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Colin Baird
University of Western Ontario
London. Ontario, Canada
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
-~- ~~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

the energy required (3)to excite the molecule from its ground state to the A three-electron hond between the nitrogens in the HNN' radical reduces the N-H bond dissociation energy of diimide triplet n a * state is 72 kcal mole-'.~In the twisted conformation. In the carbon-oxygen system. H. Recent calculations also indicate that the preferred mnlerular getmetry in this I~nvesttriplet state has lor HNN' - A B INITIO (4-31G) SURFACE H ' r N2 the molecule twisted YOo rather than planar as in the ground . theoretical carbon singly occupied 2p. 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. i t follows that the comhination of the single HN=NH. compared to H' reaction have been corrected semiempiricallyfor the correlation - energy changes by adding 14.4 1. twice as large as in the isoelectronic carhon-oxygen sy~tem.orbital on one nitroeen' and a doubly occupied ~ o n e .08 A for N2 and 1.0 kcal mole-'. On a time-averaged basis. .In addition. Since this value is close to to 61 kcal mole-' (calcd) compared to 104 for NH3. Indeed. Since the latter structure corresponds to k-0+. Although three-electron bonding. both Of nitrogen atoms are equivalent in their T orbidstahility. about 30 kcal mole-' less energy than does the same transition in formaldehyde. The hond the 74 kcal mole-' difference between a double hond and a length predicted (10) for the ground state of HNN' is 1. The energy surface generated confirmation is by the experimental finding (5)that for this radical decomposition reaction is illustrated in Figure the hvdroaen-carbon hond dissociation energy in methanol 3. the barrier to rotate the NH bond of the diwrdinate HNN' does hond plus the 3-electron a bond in the 3na* state is only stabilize the system. the s t r e n a h of this linkage must he small.2 2.~ abibital ir on the other. Indeed.4 H-N DISTANCE Figure 3. and thus to destroy the three-electron hond.. although the optimum nitrogen-nitrogen bond length of 1. lncontrast. In the case of formaldehyde. The MO in diimide from which the electron is excited is de- \ nn* STATES localized over both nitrogens. the C-H bond dissociation enerm for the ethyl free radical. Ab initio calculations in this laboratory indicate that.8 10 1. H2NNH. i t cannot compete energetically with the one shown in Figure 2.) should spontaneously decompose. (8b).2 1. electron honds exist. ~ r o d u c is For the H Z O H free radical. the remaining n electron is localized heavily on the oxygen. in which there is no significant stakization by .18 A.+ H' reaction and for the HNNH HNM + - restricted open-shellmethod. that all HHN' radicals (and their substituted derivatives Since such twisting destroys the 3-electron hond between the RNN. Potential energy surtace for HNN' -+ (inA1 H' NI. thus HNNH vieldine a rather strona three-electron a hond.0 2. Consider first the hydrazyl radical.~ -m1 I 0. t such a strona linkaae that the dissociation of HNN. 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. 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). C1 ralculation~(6) predict that the vertical excitation from the around state to the lowest triplet in diimide requires Figure 2. this amsideration is removed for the isoelectmnic m e s e calculations use Pople's 4-31G basis set (3a)and Rwthaan's dinitrogen compounds.&islong and the geometry about the tricoordinate nitrogen is flapped. the theoretical result ~~- iinkaees of substantial streneth occur in manv svstems. ~ ~ Consider the n a * states ofdiimide. is only 40% of that for ethane (5).+N2 is probahly & exothermic process! This is not to say tional harrier for O-H bond tbrsion of about 4 kcalmole-'. each formed byintera&ion of a singly occunied D. indeed. Further mole-I to the reaciion. 292 / J m l of Chemical Education .39 . is 10. and the 3-electron a bond is weak.4 kcal mole-' in both cases. HNNH. recent ob init. 2). Ha has calculated ( 4 )a rota. the nitrogen-nitrogen triple hond in the marginally more stable than is a C-0 single hond alone. orbital and a lone-pair orbital on calculations (10) predict an energy harrier of about 23 kcal -- oxveen. two equivalent three- state (7).22 A for 91 kcal mole-'). (Although the energy is plotted against only the H--Nz is uniy 6 kGal mole-' smaller than that inethane. single hond (estimated using E(C==O) = 165 and E(C-0) = which lies between that of 1. the experimental value. Although the disparity in initial orbital stabilities prevents the formation of strong three-electron bonds between carhon and oxygen. suggest that the three-electron carbon-oxygen hond is very Kinetic Stability of Three-Electron Bonds slightly stabilizing.three-electron Both theoretical calculations and experimental evidence bond. Threeelecbon bonds in excited states. This brings the total AH of the reaction N2Ha Nz + 4H' into agreement with those of formaldehyde (Fig. The most stable electron configuration for the a system has two electrons localized on oxygen and one on carbon. recent theoretical and ex- perimental work hasshown that %electron nitrogen-nitrogen - for the N2Ha N2H3.6 18 2.

