The 18 electron rule

Just as organic chemists have their octet rule for organic

compounds, so do organometallic chemists have the 18 electron
rule. And just as the octet rule is often violated, so is the 18
electron rule. However, both serve a useful purpose in predicting
reactivity. Each derives from a simple count of the number of
electrons that may be accommodated by the available valence
orbitals (one s and three p for organic chemists; organometallic
chemists get five bonus d-orbitals in which to place their
electrons).
Counting electrons in organometallic complexes
Knowing how many valence electrons "belong to" a transition
metal complex allows us to make predictions about the
mechanisms of reactions and the possible modes of reactivity.
There are two distinct methods that are used to count electrons,
the neutral or covalent method and the effective atomic number
or ionic method. While this may seem confusing, these are simply
two different accounting systems that give us the same final
answer. Although having two systems may seem confusing, it at
least provides us a convenient way to double check our answer.
What are d-electrons, anyway?
While we teach our students in freshman chemistry that the
periodic table is filled in the order [Ar]4s23d10, this turns out to be
true only for isolated metal atoms. When we put a metal ion into an
electronic field (surround it with ligands), the d-orbitals drop in
energy and fill first. Therefore, the organometallic chemist
considers the transition metal valence electrons to all be delectrons. There are certain cases where the 4s23dx order does
occur, but we can neglect these in our first approximation.

Therefore, when we ask for the d-electron count on a transition

metal such as Ti in the zero oxidation state, we call it d 4, not d2. For
zero-valent metals, we see that the electron count simply
corresponds to the column it occupies in the periodic table. Hence,
Fe is in the eighth column and is d 8 (not d6) and Re3+ is d4 (seventh
column for Re, and then add 3 positive charges...or subtract three
negative ones). Now that we can assign a d-electron count to a
metal center, we are ready to determine the electronic contribution
of the surrounding ligands and come up with our overall electron
count.

Method 1: The ionic (charged) model

The basic premise of this method is that we remove all of the
ligands from the metal and, if necessary, add the proper number of
electrons to each ligand to bring it to a closed valence shell state.
For example, if we remove ammonia from our metal complex,
NH3 has a completed octet and acts as a neutral molecule. When it
bonds to the metal center it does so through its lone pair (in a
classic Lewis acid-base sense) and there is no need to change the
oxidation state of the metal to balance charge. We call ammonia a
neutral two-electron donor.
In contrast, if we remove a methyl group from the metal and
complete its octet, then we formally have CH3-. If we bond this
methyl anion to the metal, the lone pair forms our metal-carbon
bond and the methyl group acts as a two-electron donor ligand.
Notice that to keep charge neutrality we must oxidize the metal by
one electron (i.e. assign a positive charge to the metal). This, in
turn, reduces the d-electron count of the metal center by one. We'll
see several examples below.
Method 2: The covalent (neutral) model

The major premise of this method is that we remove all of the

ligands from the metal, but rather than take them to a closed shell
state, we do whatever is necessary to make them neutral. Let's
consider ammonia once again. When we remove it from the metal,
it is a neutral molecule with one lone pair of electrons. Therefore,
as with the ionic model, ammonia is a neutral two electron donor.
But we diverge from the ionic model when we consider a ligand
such as methyl. When we remove it from the metal and make the
methyl fragment neutral, we have a neutral methyl radical. Both
the metal and the methyl radical must donate one electron each to
form our metal-ligand bond. Therefore, the methyl group is a one
electron donor, not a two electron donor as it is under the ionic
formalism. Where did the other electron "go"? It remains on the
metal and is counted there. In the covalent method, metals retain
their full complement of d electrons because we never change the
oxidation state from zero; i.e. Fe will always count for 8 electrons
regardless of the oxidation state and Ti will always count for four.
Notice that this method does not give us any immediate
information about the formal oxidation state of the metal, so we
must go back and assign that in a separate step. For this reason,
many chemists (particularly those that work with high oxidation
state complexes) prefer the ionic method.

