In the Classroom
The Concept of Oxidation States in Metal Complexes
Dirk Steinborn
Institut für Anorganische Chemie, Martin-Luther-Universität Halle-Wittenberg, 06120 Halle, Kurt-Mothes-Straße 2,
Germany; steinborn@chemie.uni-halle.de
The concept of oxidation states is one of the most pow-
erful heuristic concepts in chemistry. It plays an important
role in teaching chemistry. To assign oxidation numbers (ON)
of atoms in molecules, most textbooks and journal articles
present a set of hierarchical rules. These sets can be quite com-
plex (up to 16 rules to construct computer driven expert sys-
tems) but, in any case, are incomplete and suffer from an
increasing number of exceptions (1). An alternative way is
to go “back to the roots” of the concept and to assign oxida-
tion numbers of atoms in molecules on the basis of their
Lewis structures. This system of splitting shared electrons in
covalent bonds heterolytically (2), according to certain prin-
ciples (see below), is less frequently explained in textbooks.
Thus, from the Lewis structure of a molecule, with knowl-
edge of the electronegativities of elements, oxidation num-
bers can be assigned. In doing this it is obvious that the
concept of oxidation states can be more than bookkeeping
of electrons to balance oxidation–reduction reactions. Fur-
thermore, limitations of the concept will be obvious in cases
where the electronic structure of a molecule cannot properly
be described by one Lewis structure.
Historical Survey
Originally, the valency of an atom was thought to be a
fundamental atomic property that was constant and invari-
able (Kekulé, around 1860). The principle of constant va-
lence numbers was successfully applied in the second half of
the 19th century for carbon compounds in organic chemis-
try. However, it proved to be wrong in inorganic chemistry
(3). For instance, contrary to experimental results lower va-
lent metal halides had to be formulated as dimers (Figure 1)
to maintain fixed valencies for metals. Thus, it was recog-
nized that valency is not an inherent property of an atom, as
for instance, the atomic mass is. Atoms may have variable
valencies (“valence numbers”) that are indicated in the names
of compounds by terminations such as “-ous” and “-ic” (e.g.,
ferrous, ferric). Later on valence numbers were placed as Ro-
man numerals in parentheses (Stock’s method; ref 4 ), which
is still used today.
The progress in understanding chemical bonding and
oxidation–reduction reactions resulted in the need to distin-
FeCl2 FeCl3 SnCl2 SnCl4
Cl Cl Cl Cl Cl Cl Cl
Fe Fe Fe Cl Sn Sn Sn
Cl Cl Cl Cl Cl Cl Cl
Figure 1. Formulas of iron and tin chlorides according to the prin-
ciple of fixed valencies for iron (trivalent) and tin (tetravalent).
1148 Journal of Chemical Education • Vol. 81 No. 8 August 2004
guish between stoichiometric and electrochemical valencies
and to define oxidation numbers. Pauling described this con-
cept in the 1947 edition of his book General Chemistry (5)
as follows: “The oxidation number of an atom is a number
which represents the electrical charge which the atom would
have if the electrons in a compound were assigned to the at-
oms in a certain way.” This way of assignment can be de-
scribed for atoms in covalent compounds of known structures
as “... the charge remaining on the atom when each shared
electron pair is assigned completely to the more electronega-
tive of the two atoms sharing it. A pair shared by two atoms
of the same element is split between them” (5). Furthermore,
Pauling also states that in compounds whose structures are
uncertain, the oxidation numbers may be calculated from a
reasonable assignment of oxidation numbers to the other el-
ements in the compounds.
Basic Considerations
The oxidation number of an atom in a molecule is de-
fined as the charge of that atom if the molecule would con-
sist of (monatomic) ions that may also be neutral atoms.
Cleavage of molecules into (hypothetical monatomic) ions
has to be based on the polarity of covalent bonds. Electrons
in polar covalent bonds are assigned to the more electrone-
gative atom whereas those in nonpolar covalent bonds are
equally shared between the bonded atoms. From this defini-
tion three statements follow: (i) Oxidation numbers are
charges of hypothetical monatomic ions that cannot be mea-
sured experimentally, in principle; (ii) Assignment of oxida-
tion numbers of atoms in a molecule is based on its electron
distribution represented by an actual Lewis structure. Ambi-
guities may arise when the electronic structure of a molecule
cannot be properly described by only one Lewis structure or
when the polarity of a covalent bond to be split is not known;
and (iii) The concept in this simple form is limited to mol-
ecules whose electronic structure can be described by appro-
priate Lewis structures. In some cases this may not be possible,
for example, in cluster compounds and in compounds with
electrons in highly delocalized molecular orbitals.
To assign oxidation numbers of atoms in molecules, the
relevant Lewis structures have to be drawn. An integral fea-
ture of (complete) Lewis structures are the formal charges of
atoms. These are charges of hypothetical monatomic ions ob-
tained by homolytic cleavage of all covalent bonds. On the
other hand, heterolytic cleavage of polar covalent bonds and
homolytic cleavage of nonpolar bonds (as described above),
result in formation of monatomic ions whose charges define
the oxidation numbers of atoms in a molecule. Thus, formal
charges and oxidation numbers reflect the two hypothetical
borderline cases of electron distribution in a molecule, namely
the “pure covalent” and the “pure electrostatic” view of polar
covalent bonds, respectively. From these definitions it follows
• www.JCE.DivCHED.org
 In the Classroom

