Principles of Bond Strength N o r m d Covalence

At the outset, a distinction should be made between (10) Covalent bonds between small atoms tend to
"sbbility" and "reactivity." Unfortunately, it is be stronger than covalent bonds between larger
common practice to confuse the two. Too frequently atoms.
a substance which is relatively reactive is called Some examples illustrating this principle are listed
"unstable" although actually its bonds may be very in Table 8. The importance of coulombic forces in
strong. I n view of this ambiguity, it would seem covalence suggests that since such forces vary in-
much more preferable to use the word "stable" only versely with the square of the distance of separation
to describe the condition of being held together by of the charges, greater strength of bonding between
strong bonds and to imply the requirement of high smaller atoms is probably the result of closer interac-
temperature to disrupt the substance without regard tions of opposite charges. Larger atoms not only
to its possible chemical reactivity. An "unstable" form longer bonds, but also have a larger number of
substance may then be unreactive or highly reactive, nonbonding electrons that may tend to weaken the
but it must be one held together by weak bonds that bonding through inter-cloud repulsions. This effect
are thermally disrupted a t relatively low temperatures. appean to outweigh the effect of attraction resulting
In an earlier paper (S),principles of chemical bond- from the increased nuclear charge.
ing were set forth to summarize the requirements of
bond formation. Here it is desirable to examine the
factors that may influence bond strength. This is Table 8. Relation of Bond Strength to Radius (or Bond
unfortunately a very complex subject, to be dealt Length)
with a t present only in a qualitative or a t best a semi-
quantitative way. But still it is possible to state
some useful generalizations. I n fact, for a t least H2
C-C
some kinds of compounds, notably the binary halides, Cl*
it has been found possible recently (4) to calculate Ss
Bra
quantitatively the total bonding energy, from applica- I*
tion of the following principle:
(9) In the binary halides, and possibly other classes
of compounds as well, the total bonding energy (per (11) Covalent bonds between atoms tend to be
equivalent) varies directly with the partial charge on weaker, the greater the difference in principal quantum
halogen and the bond order and inversely with the number of the valence shell of the two elements.
bond length. Evidently, as exemplified by the illustrations of
This principle holds regardless of the nature of the Table 9, the overlapping, or coalescence, of orbitals
bonding, as shown, for example, by the fact that all becomes less effective when the atoms are very nn-
the binary chlorides of the major group elements fall equal in size. This is particularly well illustrated by
on the same straight line connecting Cll with NaC1, the binary hydrogen compounds having covalent
formed by plotting partial charge on chlorine against bonds of relatively low polarity (5).
the function R H / n (where n is the bond order, H the
heat of atomization per equivalent, and R the bond
length). Some representative examples of the agree- Table 9. Relation of Bond Strength to Difference in Valence
Level
ment between calculated and observed bond energies
are given in Table 7. Much remains to be done in Difference Decomposi- Av. bond
Compound in n tion ("C) energy (kcal)
the development of a bonding theory to account for
these remarkable relationships; but by bringing to- CHI 1 ROO 99.4
gether 'Lionic" and "covalent" bonding within a PHs 2 300 78 0
GeH4 3 285
unified system, it promises eventually to permit the TeH2 4 25 56.9
more complete understanding needed for predicting ShH, 4 95

more precisely the direction of spontaneous change.

Table 7. Total Bonding Energy and Polarity of Some (12) Covalent bond strength tends to be greater,
Representative'Exomples the greater the bond polarity.
-Sx H(calc)" H(expp One explanation of this tendency has been provided
LiF 0.74 206 202 by Pauling (6),who considered the extra energy re-
LiI 0.53 127 129 sulting from bond polarity to be derived from sup-
NnF 0.75 181 181
NaI 0.54 120 120 plementing the covalent bond energy with the ionic
BeCL 0.23 129 128 attraction between unlike charges. He used this
MgIs 0.19 88 86 extra energy in establishing his well-known scale of
RaCI. 0 49 151 152
AIL 0.12 72 76 electronegativity. In general, a closer interaction
CF, 0.09 99 103 between bonding electrons and nuclei appears possible
" Heat of atomization per equivalent. in polar bonds because they are shorter. This shorten-
ing can be explained (7) by considering that uneven
Reverting now to the more conventional views of sharing of the electrons produces a radial contraction
bonding, we may observe certain principles that can of the partially positive atom that is greater than the
be helpful meanwhile. radial expansion caused by the acquisition of partial
16 / Journol of Chemical Education
negative charge by the other atom. A rough quantita-
tive indication of the effect of different polarity in
bonds between the same two atoms is provided by
the heats of atomization (per equivalent) of binary
compounds exhibiting different oxidation states. Some
examples are given in Table 10. Invariably, the heat
of atomization is lower the higher the positive oxida-
tion state of the central atom. This is because the
more competitors there are for the electrons of a given
atom, the less successful each will be in acquiring
negative charge, and correspondingly the less polar
its hond.