Electron donation of common ligands

In the table below are some common transition metal ligands and
the number of electrons that each donates to a metal center. Some
ligands can donate a variable number of electrons. For example, an
alkoxide, M-OR, can donate two to six electrons depending on the
hybridization of the oxygen atom.

The two methods compared: some examples

The most critical point we should remember is that like oxidation
state assignments, electron counting is a formalism and does
not necessarily reflect the distribution of electrons in the

molecule. However, these formalisms are very useful to us, and

both will give us the same final answer.
Consider the following simple examples. Notice how some ligands
donate the same number of electrons no matter which formalism
we choose, while the number of d-electrons and donation of the
other ligands can differ. All we have to do is remember to be
consistent and it will work out for us.

Self-Test
In each of the following examples, select the oxidation state of the
transition metal atom, dn count (assign it using the ionic model),
and number of valence electrons at each metal center. Then hit the
Submit Answer button for that compound to see if you are correct.

If you do not yet know your periodic table, you can either visit
the Periodic Table Challenge to test your skill or you can view a
complete periodic table in this popup window.
Oxidation
State:

Oxidation

St

dn count:
dn count:
Valence
Valence
Electrons:
This half-sandwich is used
as a gasoline anti-knock
additive.

Electro

Free hint: This is quite similar to an exam

shown above.
Submit Answ er

Submit

Oxidation
State:

Oxidation

St

dn count:
dn count:
Valence
Valence
Electrons:
Answer
for
either
equivalent Re, not both.
This was the first example
of a metal-metal quadruple

Electro

This was the first example of a Schr

alkylidene complex.
Submit Answ er

bond.
Submit Answ er

Oxidation
State:

Oxidation

State:

dn count:
dn count:
Valence Electrons:
Valence
Electrons:
Notice
that
is not a cyclopentadienyl
ligand.

A classic example of a metallocene.

Submit Answ er

Submit Answ er

Oxidation
State:

Oxidation

St

dn count:
dn count:
Valence
Valence
Electrons:
Give your answer for
either equivalent iridium
center.

Electro

This
has
t
each hydride, dihydrogen and phosphine ligand
Submit Answ er

Submit Answ er

Oxidation
State:

Oxidation

St

dn count:
dn count:
Valence
Valence
Electrons:
Hint 1: the sulfur ligands
are called dithiocarbamates
(dtc). Hint 2: look closely
at the imido ligands.

Electro

How are you going to count the alkoxide ligan

Hint: see the donation chart above.
Submit Answ er

Submit Answ er

Now, we will learning about the 18-electron rules in organometallic

chemistry. Seperti biasa saya merujuk dari buku miessler dan huheey
dan materi kuliah . Secara sederhana dan basic suatu molekul kimia
dikatakan stabil apabila telah memiliki jumlah electron menyerupai gas
mulia. Aturan ini kita kenal dengan aturan octet. Kemudian kenapa pada
kimia organologam dikenal 18-elektron dan pada molekul sederhana
hanya 8-elektron? Secara sederhana dapat kita analogkan 18-elektron
dengan 8-elektron, dan analog itu begini: aturan 8-elektron digunakan
untuk senyawaan golongan utama, yang artinya merepresentasikan
jumlah electron pada kulit valensi terisi penuh (S 2P6), sedangkan 18elektron berhubungan dengan jumlah electron valensi untuk logam