that the sum of the formal charges over all the atoms of a structures 2a–c, resulting in two different sets of oxidation
molecule and the sum of the oxidation numbers over all the numbers for sulfur atoms, ON(S): +4兾0 versus +2兾+2. An
atoms of a molecule are equal to the total charge on the mol- argument to favor the first set of oxidation numbers may be
ecule. that the Lewis structure 2a does not involve a (p–d) π bond
Neither of these charges reflect the real existing charge between third-row elements. This assignment also corre-
distributions in molecules. To get the charge distributions, the sponds with the formation of thiosulfate from sulfite and sul-
concept of partial or effective charges on atoms in molecules fur and its decay in acidic solution yielding sulfur dioxide
has to be applied. They can be derived from some spectro- and sulfur. Oxidation of thiosulfate with iodine results in the
scopic measurements, such as photoelectron and Mössbauer formation of tetrathionate, 3, with oxidation numbers of +4
spectroscopic measurements. However, usually, they are cal- and +1 for the sulfur atoms. Thus, reaction 2 → 3 is under-
culated quantum chemically by population analysis that par- stood as formal oxidation of terminal sulfur in S2O32− fol-
tition the total charge among the atoms in molecules. lowed by S
S bond formation. SCN− (4), OCN− (5), and
molecules like HC(O)NH2 (6) are given in the literature (1d)
Oxidation Numbers in Nonmetal Compounds as examples where sets of oxidation-number rules failed to
assign oxidation numbers. Oxidation numbers derived from
Although several Lewis structures have to be considered the relevant Lewis structures using the heterolytic bond cleav-
for SO42− (Figure 2, structures 1a–c), the assignment of oxi- age procedure are given in Figure 2. If the electronic struc-
dation numbers is unambiguous. Owing to higher electrone- ture of a molecule has to be described by a resonance hybrid
gativity of oxygen, χ(O) > χ(S), heterolytic cleavage of of two or more (nearly) equivalent Lewis structures, then the
sulfur–oxygen bonds results in the formation of hypotheti- mean values of oxidation numbers can be given. This may
cal O2 and S6+ ions (ON(O) = 2 and ON(S) = +6). This is result in nonintegral oxidation numbers clearly indicating an
not the case in the thiosulfate anion S2O32−: Consider the extension of the original concept. Examples are the oxida-
group electronegativities (6) χ(SO3) > χ(S), the sulfur–sulfur tion numbers of oxygen in the superoxo anion O2− (ON(O)
bond should be cleaved heterolytically as shown in Figure 2, = −1兾2) and the dioxygenyl cation O2+ (ON(O) = +1/2).
Ambiguities in determining oxidation numbers from
Lewis structures may arise when adjacent atoms have small
electronegativity differences and when more than one Lewis
structure has to be taken into account, also see the discus-
ON(S): + 6 +6 +6 sion in ref 2.
2− 2− 2−
O O O
Oxidation Numbers in Metal Complexes
O S O O S O O S O etc.
O O O To assign oxidation numbers of all atoms in metal com-
plexes, the same procedure as described above can be applied.
1a 1b 1c
However, frequently the oxidation numbers of central met-
als are the only ones of interest and therefore the following
ON(S): + 4 0 +2 +2 +2 +2 discussion will be restricted to these. Owing to the highly
O
2−
O
2−
O
2− electropositive character of metals, electrons involved in
metal–ligand bonds are assigned to the ligands. Thus, ligands
O S S O S S O S S etc.
(L) are cleaved off taking electrons from the M–L bonds with
O O O them:
2a 2b 2c [MLx]n → Mz + x:Lm
The oxidation number of the metal equals the charge n of
ON(S): + 4 +1 +1 + 4 complex minus the sum of the charges of all ligands (z = n −
O O
2− xm). In doing so, heterolytic cleavage of all ligands L from a
metal complex results in a (monatomic) metal ion Mz (or
O S S S S O neutral metal atom)1 whose ionic charge z defines the oxida-
O O tion number of M in the complex [MLx]n. Examples are given
in Figure 3.
3
− 2 +1
ON: 0 + 2 −3 − 2 + 4 −3 +1 +2 −3 +1
Ligand charges: 0 −1 0 0
− − O 3+
S C N O C N H C H [Co(NH3)6] [CoH(CO)4 ] [Co(CO)4] −
N
H ON(M): +3 +1 −1
4 5 6 7a 7b 7c

