ± 0.2

(pure) 18.5 ± 0.3 4.41 2.5
18.6 ±0.3 4.38 -19.0
O 0
II II

ch8cch2cch8 10.4 ± 0.2 8.62 37.3 -1.8 ±0.1 -1.4 ± 0.2

. 5 mole fraction in CeHu) 7.4 ± 0.3 12.51 0.0
5.8 ± ~1 16.2 -18.5
O O
II II
1! ¡1

CHsCCDeCCH, 11.0 ±0.2 8.09 37.3 0.09 ± 0.12 4.5 ± 0.4

. 5 mole fraction in CeHu) 10.7 ± 0.3 8.34 0.0
11.4 ±0.3 7.77 -18.5
1

Standard deviation. 6
Probable error.

absorption band. With the assumption that the molar
absorptivity for 2,4-pentanedione does not change upon
substitution of deuterium into the 3 position, uv data at
25° for dilute (co. 10~6 M) cyclohexane solutions of 2,4-
pentanedione and 3,3-dideuterio-2,4-pentanedione un-
ambiguously show that Ku is significantly larger than
KD.
Discussion
The magnitudes, Table I, of AHenotation for both pure
2,4-pentanedione and a 50:50 2,4-pentanedione-cyclo-
hexane solution are much more negative than those of
the deuterated analog. As reported earlier,11 the in-
tensity of the 1712 cm-1 peak, due to carbonyl stretch-
ing, in the infrared spectrum of 2,4-pentanedione in
cyclohexane is considerably smaller than for the deu-
terium analog, Also, uv studies of dilute solutions,
co. 10-8 M, of 2,4-pentanedione in cyclohexane at
25° show that the enol content is significantly larger
than in a comparable solution of 3,3-dideuterio-2,4-
pentanedione. If stabilization of the enol tautomer
by intramolecular hydrogen bonding is an important
factor in determining the overall enthalpy of enolization,
protium apparently forms a stronger hydrogen bond
in this system than does deuterium.
For the normal protium-containing compound, both
pure and in cyclohexane solutions, the AH and AS val-
ues in Table I are comparable to other recently reported
values.12-14
ated enol tautomer being less ordered as a consequence
of less intramolecular hydrogen bonding. Both inter-
molecular hydrogen bonding and the existence of some
nonhydrogen-bonded enol tautomer would make AS
more positive. Free hydroxyl groups in the gas phase
and in carbon tetrachloride solutions have been ob-
served by ir.11 Evidence for molecular association
comes from both nmr spectra and cryoscopie measure-
ments. Rogers and Burdett16 concluded from the
chemical shifts of 2,4-pentanedione in various concen-
trations of cyclohexane and from temperature studies
that intermolecular association is important. Our
chemical shift measurements confirm the work of Rogers
and Burdett and furthermore show sigmoid variations
at concentrations below 0.2 mole fractions, thus prob-
ably explaining why others12·13 reported no chemical
shifts for this system. Freezing point depressions of
2,4-pentanedione-cyclohexane solutions are consistent
with intermolecular association. For example, the
apparent molecular weight of 2,4-pentanedione is 105
in 0.10 m solution and 113 in 0.18 m solution, whereas
the true molecular weight is 100.
The large differences in enol-keto ratios and thermo-
dynamic constants for 2,4-pentanedione and 3,3-dideu-
terio-2,4-pentanedione are difficult to explain. Isotope
(11) S. Bratoz, D. Hadzi, and G. Rossmy, Trans. Faraday Soc., 52,
464 (1956).
(12) L. W. Reeves, Can. J. Chem., 35, 1351 (1957).

The entropy of enolization is much more positive for (13) G. Allen and R. A. Dwek, J. Chem. Soc. B, 161 (1966).
(14) J. Kuo, Dies. Abstr. B, 27, 3064 (1967).
3,3-dideuterio-2,4-pentanedione than for 2,4-pentane- (15) . T. Rogers and J. L. Burdett, Can. J. Chem., 43, 1516
dione. This difference can be attributed to the deuter- (1965).

