N.

Colin Baird
University of Western Ontario
London. Ontario, Canada
I
The similarity between one-electron and three-electron
bonds is evident from the simple molecular orbital (MO)
The Three-Electron Bond
the overlan between the orbitals is not too h e . Interestingly,
the energy match requirement appears also ;n the ~imple;~a-
theory. For a single electron, occupancy of the bonding M O lence-bond model for three-electron tmnds. In particular, for
yields a bond order of %. Although a second electron can also the two structures shown below for a 3-electron bond between
occupy the bonding MO,the stabilization it provides is can- atoms A and B, resonance will occur significantly only if the
celled by the destabilization of the third electron due to its structures are of almost equal energy
occupancy of the antibonding MO.At the simplest theoretical
level, the stabilization of the bonding M O is equal but opposite
to the destabilization of the anti-bonding level. Thus the net
A: B - A. :B

Therrnodvnarnlc Stabllltles of Three-Electron Systems

stabilization energy for such three-electron bonds is predicted
nlwavs
-~- ~~A~
to be half the streneth of a two-electron bond. The
~ ~~
The prototype Lhree-electron bond with initially degenerate
equality between the stabilkation of the lower level and the levels occurs in the dihelium wsitive ion, He?'. This system
destahilization of the upper holds a t the simple Huckel level as
is known(1) spectroscopically t o be stable predicted; the
even when the levels initially are nondegenerate. dissociation enerev is about 57 kcal mole-' and the bond
Although the simple Huckel method with overlap integrals distance is 1.08 A:~he prototype for a 3-electron bond with
neglected predicts that a three-electron bond is always sta- initial levels of very different stability is the hydride of helium,
bilizing, this is not true if the overlap is included. The inter- HeH. The ground state of this system is dissociative ( 2 ) ,thus
actions associated with a three-electron bond involving two confirming the argument that the net effect of this type of
initially degenerate levels is net destabilizing if the overlap three-electron bond is net destabilizing.
integral exceeds U;for nondegenerate levels the crossover from The most commonly encountered three-electron bond in
stabilization to destabilization occurs at even smaller overlaps. organic chemistry is that between carbon and oxygen.
The quantum-mechanical origin of this strange hehavior for
three-electron bonds is illustrated by the orbital-splitting
diagram in Figure 1. The bonding level is stabilized by an
+
amount proportional to 1/(1 S ) , where S is the "overlap IF OVERLAP INCLUDED
integral" between the orbitals. The antibonding level is de-
stabilized in proportion to 1/(1-S). If S > 0,then the anti-
bondine leuel is more destabilized than the bond in^ level is
stabilized (see Fig. 1).Since the advantage in magnitude of
destabilization over stabilization increases with S, then under
some circumstances the destabiliation of a single electron
occu~vinrtheantibondine M O will outweinh the total stabi-
lizatio"n o? two electrons occupying the boGding MO.As the
eaD in enerev between the initial levels is increased, the nu-
k r i c a l advantage held hy desrabilization of the antibonding
M O over stabilization of the bondina M O increases. In fact,
Huckel theory with overlap integralsincluded predicts that
a three-electron bond is significantly stabilizing only when STABILIZATION IF s<$
the two levels i n i t i i y are of equal or almmt equal energy, and
'Presented, in part, at the VIll InternationalConference on Pho- DESTABILIZATION IF s>$
tochemistry, Edmonton, Alberta, Canada, August 7-13, 1915. Re-
search supported by the National Research Council of Canada. Figure 1. Orbital splftting diagram.