Figure 2. Oxidation numbers for some nonmetal compounds. The Figure 3. Oxidation numbers of metals in complexes.
curved lines show heterolytic cleavage of the bonds and the straight
vertical lines show homolytic cleavage of the bonds.

www.JCE.DivCHED.org • Vol. 81 No. 8 August 2004 • Journal of Chemical Education 1149

 In the Classroom
M–L interaction
M–L σ bond
Figure 4. Classification of ligands, orbital type of L
L, in metal complexes. Orbital rep-
resentations are shown schemati-
cally. Arrows are directed from M–L π bond
the (filled) donor orbital to the
(empty) acceptor orbital.
orbital type of L
examples OH2, OR2,
NH3, H , ...
−,
Ligands may be classified according to the types of or-
bitals used for metal–ligand bonds (Figure 4): ligand orbit-
als forming the σ M
L bonds may be non, π, or σ bonded
resulting in formation of n, π, and σ complexes,2 respectively.
Additionally, n ligands may act as π donors or as π accep-
tors. To stabilize binding of π and σ ligands, strengthening
of metal–ligand bonds by π and σ back-donation, respec-
tively, is usually necessary. These additional bondings may
cause ambiguities in assigning the oxidation numbers of the
central metals.
n Ligands
The vast majority of ligands are n ligands (e.g., NH3,
py, MeCN, PR3, P(OR)3, H2O, Et2O, R2S, CO, F−, Cl−,
HO−, O2−, RS−, S2−, and H−). Typical π-donating ligands are
oxo (O2−) and fluoro (F−) ligands but this type of π bonding
does not affect the assigning of oxidation numbers (Figure
5). This does not hold for π-acceptor ligands; CO is a typi-
cal example. Here the electrons forming the π M
L bonds
are d electrons from the metal. As a result of the doubly de-
generate LUMO of CO, there is the capacity for two π-type
back-bonds. The increase of M
CO bond order is associ-
ated with the decrease of C
O bond order (Figure 6, 8a →
8b → 8c). Thus, Lewis structures 8b and 8c represent a metal
in an oxidation number being two and four units, respec-
tively, higher than that in 8a. Thus (formally) CO2 (8b) and
Lx M O Lx M O
ON(O) −2 −2
Lx M F Lx M F angle in Na2[Fe(CN)5(NO)]2H2O is 178 and ν(N
O) =
ON(F) −1 −1
Figure 5. Examples of π-donating ligands.
1150 Journal of Chemical Education • Vol. 81 No. 8 August 2004
n -ligands π-ligands σ-ligands
n-donor (lone pair) π-donor σ-donor
none π-donor π*-acceptor π*-acceptor σ*-acceptor
O2−, F − , ... CO, NO, PF3, olefins, dienes, H H
−
η1-N , ... alkynes, aro- H , SiR3 , ...
2
matics, Cp
η2-N2, ...