Toble 10. Heots of Atomization of Some Binary Com-
pounds (kcol/equiv) (2)
CrF* TiBn
CrF, TiBn
hhF3 TiBn
MnF. CuBr
PhF2 CuRrr
PhF4 Snlh
CIF SnRn
CIFs PBra
BrF PBrr
BrF, FeO
SO* Fe201
SO.
Bonds between hydrogen and highly electronegative
elements such as fluorine, oxygen, and chlorine are
especially strong, the relatively positive hydrogen atom
having no underlying electron shells to restrict the
closeness of interaction with the other atom. The
significance of this extra strength in influencing the
course of reaction will he mentioned later.
(13) Covalent bonds between atoms each bearing
partial positive charge tend to be less stable.
Instead of being shorter than normal, as might he
predicted from the fact that positive charge should
correspond to contracted electronic spheres, such
bonds tend to be as long or longer than expected from
their nonpolar covalent radii. This corresponds gen-
erally to a bond weakening, that may he the result of
reduced availability of outer electrons for sharing.
Table 11. Some Unstable Molecules Having Bonds
between Positivelv Choraed Atoms
Chsree on Element
Some examples of molecules whose instability may
a t least in part be ascribed to such causes are listed,
with the positive charge on adjacent a t o m , in Table
11. (Notable exceptions are the fluorocarbons, whose
C-C bonds appear to be unweakened by the relatively
high partial positive charge on the carbons. Perhaps
the weakening does exist, but is compensated for by
coulombic attractions between positive carbon and
the negative fluorines attached to its immediate
neighbors.)
(14) Covalent bonds having partial mnltiplicity a s a
result of resonance are more stable than single bonds
or than the equivalent of partial mnltiplicity in separate
single and integral multiple bonds.
The validityof this ptinciple appears to be established
by the existence of resonance--by the equalization of
bonds toward partial multiplicity, wherever possible,
instead of by separate single and double bonds.
The explanation may perhaps be found in the ap-
parent increase in interelectronic repulsions that
occur when an atom acquires electrons. This in-
crease seem to mean that the shared electrons con-
tribute most to the stability as they are first acquired
partially. Greater stability therefore results when
two a t o m (or sometimes more) each hold the bonding
electrons partially than when each simply holds its
own completely. This is why covalent bonds form,
and why their mpture always costs energy. Similarly,
then, if a double bond might be in one of two places
in a molecule but cannot be in hoth places a t once,
it tends to become distributed partially in hoth loca-
tions, rather than totally in one to the exclusion of the
other. This kind of situation is called resonunee;
it occurs wherever it is possible because it produces
greater stability. I n fact, wherever formation of
single covalent bonds would leave a t least one other-
wise vacant orbital on one atom and one or more pairs
of otherwise nnshared outer electrons on adjacent
atoms, we may expect further interaction in which a t
least partial use of these orbitals and electron pairs
is made to strengthen the bonding through multiplicity.
Some of the most significant examples of bonds where
partial multiplicity is to be expected occur in com-
pounds of fluorine and oxygen with elements whose
atoms have outer vacant orbitals available. Fluorine,
being highest of all elements in electronegativity and
having but one valence orbital vacancy, is generally
considered capable of forming only a single covalent
hond. Several facts suggest, however, that such a
hond can be partly multiple under appropriate con-
ditions. The fluoride ion is known to act as donor
in many complexes; partially negative fluorine may
act likewise, although probably to a lesser degree.
The weakness of the bond in Fz has been explained as
resulting from interference of nonbonding outer
electron pairs on the two atoms, suggesting that such
pairs are in a position to interact attractively with
another atom if it has vacant orbitals available.
Furthermore, bonds of other elements to fluorine are
frequently disproportionately strong and unexpectedly
short, both of which suggest partial multiplicity.
The bond lengths in fluorides of other highly elec-
tronegative elements are as would be predicted from
adding the covalent radii; but to less electronegative
elements the calculated radius sum commonly must be
divided by 0.94 to give the observed bond length,
indicating a bond order approximating 1.5.
Further evidence in support of the partiil mul-
tiplicity in fluorine bonding is available from its re-
semblance to oxygen, which, forming two bonds,
discloses something of the nature of its bonding by
the bond angle. Although two single bonds to oxygen
would be expected to make an angle not exceeding
109' (CLO, 110.8'; FzO, 103.2"; HIO, 104.5'), many
examples are known where the angle is much larger,
even approaching 180'. For example, in numerous
Volume 41, Number I, January 1964 / 17
silicates and the silicones, the S i 4 S i angle is in
the range 140-150'; in PnOs the P-0-P angle is
12S0, as it is also in As-0-As and S b - O S h ;
and in various borates the B-0-B angle may he in
the range of 120-140'. All such wider-than-expected
angles suggest partial utilization of the two other-
wise unused pairs of outer electrons on the oxygen,
involving the fourth spa orbital of boron or outer
d orbitals of the silicon, phosphorus, and others. If
oxygen can enter into such partial multiplicity, there
seems to he no reason why fluorine cannot do so
similarly.