The Journal of Physical Chemistry, Vol. 76, No. 8, 1971

Notes
effects of the keto form are doubtless small and mainly
confined by zero point energy differences of vibrations
involving the methylene group. The maximum dif-
ference in bond dissociation energies for [Z?0(O-H)
Eo(C-H)] -
[Eo(O-D) So(C-D)]16 is too small to
~
account for the differences in enthalpy values in Table
I. Conceivably, enolization of 3,3-dideuterio-2,4-pen-
tanedione is less favored as a consequence of the mean
O-D bond length being less than that of OH, and there-
fore the hydrogen bond, -D-O, being longer and
weaker. Normal bonds, for example -O-D, involving
deuterium always are shorter than analogous protium
bonds due to anharmonic vibrations.17 Williams re-
ported18 the following bond distances and angles from
an investigation by X-ray crystallography
2.468 A
If this planar, chelated enol structure had involved
average17 bond lengths (rc_c = 1.537 A, rc=o = 1.335,
rC-o = 1.426, rC-o = 1.215) and bond angles of
either 120° or 105°, the 0-0 separation would be 2.50
Á and the hydrogen atom would be >0.30 Á from the
0-0 line. The actual O-H distance above is ~0.22 Á
greater than the average O-H distance17 in nonhydrogen
bonded compounds. Thus, formation of the enol ring
apparently is accompanied by bond strains, and the
small difference in O-H and O-D bond lengths may be
unusually important.
The data presented here indicate that acidity con-
stant data4 and keto-enol equilibrium data1-3 for
/3-diketones in light and heavy water are indeed best
explained in terms of protium forming a stronger intra-
molecular hydrogen bond than deuterium in these sys-
tems and that solvent differences between light and
heavy water are not dominant.
Acknowledgments. D. W. T. expresses appreciation
for a predoctoral fellowship from the Division of General
Medical Sciences, United States Public Health Service.
This research was supported in part by the Advanced
(16) K. B. Wiberg, Chem. Rev., 55, 713 (1955).
(17) L. E. Sutton, “Tables of Interatomic Distances and Configura-
tion in Molecules and Ions” (Special Publication No. 18), The
Chemical Society, London, 1965.
(18) D. E. Williams, Acta CrystaUogr., 21, 340 (1966).
435
Research Projects Agency of the Department of De-
fense, through the Northwestern University Materials
Research Center.
—
Comparative Ligand Field Studies of
Manganese(II) Spectra
by A. Mehra
College of Environmental Sciences, University of Wisconsin—Green
Bay, Green Bay, Wisconsin 54305 (Received May 18, 1970)
Publication costs assisted by the University of Wisconsin—Green Bay
A comparative study of Mn2+ spectra in different
ligand coordinations is undertaken in this work. The
large number of bands in the spectrum of Mn2+ allows a
free variation of various parameters and provides a
good check on ligand field calculations. Spectra in
hydrated, fluoride, chloride, and bromide complexes
are investigated and regularities have been observed.
The energy levels from d6 configuration of Mn2+ and
the general features of observed spectra have been
reviewed earlier.1-3 The observed band positions in
several cases are given in Tables I and II. Several
schemes for fitting the band energies have been sug-
gested.4-8 One of the best is that of Heidt, Koster,
and Johnson4 using free variation of the three crystal
field parameters B, C, and Dq. However, it is found
that these three parameters are not enough to give
good agreement with all the band energies. A similar
case is encountered for the free ion where the use of
only two electrostatic parameters B and C does not give
good agreement for all the terms.9-11 Consequently,
several correction terms for fitting the free ion term
values have been suggested. Among these, Trees’
correction term is found to be most important.10·11
Following its success for the free ion, we have included
this term in our ligand field calculations. The signifi-
cance of this correction11 and the matrix elements in
(1) N. 8. Hush and R. J. H. Hobbs, Progr. Inorg. Chem., 10, 259
(1968).
(2) D. S. McClure, Solid State Phys., 9, 399 (1969).
(3) C. . Ballhausen, "Introduction to Ligand Field Theory,”
McGraw-Hill, New York, N. Y., 1962.
(4) L. J. Heidt, G. F. Koster, and A. M. Johnson, J. Amer. Chem.
Soc., 80, 6471 (1958).
(5) L. E. Orgel, J. Chem. Phys., 23, 1004 (1955).
(6) J. W. Stout, ibid., 31, 709 (1959).
(7) W. Low and G. Rosengarten, J. Mol. Spectrosc., 12, 319 (1964).
(8) A. Mehra and P. Venkateswarlu, J. Chem. Phys., 45, 3381
(1966).
(9) J. C. Slater, “Quantum Theory of Atomic Structure," McGraw-
Hill, New York, N. Y., 1960.
(10) R. E. Trees, Phys. Rev., 83, 756 (1951); 84, 1089 (1951); and
85, 382 (1952).
(11) G. Racah, ibid., 85, 381 (1952).
The Journal of Physical Chemistry, Vol. 76, No. S, 1971