CO4 (8c) ligands exist in these complexes. The ν(C
O)
stretching frequencies for a series of mononuclear
tetracarbonyl–metal complexes having a total of 18 valence
electrons is shown in Figure 6 (7). Successive reduction gives
rise to substantial lowering of the C
O stretching frequen-
cies. The ν(C
O) in the “super-reduced” chromium species
is in-between the typical C
O double and single bonds,
where the CO ligands may be formulated as carbyne-like
ligands. The number of π bonds formulated in Lewis struc-
tures (on which the determination of oxidation numbers is
based) has to be in accord with the nine-orbital rule and the
symmetry of orbitals.3 Furthermore, valence states of central
atoms (ions) after (heterolytic) cleavage of all ligands have to
be evaluated for proper assignment of oxidation states. As-
signment of d10 valence electron configurations of M and oxi-
dation numbers ranging from 0 (M = Ni) up to 4 (M = Cr)
in complexes [M(CO)4]n (Figure 6) is consistent with all
these aspects.
Further instructive examples are nitrosyl complexes of
transition metals (8). There are two types, “linear” complexes,
M
N
O 160–180, and bent complexes, M
N
O 120–
140, with sp- and sp2-hybridized nitrogen atoms, respec-
tively. Relevant Lewis structures are shown in Figure 7. Of
particular interest is the lone electron pair on N in the bent
complexes, 10a and 10b, which have σ symmetry and may
not be included into the resonance of the π system. To choose
appropriate oxidation numbers, experimental data are nec-
essary on the bending of the M
N
O unit and on the ex-
tent of π back-donation. Owing to overlapping, IR
spectroscopy cannot serve as a diagnostic tool for unambigu-
ous structural assignments: Typical ranges of ν(N
O) in lin-
ear and bent NO complexes are 1600–1950 cm 1 and
1520–1720 cm 1 , respectively (for comparison,
noncoordinated NO: ν(N
O) = 1878 cm1). The Fe
N
O
1944 cm1. This clearly indicates a linear-type complex, FeΙΙ
and a bound NO+ ligand. [IrCl(NO)(CO)(PPh3)2](BF4) is a
bent-type complex, Ir
N
O 124 and ν(N
O) = 1680
cm–1. Hence, it has to be formulated as an IrIII complex hav-
ing a bound NO− ligand. The classic “brown-ring” reaction
• www.JCE.DivCHED.org
 In the Classroom

Lx M C O Lx M C O Lx M C O

ON(M): 0 +2 +4
2− −
Figure 6. Lewis structures and Ligand: CO CO CO4
ν(C
O) stretching frequen- 8a 8b 8c
cies of some tetracarbonyl
complexes. L is a neutral
ligand.
CO C O C O

(1000 –1300 cm–1)