transisi (s2p6d10). Dari penjelasan tersebut dapat diketahui mengapa

organologam menggunakan aturan 18-elektron, karena organologam
merupakan senyawaan yang mengandung atom pusat logam transisi
(sebagian besar) dan senyawa organic (hidrokarbon).
Oke setelah tahu penjelasan singkat tentang aturan 18-elektron, sekaran
mari menginjak ke bagaimana cara menghitung jumlah electron senyawa
organologam dengan system 18-elektron. Aturan 18-elektron ini terbagi
menjadi dua metode, pertama adalah metode Donor Pair dan yang
kedua metode Neutral Ligand.
1. Donor Pair Method (Method A)
Pada metode ini melibatkan ligan sebagai pendonor pasangan electron
ke logam. Untuk menentukan jumlah total electron, kita harus
menghitung juga muatan setiap ligand dan menentukan tingkat atau
bilangan oksidasi formal dari atom pusat.
Contoh: dikarbonil kloro pentahapto siklopentadienil besi (II) (5C5H5)Fe(CO)2Cl
5-C5H5-mendonorkan 3 pasang e-, CO mendonorkan 2 elektron (karena
terdapat 2 CO maka dikali 2), Fe(II) = [Ar]4s03d6 jadi mendonorkan 6
elektron, sehingga jika dijumlahkan:
Fe (II)
: 6 e5
-C5H5 : 6 e2(CO)
: 4 eCl: 2 eTotal eletron : 18 elektron
2. Neutral Ligand Method (Method B)
Pada metode ini kita akan menggunakan jumlah electron yang akan
didonasikan oleh ligand tetapi dalam keadaan netral. Pada ligan
anorganik sederhana, jumlah electron yang didonasikan sama dengan
muatan negatifnya sebagai ion bebeas. Misalnya Cl donor 1 e- (muatan
ion bebas -1), O donor 2 e- (muatan ion bebeas -2), N donor 3 e(muatan ion bebas -3). Pada metode ini kita tidak memerlukan
penentuan bilangan oksidasi dari atom pusat.

Contoh: dikarbonil kloro pentahapto siklopentadienil besi (II) (5C5H5)Fe(CO)2Cl

Fe mendonorkan 8 e- sesuai konfigurasi elektronnya, 5C5H5 mendonorkan 5 e- (kita mempertimbangan ligan ini sebagai ligan
netral), CO mendonorkan 2 e-, dan Cl mendonorkan 1 e- (sebagai
spesies netral)
Fe
: 8 e5
-C5H5 : 5 e2(CO)
: 4 eCl
: 1 eTotal
= 18 e-

18-Electron rule
From Wikipedia, the free encyclopedia
The 18-electron rule is a rule used primarily for predicting formulae for
stable metal complexes.[1] The rule is based on the fact that the valence
shells of transition metals consist of nine valence orbitals, which
collectively can accommodate 18 electrons as either bonding or
nonbonding electron pairs. This means that, the combination of these
nine atomic
orbitals with ligand orbitals
creates
nine molecular

orbitals that are either metal-ligand bonding or non-bonding. When a

metal complex has 18 valence electrons, it is said to have achieved the
same electron configuration as the noble gas in the period. The rule and
its exceptions are similar to the application of the octet rule to main
group elements. The rule is not helpful for complexes of metals that are
not transition metals, and interesting or useful transition metal
complexes will violate the rule because of the consequences deviating
from the rule bears on reactivity. The rule was first proposed by
American chemist Irving Langmuir in 1921.[1][2]
Contents
[hide]

o
o

1 Applicability of the 18-electron rule

1.1 Consequences for reactivity
1.2 Alternative analysis
2 Exceptions to the 18-electron rule

2.1 16electron rule

2.2 Bulky ligands

2.3 High-spin complexes

2.4 Pi-donating ligands

2.5 Combinations of effects

2.6 Higher electron counts

3 See also

4 References

5 Further reading

Applicability of the 18-electron rule[edit]