J. certain point. lbl sociates.. Dissociation of the C H bond the decomposition of the dissociative three-electron HC (or gives an excited state of carbon monoxide if one starts from HN) hond. and hydrogen. 0..and Wshl.. Enslowmd Cliffs... W.H. J.5188 (1970). C.. chem ~ i n r h 6. "MolecularSpeetmand MolcollarSuueture.Vol 1.N.. 32. Once this hond lengthening proceeds beyond a The origin of the rather substantial harriers to decompo.179 (19601. linear geometry are nonequivalent in the bent conformation. and of linear HCO' and CO are shown in Figure 5. A..721 119711.T. N.J.) The potential surface for the decompo- sition of the isoelectronic HCO' free radical is similar to that for HNN. 1957. the origin of the upward Inc.Vul. Phys.465 (19561.and word. e l e c t r k in th. a three-electron H-C (or H-N) link and a triple rather than Consider a linear HCO' species.e. RuoUlaan. HCO' correlates with the ground states of carbon monoxide 1111 Sea Henhew. C. In chemical terms. 18) la1 Ditchfield. Chem Re". the most stable bonding structure switches to sition of such radicals was explained some time ago (11). Chem Phys..6uenker. Phyx. The placed in either one of the two n*co MO's or else in a o * c ~ downward slope portion of the energy profile corresponds to orbital (see left side of Fig. 7. symmetry. 17) Baird.. Princetan..J.0 kcal mole-'..N.sndSchindkr.Azumi. in an MO Literature Cited antisymmetric with respect to reflection in the plane of the (11 Sw Gilbrt. although the former reaction is endothermic rather energy in the two-electron H-C (or H-N) link as i t is than exothermic. Exper~mentally is artificial since it assumes that the molecule is linear. since in its ground state H C D is distinctly bent. L.157 11975). they do not cross each other as the molecule dis. 74. (2) Henbrg. b* 'MO. R.Vaz NoatrandCo. 65..E. + CO H.. slope to the decomposition energy surface is the loss of bond 1121 walkinn. K.R. R. C h m Phyn.K. J.T-K. The ground state of I91 Schurath.84.379119751. (19741. Correlation of bem states. Mod.D..w.ftheTriplet State.J.5097 119731. Since t6ese states are of the same 15) Vasudevsn. Decomposition of linear species: HCO' K + CO. P...T." D.andSwenson. the a state in which the odd electron of linear HCO' occupies a T * "crossover" point occurs late so that the activation energy is orbital-see top of Figure 4. HCCS H'+CO Figure 5. The important consequence of this 131 MeClynn.. N. ChwxPhya.and Kinashits. Can. M. Phys Lett..w.. (LO1 6aird. 30. thus these radicals nossess some kinetic stahilitv even thoueh " The picture developed above for the decomposition of HCO' they are rather unstable thermodynamically. prefers a bent geometry.. Ri. May 1977 / 293 .RPu. 51. Correlation of linearstates HCO' W+CO distance... J. In fact.Chrm..J." Prentie-Hall.and Hsu. J Chem. Figure 6. Phys Chsm.. A..J.J. In all cases investigated theoretically so far. Number 5..855 .. Electron distribution in bent geometries of HCO.R. W. N. Volume 54. whereas the A' state with the odd electron in an in-plane MO Prineefon...5247 (19711and referencneitcd th~rein nuclei) is of higher energy and prefers a linear geometry.0. PeyerimhoffS. the A" state which has an odd "d' electron (i. 4)..J. the "odd" electron could be a double carhon-oxygen (or nitrogen-nitrogen) hond.. W. the nitrogen-nitrogen distance was reoptimized a t Figure 7 . nonlinearity is that the bent ground state of the HCO has the (41 Ha.'D. C. every point shown. 55."Molaeular Spectra and Moleeulsr Structure.355. U.458. of the type shown in Figure 7. BEND IN X Z PLANE i z T STATES EXCITED STATE dW HIGHER I: STATE GROUND STATE w - Of Figure 4. and the state correlation diagram for bent HCO'.. J. same svm&etrv (A') as does the unner state which has the odd (5) Kerr... A. end Paple.Van Nustrand Co.Inc. Chem.snd Kammer.2ndEd. J.1950.. G. the two states which had a* odd electrons in their ermicity by 6. N.p.C.5C4 (L9761.lnr. S..."Moleeular Speetrmnlpy c. As illustrated in the act~vationenergy for decomposition exceeds the endoth- Figure 6. Hehrs. 62.. The correlations between states significantly larger than the enthalpy of decomposition. III.p. stretched. J. this point has been confirmed (12) for the acetyl radical.C.