νCO / cm-1 2000 1800 1600 1400

−
[Ni(CO)4] [Co(CO)4] − −
[Fe(CO)4] 2 [Cr(CO)4]4

−
[Mn(CO)4]3

to detect nitrate-ions results in formation of a bent-type com- (magnetic, Mössbauer, and ESR measurements) or on quan-
plex, [FeIII(NO)(H2O)5]2+, and not a linear-type complex, tum chemical calculations. As shown in Figure 8, at first the
[FeI(NO)(H2O)5]2+, as is usually quoted in undergraduate central atom is reduced to Fe0 and is followed by reduction
textbooks (9). of the ligand up to pc4.
Structurally similar metal complexes differing only in the
number of electrons are also of interest with respect to as-
signing oxidation numbers. Such an electron variability has
been found in an unusually broad range of phthalocyanine–
metal complexes. As an example iron–phthalocyaninato com-
z
plexes, [Fe(pc)]n (H2pc = phthalocyanine), are shown in
Figure 8 (10). The question to be answered is whether the
stepwise reduction of [Fe(pc)] results in reduction of the iron
atom or of the ligand. The decision whether the additional
electrons enters a metal-centered or a ligand-centered orbital N N N
can only be made on the basis of experimental investigations
N Fe N

N N N

Lx M N O Lx M N O LxM N O
ON(M): −1 +1 +3
Ligand: NO+ NO− NO3−
9a 9b 9c
complex z ON(Fe) ligand
−
[FeBr(pc)] 1+ +3 pc2
−
LxM N LxM N [Fe(pc)] 0 +2 pc2
O +1 2−
O Li[Fe(pc)]·4.5thf 1− pc
ON(M): +1 +3 −
Li2[Fe(pc)]·5.5thf 2− 0 pc2
Ligand: NO− NO3− Li3[Fe(pc)]·8thf 3− 0 pc 3−
−
10a 10b Li4[Fe(pc)]·9thf 4− 0 pc4

Figure 7. Lewis structures of metal–nitrosyl complexes. L is a neu- Figure 8. Reduction of the iron–phthalocyanine complex.
tral ligand.

www.JCE.DivCHED.org • Vol. 81 No. 8 August 2004 • Journal of Chemical Education 1151

 In the Classroom

π Ligands
CH2 CH2 CH2
The electron balance of π-donor–π-acceptor ligands has : Lx M
Lx M Lx M
to be handled in the same way as for n-donor–π-acceptor CH2 CH2 CH2
ligands. As an example, in Figure 9 the two relevant Lewis
structures 11a and 11b are shown for an η2-ethene complex ON(M): 0 +2
(11). Exceptionally high π back-donation results in increas- Ligand: C2H4 C2H42 −
ing the oxidation number of the metal by two units (n ver- 11 11a 11b
sus n + 2) and reducing the ligand (C2H4 versus C2H42−).
11a represents a π ethene and 11b a metallacyclopropane
complex. Real electronic structures of all η2-ethene complexes R
R R
(11) have to be described as resonance hybrids, as they are a
C C C
weighted average of these two canonical forms. To ascribe : Lx M Lx M
Lx M
oxidation numbers means to decide which formula contrib- C C C
utes most to the resonance hybrid. This decision has to be R R R
based on experimental data, especially the information gained ON(M): 0 +2
about the coordination induced lengthening of the olefinic
Ligand: C2R2 C2R22 −
C
C bond and the degree of back bending of the substitu-
ents on olefinic carbon atoms (Figure 10). 12 12a 12b
Zeise’s salt, K[PtCl3(η2-C2H4)]H2O, is the classic ex-
ample of a π-ethene complex, C
C 1.375(4) Å and α = Figure 9. η2-Ethene and η2-alkyne metal complexes. L is a neutral
16.2 (11), with a small degree of back-donation only as com- ligand.
parison with uncoordinated ethene, C
C 1.339 Å and α =
0, shows. On the other hand, X-ray structural analyses of
[Os(CO)4(η2-C2H4)] and mer-[W(CO)3(η2-C2H4)(η4-nbd)]
(nbd = norbornadiene) exhibit metallacyclopropane structures
(12), where the C
C bonds, 1.49(2) and 1.48(1) Å, respec- back
tively, in the η2-C2H4 ligands are nearly as long as that in α
bending
cyclopropane, 1.512 Å.
Analogously, η2-alkyne complexes (Figure 9, structure R2 R2
12) have to be considered as resonance hybrids between π- R R C
alkyne (12a) and metallacyclopropene (12b) complexes.4 C
M elongation
Diphenylacetylene, for example, forms complexes of both C C
types as shown by the following complexes (13): cis- R R
R2 R2
[Pt(C 6 F 5 ) 2 (η 2 -PhC⬅CPh) 2 ], C
C 1.203(7) Å and
[WCl2(η2-PhC⬅CPh)L(PMe3)2], L = CO, C
C 1.341(6) front free coordinated
Å; L = PMe3, C
C 1.33(2) Å. Designation of these com- view side view
plexes as “π-diphenylacetyleneplatinum(II)” and “tungsta(IV)-
cyclopropene” is justified by comparison the C
C bond
lengths in the complexes with those in noncoordinated Figure 10. Schematic showing of the coordination induced C
C
diphenylacetylene, 1.21 Å, and 1,2-diphenylcyclopropene, bond elongation and back bending of the R groups in η2-olefin
≈1.34 Å. complexes.

