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Delocalization
'The molecular orbitals are the result of single determinantal abinitio SCF calculations using the 3G basis set. See Ref: ( 1 5 ) .
<
C3
to stahility.
R - R'
Hi"H
'
L q d*
Figure 1. Total electronic density diagram for non-bonded pairs.
- . ..
.~
c+/"
H'
The electron has a maximum dipole moment when occupying a hybridized nonbondingorhital having A equal to f1,
and these correspond to the two s p hyhrids. I t may be of interest togive the values of thequantity U ( 1 + A2) for the more
common values of A, and we do that in Tahle 2.
The last value in
Tahle 2 is obtained
Table 2. TheValuesaf hl(1 + A 2 ) for
either by using
s, sp, sp', sp: and p orbitals
L'HBpital's rule or
by rewriting the
"('
+
quantity as I/(X
1/X) and letting A
approach infinity.
3%
0.433
Starting with pure s
orbital, mixing in p
character brings
about a rapid increase in the dipole moment. The average position of the
electron moves away from the nucleus. The maximum occurs
when equal amounts of s and p have been mixed. Continued
increase i n p character gradually reduces the dipole moment
back to zero. It may come as a surprise that the maximum
moment is associated with the s p hybrid rather than the sp3.
This result and some of those stemmine- from delocalization
arguments indicate that even our most basic assumptions
should continuallv he reexamined. For example, do the six
r-electrons in beizene really acruunt for its s ~ n h i l i tor
~ ,arr
the 36 o-electrons actuallv responsible (If?)? Even tndnv, this
cannot he answered with cervery fundamental
tainty.
"'
).
.o'
H
If one uses the localized picture for the nonbonding pairs,
this structure corresponds to a completely staggered conformation with a carbon-hydrogen hond in the region between
the lone-pairs on the oxygen atom, but this satisfying picture
is lost if one uses a more accurate description such as the one
just presented for water.
The pictures we present in the introductory organic
chemistry courses a m both simple and appealing and generally
lead to correct predictions ahout the behavior of organic systems. Nevertheless, they do not hold up under rigorous scrutiny.
The idea of localized lone pairs in nonbonded hybridized
orbitals is so well ingrained and works so successfully that it
seems worthwhile to examine more closely some of the predictions of this approach, for even here the conclusions are not
obvious. Consider, for example, which type of nonhonded
hybrid-sp, sp2, sp3-gives rise to the largest dipole moment.
A hybridized nonbonding orbital h can be written as2
h = (1 + h2)-'" ( S + Ap)
where A takes on the values 3lf2, 2112,and 1for the common
sp" sp2, and s p hybrids. The dipole moment p of an electron
in such a nonbonded hybrid is
p = jhedhdu
where e is the electronic charge and d its distance from the
nuclear center.
Subsituting for h and expanding leads to
p =
1 t A
J(s
+ Ap)ed(s + Apldu
Conclusion
The ideas iust oresented are neither verv difficult nor very
mathematical, A d their introduction -into the organic
chemistry course would not take much time. They may give
the student a better idea of some fundamental concepts.
All electrons are delocalized, and such delocalization, if it
is truly to account for the difference in energy between stationarv states. must result in a lowerinn of the potential energy. The kinetic energy must increase with increased stahility
of the svstem. Alternatively, certain processes, considered to
he del&alizations, may actually bd localizations, e.g., the
formation of the covalent hond in the hydrogen molecule.
Even then, the kinetic energy must increase, and greater
stability must come from a lowering of the potential energY.
Acknowledgment
This work was done a t the Universitv of California.
Berkeley.
The author is verv much indebted to the Facultv of the
Chemistry ~ e ~ a r t m e na t the University of ~aiifornia,
Volume 54, Number 8. August 1977 1 481
;I 2:;.~:~&~~,"~;a
Hill,Nw
~ o r k 1963,
.
Chapter 3.
(7) ~ e i t l e rw.,
, and h n d o n , F,z ~ h y s i k 44.4%
,
(19271.
(81 Wsng, S. C., Phys Rau. 31.579 (1928).
(9) Rosen, N., Phyr. Re".. 38,2099 (19311.
(10) Eile.8, J. E.. and Liberlr*. A,, J , Arne?. Chem Soc., 97,4183 (19751.
(11) Liberles.A.,Greenherg,A..and Eilers, J.E., J.CHEM. EDUC.,60,676 (19731.
(12) Dewar, M. J. S., and Wor1ey.S. D., J. Chem. Phys, 50,654 (19691.
(13)
figurea are taken from Streifwieser, h.,A,, and Owens. P. H., "Orbital and
~ These
,
Electron Density Disgrsms," Maemillsn, New York. 1973. p. 123.
(14) Ivash, E. V.,and Dennisan, D. M . , J Chem. P k m 21.1804 U953).
(15) Hehre, W. J., Stewart, R. F.,snd Pople, J. A., J. Chem. Phys. 51.2657 (1969).
(16) Wiherg, K. B.. " P h y s i d Olganic Chemistry," John Wileyand Sons.lne.. New York,
1964, p. 66 (seefootnote 23 therein).