Volume 54, Number 5, May 1977 / 291


\ nn* STATES
Of
HNNH
Figure 2. Threeelecbon bonds in excited states.
lor HNN' -
A B INITIO (4-31G) SURFACE
H ' r N2
-m1
0.8 10 1.2 1.4 1.6 18 2.0 2.2
H-N DISTANCE
Figure 3. Potential energy surtace for HNN' -+
(inA1
H' NI.
Both theoretical calculations and experimental evidence
suggest that the three-electron carbon-oxygen hond is very
slightly stabilizing. In the case of formaldehyde, the energy
required (3)to excite the molecule from its ground state to the
triplet n a * state is 72 kcal mole-'. Since this value is close to
the 74 kcal mole-' difference between a double hond and a
single hond (estimated using E(C==O) = 165 and E(C-0) =
91 kcal mole-'), i t follows that the comhination of the single
hond plus the 3-electron a bond in the 3na* state is only
marginally more stable than is a C-0 single hond alone.
For the H Z O H free radical. Ha has calculated ( 4 )a rota-
tional harrier for O-H bond tbrsion of about 4 kcalmole-'.
Since such twisting destroys the 3-electron hond between the
carbon singly occupied 2p, orbital and a lone-pair orbital on
--
oxveen.. the s t r e n a h of this linkage must he small. Further
confirmation is by the experimental finding (5)that
the hvdroaen-carbon hond dissociation energy in methanol
is uniy 6 kGal mole-' smaller than that inethane.
Although the disparity in initial orbital stabilities prevents
the formation of strong three-electron bonds between carhon
and oxygen, this amsideration is removed for the isoelectmnic
dinitrogen compounds. Indeed, recent theoretical and ex-
perimental work hasshown that %electron nitrogen-nitrogen
~~-
iinkaees of substantial streneth occur in manv svstems.
~ ~
Consider the n a * states ofdiimide, HNNH, compared to
those of formaldehyde (Fig. 2). In the carbon-oxygen system,
292 / J m l of Chemical Education
the remaining n electron is localized heavily on the oxygen.
The most stable electron configuration for the a system has
two electrons localized on oxygen and one on carbon. A strong
3-electron hond would result only if a structure of near-equal
stability resulted when two a electrons were localized on
carbon and onlv one on oxvgen. Since the latter structure
corresponds to k-0+, i t cannot compete energetically with
the one shown in Figure 2, and the 3-electron a bond is weak.
The MO in diimide from which the electron is excited is de-
localized over both nitrogens. On a time-averaged basis, both
nitrogen atoms are equivalent in their T orbidstahility, thus
vieldine a rather strona three-electron a hond. Indeed, recent
ob init; C1 ralculation~(6) predict that the vertical excitation
from the around state to the lowest triplet in diimide requires
about 30 kcal mole-' less energy than does the same transition
in formaldehyde. Recent calculations also indicate that the
preferred mnlerular getmetry in this I~nvesttriplet state has
the molecule twisted YOo rather than planar as in the ground
. .~In the twisted conformation. two equivalent three-
state (7).
electron honds exist, each formed byintera&ion of a singly
occunied D- orbital on one nitroeen' and a doubly occupied
~ o n e - ~ abibital
ir on the other.
The existence of stabilizing three-electron bonds also has
a profound effect on the bond dissociation enthalpies of the
dinitrogen hydrides (and presumably their substituted de-
rivatives). Consider first the hydrazyl radical, H2NNH. Ab
initio calculations in this laboratory indicate that, although
the optimum nitrogen-nitrogen bond length of 1.39 .&islong
and the geometry about the tricoordinate nitrogen is flapped,
the barrier to rotate the NH bond of the diwrdinate nitrogen,
and thus to destroy the three-electron hond, is 10.0 kcal
mole-', twice as large as in the isoelectronic carhon-oxygen
sy~tem.~
I
2.4
The extra stability imparted by the three-electron hond is
responsible partially for the rather low N-H hond dissocia-
tion energy of 82 kcal mole-' (76 f 5 experimental ( 9 ) )pre-
dicted2 for hydrazine compared to 104 kcal mole-' for am-
monia. The nredicted enthalnv of dissociation of HzNNH to
~~~ ~~
yield trans-iiimide in 62% oiihat for hydrazine. lncontrast.
the C-H bond dissociation enerm for the ethyl free radical,
in which there is no significant stakization by ;three-electron
bond, is only 40% of that for ethane (5).
Kinetic Stability of Three-Electron Bonds
A three-electron hond between the nitrogens in the HNN'
radical reduces the N-H bond dissociation energy of diimide
to 61 kcal mole-' (calcd) compared to 104 for NH3. The hond
length predicted (10) for the ground state of HNN' is 1.18 A,
which lies between that of 1.08 A for N2 and 1.22 A for
HN=NH. Although three-electron bonding.in HNN' does
stabilize the system, the nitrogen-nitrogen triple hond in the
t such a strona linkaae that the dissociation of HNN.
~ r o d u c is
H.+N2 is probahly & exothermic process! This is not to say
that all HHN' radicals (and their substituted derivatives