σ Ligands
Oxidative addition reactions of dihydrogen to low-va-
lent metal complexes yielding dihydridometal complexes are
very common and may proceed in a concerted mechanism H H
with η2-H2 complexes as intermediates (Figure 11, structures Lx M + H2 Lx M Lx M
13–15). Such complexes have been isolated and fully char- H H
acterized spectroscopically and structurally (14). These are ON(M): 0 +2
the prototypes of σ complexes. As a result of the exception- 13 14 15
ally low donor strength of H2, stable dihydrogen complexes
will not exist without a substantial degree of donation of d H H
electrons of the metal atoms into the antibonding σ* H
H Lx M Lx M
orbital. However, balance is important; a too great extent of H H
back-donation results in breaking the underlying σ H
H ON(M): 0 +2
bond and oxidative addition occurs, yielding 15.
14a 14b
η2-H2 complexes 14 have to be represented by the two
Lewis structures 14a and 14b.5 The first isolated stable com-
plex was [W(CO)3(η2-H2){P(i-Pr)3}2] (Kubas, 1984) exhib- Figure 11. Oxidative addition of dihydrogen to low-valence metal
iting a significantly longer H
H bond than in free H2, complexes via η2-dihydrogen complexes. L is a neutral ligand.

1152 Journal of Chemical Education • Vol. 81 No. 8 August 2004 • www.JCE.DivCHED.org


molecular topological
formula formula
Figure 12. Concepts of Lewis
structures and oxidation num-
bers in teaching molecular
chemistry (above) with SO2
as an example (below).
SO2 O S O O
0.82(1) versus 0.74 Å. The ν(H
H) stretching frequencies
in dihydrogen complexes are typically lowered by more than
1000 cm1 compared with free H2. Furthermore, there are
η2-H2 complexes with elongated H
H bonds, 1.2–1.4 Å;
for example, [ReH5(η2-H2)(PR3)2], that have to be described
in terms of resonance theory by a higher contribution of ca-
nonical form 14b.
Concluding Remarks
To apply the concept of oxidation numbers means elec-
trons that are shared between atoms in molecules are assigned
to a specific atom. From this it follows that oxidation num-
bers, in general, do not reflect the “properties” of atoms in
molecules but the concept is used to systematize chemistry.
Furthermore, inherent in this concept is that there may be
alternative assignments of oxidation numbers to atoms of a
molecule (as it happens quite often in metal complexes). To
select the “best” set of oxidation numbers may be—within
certain limits—arbitrary and may also depend on the appli-
cation one is interested in. If need be, experimental infor-
mation (structural data, results from IR, Raman, or
Mössbauer measurements) and theoretical calculations have
to be considered. To do so, the concept of oxidation states is
complementary to other “rules” (like the 18-electron rule)
already in use. Furthermore, the concept proved to be a valu-
able framework to systematize and to analyze coordination
compounds structurally and electronically (15).
The concept of oxidation states is embedded in the teach-
ing process of molecular chemistry for early chemistry stu-
dents as shown in Figure 12. Starting from molecular
formulas (giving the composition of molecules) via topologi-
cal formulas6 (representing the constitution of molecules, that
www.JCE.DivCHED.org • Vol. 81 No. 8 August 2004
In the Classroom
VSEPR
model geometric
structure
electronic
structure
Lewis
structure(s)
formal
charges
oxidation
electro- numbers
negativity
S
O O trigonal planar (C2v symmetry)
VSEPR: O-S-O ca. 120°
exper.: O-S-O 119.5°