As a probable consequence of such partial mul-
tiplicity, heats of atomization (per equivalent) of
BFI (154.5), B201 (126.9), A ~ F I(148.5), AlaOs (121.9),
SiFl (137.8), SiOl (107.2), AsF3 (114.9), and similar
compounds are appreciably higher than would be
expected from polarity. When the average bond
energies for all the gaseous molecules listed in NBS
Circular 500 (8) are arranged in descending order,
the leaders are: B-F, Si-F, H-F, Li-C1, Na-F,
As-F, H - 4 . As will he seen, these facts become es-
pecially important when one attempts to predict the
course of reactions involving such compounds.
Coordination
This topic could easily lead us into mow elaborate
and lengthy discussions than would be appropriate
to our primary purpose of establishing practical rules
for understanding chemical reactivity. Such dis-
cussions would pertain to the chemistry of transition
metal complex ions, and would involve exposition of
ligand field theory more specialized and detailed than
was intended for this paper. This is an interesting
and active area of research hut cannot be included
here. Instead, let us consider some of the more
general aspects of coordination bond formation, as it
occurs in both molecular addition compounds and
complex ions in general.
(15) Coordination bonds tend to he stronger, the
more readily the donor atom can supply electrons.
Factors influencing the ability of a donor atom to
furnish a pair of electrons to an acceptor may include
the following:
(a) Its Partial Charge. An electron pair is not
readily donated by an atom from which other electrons
have been partially withdrawn. For example, neither
nitrogen trifluoride nor (CF&N, in which the nitrogen
a t o m bear partial positive charge, are effective donors.
Even when other electrons have not been withdrawn
from the donor atom, hut the donor atom is of a
highly electronegative element and only bears small
partial negative charge in the compound, it is not an
effective donor. For example, the oxygen in the
nitrate ion or the sulfate ion is not highly negative
and does not donate electrons very easily (see also
under (e)). On the other hand, if the donor atom is
highly negative, even though it may initially have been
high in electronegativity, it can function well as donor.
Oxygen in state of relatively high negative charge is
effectiveas a donor; for example, hydroxide ion (charge
on oxygen -0.67) is a better donor than water (charge
on oxygen -0.25).
When two or more elements are joined together in a
18 / Journol o f Chemicol Education
negative ion, and atoms of each contain unshared
electrons in the outer shell, these electrons are ex-
pected to be donated more readily, the less electronega-
tive the original element. For example, in a cyanide
ion, both carbon and nitrogen hear unshared electron
pairs hut the carbon is probably the more ready donor.
Inanions containing both nitrogen and oxygen as poten-
tial donors, it is probably the nitrogen that donates more
readily. When the original element is only inter-
mediate in electronegativity, such as phosphorus, then
it can act as donor in compounds where it even has a
small partial positive charge, as in P(CH&, especially
provided the attached atoms or groups are good elec-
tron suppliers (see (c) below).
Closely related to this donor ability is the observa-
tion that the higher the negative charge on a donor,
the greater its coordination number in a crystal lattice
(4).
(b) Involvement of the Donor in Bond Multiplicity.
An electron pair is less available for coordinate hond
formation when it would otherwise he involved ir
multiple bonding through resonance. For example,
the partial charge on nitrogen in trisilylamine, (SiH&N,
should he more negative than that in trimethylamine,
since silicon is less electronegative than carbon. There-
fore trisilylamine should he a better donor, hut in
fact it is scarcely effective. The reason is believed to
be that the outer d orhitals of the silicon are able to
involve the "unshared" pair of electrons on the nitrogen
to such an extent that they are effectively utilized
in nitrogen-silicon "pi" bonding and thus unavailable
for donor action, toward an outside acceptor.
(c) Capacity of the Reservoir Attached to the Donor.
Donor atoms appear to be better able to supply elec-
trons, the better the electron reservoir that is made
available to them by other atoms covalently bonded
to them. For example, P(CH& is a better donor
than pHa; this may be ascribed to the fact that the
methyl groups supply electrons to the phosphorus
more effectively than the hydrogen atoms can, thus
permittmg phosphorus atom t o share its extra pair
of electrons more easily with an outside acceptor.
(d) Polarizability of the Donor. The donor may
be more effective in some combinations if it is relatively
easily polarized, as for example, the iodide ion com-
pared to the fluoride ion.
(e) Concentration of the Donor Electron Pair. Donor
atoms may be able to function better, especially toward
small atom acceptors, when their electron pairs are
concentrated within a relatively narrow region rather
than spread out. For example, alcohols and ethers
are generally better donors than ketones or carboxy-
lates, for the probable reason that in the former the
oxygen is already involved in two single bonds, whereas
in the latter, it is involved in one double bond. Al-
though in both cases the oxygen has two "free pairs" of
electrons, these electrons have more room to spread
out when the other electrons are localized in the double
bond rather than distributed in two single bonds.
This is especiauy important in protonic bridging
or indeed in any bonding to hydrogen. For a covalent
hond to hydrogen may sometimes usefully he considered
a coordmation bond in which a proton is attached to a
donor, and a protonic bridge is similar in that a par-
tially positive hydrogen (instead of a bare proton) is