RNN.) should spontaneously decompose; indeed, theoretical
calculations (10) predict an energy harrier of about 23 kcal
mole-I to the reaciion. The energy surface generated
for this radical decomposition reaction is illustrated in Figure
3. (Although the energy is plotted against only the H--Nz
m e s e calculations use Pople's 4-31G basis set (3a)and Rwthaan's
-
for the N2Ha N2H3.+ H' reaction and for the HNNH HNM + -
restricted open-shellmethod. (8b).In addition, the theoretical result
H' reaction have been corrected semiempiricallyfor the correlation
-
energy changes by adding 14.4 kcal mole-' in both cases. This brings
the total AH of the reaction N2Ha Nz + 4H' into agreement with
the experimental value.

T STATES EXCITED STATE
dW
HIGHER I: STATE GROUND STATE
w
-
Of
Figure 4. Decomposition of linear species: HCO' K + CO.
HCCS H'+CO
Figure 5. Correlation of linearstates
distance, the nitrogen-nitrogen distance was reoptimized a t
every point shown.) The potential surface for the decompo-
sition of the isoelectronic HCO' free radical is similar to that
for HNN, although the former reaction is endothermic rather
than exothermic.
The origin of the rather substantial harriers to decompo-
sition of such radicals was explained some time ago (11).
Consider a linear HCO' species; the "odd" electron could be
placed in either one of the two n*co MO's or else in a o * c ~
orbital (see left side of Fig. 4). Dissociation of the C H bond
gives an excited state of carbon monoxide if one starts from
a state in which the odd electron of linear HCO' occupies a T *
orbital-see top of Figure 4. The correlations between states
of linear HCO' and CO are shown in Figure 5.
The picture developed above for the decomposition of HCO'
is artificial since it assumes that the molecule is linear. In fact,
in its ground state H C D is distinctly bent. As illustrated in
Figure 6, the two states which had a* odd electrons in their
linear geometry are nonequivalent in the bent conformation;
the A" state which has an odd "d' electron (i.e., in an MO
antisymmetric with respect to reflection in the plane of the
nuclei) is of higher energy and prefers a linear geometry,
whereas the A' state with the odd electron in an in-plane MO
prefers a bent geometry. The important consequence of this
nonlinearity is that the bent ground state of the HCO has the
same svm&etrv (A') as does the unner state which has the odd
e l e c t r k in th; b* 'MO. Since t6ese states are of the same
symmetry, they do not cross each other as the molecule dis-
sociates, and the state correlation diagram for bent HCO'-
+
CO H.is of the type shown in Figure 7. The ground state of
HCO' correlates with the ground states of carbon monoxide
and hydrogen. In chemical terms, the origin of the upward
slope to the decomposition energy surface is the loss of bond
BEND IN X Z PLANE
i z
Figure 6. Electron distribution in bent geometries of HCO.
HCO' W+CO
Figure 7 . Correlation of bem states.
energy in the two-electron H-C (or H-N) link as i t is
stretched. Once this hond lengthening proceeds beyond a
certain point, the most stable bonding structure switches to
a three-electron H-C (or H-N) link and a triple rather than
a double carhon-oxygen (or nitrogen-nitrogen) hond. The
downward slope portion of the energy profile corresponds to
the decomposition of the dissociative three-electron HC (or
HN) hond. In all cases investigated theoretically so far, the
"crossover" point occurs late so that the activation energy is
significantly larger than the enthalpy of decomposition, and
thus these radicals nossess some kinetic stahilitv even thoueh "
they are rather unstable thermodynamically. Exper~mentally
this point has been confirmed (12) for the acetyl radical, since
the act~vationenergy for decomposition exceeds the endoth-
ermicity by 6.0 kcal mole-'.
Literature Cited
(11 Sw Gilbrt,T. L.,and Wshl, A. C.J. C h m Phyn., 55,5247 (19711and referencneitcd
th~rein
(2) Henbrg.0.. "MolecularSpeetmand MolcollarSuueture..'D.Vaz NoatrandCo.Inc.,
Prineefon,N.J.,Vol 1,2ndEd.,1950.p.355.
131 MeClynn. S. P.,Azumi,T..and Kinashits, M.,"Moleeular Speetrmnlpy c,ftheTriplet
State," Prentie-Hall, lnc.. Enslowmd Cliffs, N.,J., 0.84.
(41 Ha,T-K.,Chrm. Phys Lett., 30.379119751.
(5) Kerr,J. A,. Chem Re"., 65,465 (19561.
15) Vasudevsn,K., PeyerimhoffS.D.6uenker.R.J.snd Kammer. W.E..and Hsu.H..
ChwxPhya., 7.157 11975).
17) Baird, N. C.,andSwenson, J. R., Can. J Chem.. 51.5097 119731.
18) la1 Ditchfield. R.. Hehrs, W. J.. end Paple. J. A. J. Chem. Phyx.. Ri.721 119711. lbl
RuoUlaan,C. C. J.,RPu. Mod. Phys., 32.179 (19601.
I91 Schurath. U..sndSchindkr,R. N., J. Phys Chsm.. 74,5188 (1970).
(LO1 6aird.N.C..J. Chem Phys., 62,5C4 (L9761.
1111 Sea Henhew, G.."Molaeular Spectra and Moleeulsr Structure." D.Van Nustrand Co.
Inc., Princetan, N.J., 1957,Vul. III.p.458.
1121 walkinn, K.w.,and word. W.w.lnr. J. chem ~ i n r h 6,855 . (19741.
Volume 54. Number 5, May 1977 / 293