S sp2 hybridized
S
O - delocalized (O-S-O) π system
- lone pair of S has σ symmetry
ON(S) = +4
etc. ON(O) = – 2
is, the connectivity of atoms in molecules) the Lewis formu-
las are derived. They show the pattern and numbers of bonds
and nonbonding electrons or electron pairs and play a cen-
tral role to the understanding of molecular chemistry. Lewis
formulas give a first insight into geometric structures (by ap-
plying the VSEPR model) and electronic structures of mol-
ecules as well. Homolytic and heterolytic cleavage of covalent
bonds are indicated via the formal charges and the oxidation
numbers the (hypothetical) borderline cases. These are the
“pure covalent” and “pure electrostatic” views of covalent
bonds, respectively.
From the didactical point of view this is the most infor-
mative way for students to understand the underlying prin-
ciples of the concept of oxidation states7 and the model
character of oxidation numbers. This view neither overesti-
mates the meaning nor reduces the concept to a formal nu-
merical tool for bookkeeping electrons in reduction–oxidation
reactions. This is especially true when the electronic struc-
ture of a molecule can only be properly described by a reso-
nance hybrid. By evaluating the oxidation numbers in all
relevant resonance forms, the students will recognize directly
the model character of the concept and get a sense of the
limitations of the concept. Thus students will learn where
no oxidation numbers should be given at all because they
are meaningless or where alternative sets of oxidation num-
bers should be discussed to understand different aspects of
electronic structures of molecules under consideration. For
the formal bookkeeping of electrons in redox equations, it
may also be enough to give a reasonable set of oxidation num-
bers without detailed analysis of small differences in electrone-
gativities of bonding partners or of π-bonding effects. This
also holds for all molecules that cannot be properly described
by Lewis structures.
• Journal of Chemical Education 1153
 In the Classroom
Acknowledgments
I am indebted to Rudolf Taube (Halle) for stimulating
discussions, to Amanda Elliott (Loghborough) for language
polishing, and to the Fonds der Chemischen Industrie for
financial support.
Notes
1. When we do not allow a rearrangement of electrons, then
we get the valence state of Mz in the complex. If there is more than
one reasonable possibility of (formal) cleavage of the ligands then
the valence states of M in the alternatives may be inspected to find
out what might be the more plausible oxidation number in this
instance (16).
2. Of particular interest is the designation of the σ complex.
This is a complex where a ligand donates electrons from a σ bond
into an empty metal orbital, as in the case of complexes of dihy-
drogen (see Figure 11 for an example). Before complexes of this
type were known, one could only distinguish between n and π com-
plexes; typically in this case the former ones were frequently named
as σ complexes.
3. Transition metals have nine valence orbitals [5(n – 1)d +
1ns + 3np; n is the principal quantum number]. Hence, Lewis struc-
tures that make use of more than nine orbitals are not valid. Fur-
thermore, the number of π bonds has to be in accord with orbital
symmetry.
4. This is a simplified picture in that owing to the orthogo-
nal π bonds alkynes may act as four-electron donors and as four-
electron acceptors.
5. Taking into consideration that resonance structures are de-
fined as alternative representations of the electronic configuration
of a fixed set of nuclei, it will be evident that formula 14b (repre-
senting one of the two canonical forms of an η2-H2 complex 14)
has another meaning different from Lewis structure 15 (represent-
ing a real existing dihydrido complex).
6. In topological formulas two atoms are connected by a line
when a bond between them exists, irrespective of the bond type.
Hence, these lines do not represent electron pairs as it is the case
in Lewis structures.
7. Experience shows that students who have mastered writ-
ing a Lewis formula of a molecule are capable of assigning the oxi-
dation numbers correctly in most cases. On the other hand, students
who fail to draw a Lewis formula of a molecule successfully often
fail to correctly use a set of hierarchical oxidation number rules.
Instructors can check tutorials for the treatment of S2O82− as a useful
example .
1154 Journal of Chemical Education • Vol. 81 No. 8 August 2004
Literature Cited
1. (a) Eggert, A. A.; Middlecamp, C.; Kean, E. J. Chem. Inf.
Comput. Sci. 1990, 30, 181. (b) Birk, J. P. J. Chem. Educ. 1992,
69, 294. (c) Calzaferri, G. J. Chem. Educ. 1999, 76, 362. (d)
Holder, D. A.; Johnson, B. G.; Karol, P. J. J. Chem. Educ.
2002, 79, 465.
2. (a) Kauffmann, J. M. J. Chem. Educ. 1986, 63, 474. (b) Woolf,
A. A. J. Chem. Educ. 1988, 65, 45. (c) Packer, J. E.; Woodgate,
S. D. J. Chem. Educ. 1991, 68, 456.
3. Werner, A. Neuere Anschauungen auf dem Gebiete der Anorgan-
ischen Chemie; Vieweg: Braunschweig, Germany, 1920.
4. Stock, A. Angew. Chem. 1919, 32, 373.
5. Pauling, L. General Chemistry; Freeman: San Francisco, CA,
1947; p 173.
6. Mullay, J. Struct. Bond. 1987, 66, 1.
7. (a) Ellis, J. E. Adv. Organometal. Chem. 1990, 31, 1. (b) Beck,
W. Angew. Chem. 1991, 103, 173.
8. (a) Mingos, D. M. P.; Sherman, D. J. Adv. Inorg. Chem. 1989,
34, 293. (b) Johnson, B. F. G.; Haymore, B. L.; Dilworth, J.
R. In Comprehensive Coordination Chemistry; Wilkinson, G.,
Gillard, R. D., McCleverty, J. A., Eds.; Pergamon: Oxford
1987; Vol. 2, p 99.
9. Wanat, A.; Schneppensieper, T.; Stochel, G.; van Eldik, R.;
Bill, E.; Wieghardt, K. Inorg. Chem. 2002, 41, 4.
10. Taube, R. Pure Appl. Chem. 1974, 38, 427.
11. Love, R. A.; Koetzle, T. F.; Williams, G. J. B.; Andrews, L.
C.; Bau, R. Inorg. Chem. 1975, 14, 2653.
12. (a) Bender, B. R.; Norton, J. R.; Miller, M. M.; Anderson, O.
P.; Rappé, A. K. Organometallics 1992, 11, 3427. (b) Grevels,
F.-W.; Jacke, J.; Betz, P.; Krüger, C.; Tsay, Y.-H. Organometal-
lics 1989, 8, 293.
13. (a) Usón, R.; Forniés, J.; Tomás, M.; Menjón, B.; Fortuno,
C.; Welch, A. J.; Smith, D. E. J. Chem. Soc., Dalton Trans.
1993, 275. (b) Clark, G. R.; Nielson, A. J.; Rae, A. D.;
Rickard, C. E. F. J. Chem. Soc., Dalton Trans. 1994, 1783. (c)
Nielson, A. J.; Boyd, P. D. W.; Clark, G. R.; Hunt, P. A.;
Hursthouse, M. B.; Metson, J. B.; Rickard, C. E. F.;
Schwerdtfeger, P. A. J. Chem. Soc., Dalton Trans. 1995, 1153.
14. (a) Kubas, G. J. Acc. Chem. Res. 1988, 21, 120. (b) Crabtree,
R. H. Angew. Chem. 1993, 105, 828.
15. Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M.
Advanced Inorganic Chemistry; Wiley: New York, 1999.
16. (a) Nyholm, R. S.; Tobe, M. L. Adv. Inorg. Chem. Radiochem.
1963, 5, 1. (b) Taube, R. In Internationales Döbereiner-
Kolloquium; Bolck, F., Ed.; University Press: Friedrich-Schiller
University of Jena, Germany, 1981; p 73.
• www.JCE.DivCHED.org