The rule usefully predicts the formulae for low-spin complexes of the
Cr, Mn, Fe, and Co triads. Well-known examples include ferrocene, iron
pentacarbonyl, chromium carbonyl, and nickel carbonyl.
Ligands in a complex determine the applicability of the 18-electron rule.
In general, complexes that obey the rule are composed at least partly
of pi-acceptor ligands (also known as -acids). This kind of ligand exerts
a very strong ligand field, which lowers the energies of the resultant
molecular orbitals and thus favorably occupied. Typical ligands
includeolefins, phosphines, and CO. Complexes of -acids typically
feature metal in a low-oxidation state. The relationship between
oxidation state and the nature of the ligands is rationalized within the
framework of backbonding.
Consequences for reactivity[edit]
Compounds that obey the 18 VE rule are typically "exchange inert."
Examples include [Co(NH3)5Cl]2+, Mo(CO)6, and [Fe(CN)6]4. In such
cases, in general ligand exchange occurs via dissociative
substitution mechanisms, wherein the rate of reaction is determined by
the rate of dissociation of a ligand. On the other hand, 18-electron
compounds can be highly reactive toward electrophiles such as protons,
and such reactions are associative in mechanism, being acid-base
reactions.
Complexes with fewer than 18 valence electrons tend to show enhanced
reactivity. Thus, the 18-electron rule is often a recipe for non-reactivity
in either a stoichiometric or acatalytic sense.
Alternative analysis[edit]
In the prevalent ligand field analysis, the valence p orbitals on the metal
participate in metal-ligand bonding, albeit weakly. Some new theoretical
treatments do not count the metal p-orbitals in metal-ligand bonding,
[3]
although these orbitals are still included as polarization functions. This
results in a duodectet[3] (12) rule which accommodates all low-spin
complexes including linear 14e complexes such as Tollen's reagent and

square planar 16e complexes as well as implies that such transition metal
complexes arehypervalent, but has yet to be adopted by the general
chemistry community.
Exceptions to the 18-electron rule[edit]
-donor or -donor ligands with small interactions with the metal
orbitals lead to a weak ligand field which increases the energies of
t2g orbitals. These molecular orbitals becomenon-bonding or weakly antibonding orbitals (small oct). Therefore, addition or removal of electron
has little effect on complex stability. In this case, there is no restriction
on the number of d-electrons and complexes with 12 -22 electrons are
possible. Small oct makes filling eg* possible ( > 18e-) and -donor
ligands can make t2g antibonding ( < 18 e-). These types of ligand are
located in low to medium of the spectrochemical series. For example:
[TiF6]2 (Ti4+, d0, 12 e), [Co(NH3)6]3+ (Co3+, d6, 18 e), [Cu(OH2)6]2+ (Cu2+,
d9, 21 e) In tems of metal ions, oct increases down a group as well as
increasing oxidation number. Strong ligand fields lead to lowspin complexes which cause some exceptions to 18-electron rule.
16electron rule[edit]
A popular class of complexes that violate the 18e rule are the 16e
complexes with d8 configurations. All high-spin d8metal ions
are octahedral (or tetrahedral), but the low-spin d8metal ions are all
square planar (Jahn-Teller distortion). Important examples of squareplanar low-spin d8 metal Ions are Ni(II), Pd(II), and Pt(II). At picture
below is shown the splitting of the d sub-shell in low-spin square-planar
complexes. Examples are especially prevalent for derivatives of the
cobalt and nickel triads. Such compounds are typicallysquare-planar.
The most famous example is Vaska's complex (IrCl(CO)(PPh3)2),
[PtCl4]2, and Zeise's salt [PtCl3(2-C2H4)]. In such complexes, the
dz2 orbital is doubly occupied and nonbonding.

Many catalytic cycles operate via complexes that alternate between

18e and square-planar 16 configurations. Examples include Monsanto
acetic acid synthesis, hydrogenations,hydroformylations, olefin
isomerizations, and some alkene polymerizations.
Other violations can be classified according to the kinds of ligands on
the metal center.
Bulky ligands[edit]
Bulky ligands can preclude the approach of the full complement of
ligands that would allow the metal to achieve the 18 electron
configuration. Examples:

Ti(neopentyl)4 (8 VE)
Cp*2Ti(C2H4) (16 VE)

V(CO)6 (17 VE)

Cp*Cr(CO)3 (17 VE)

Pt(PtBu3)2 (14 VE)

Co(norbornyl)4 (13 VE)

[FeCp2]+ (17 VE)

Sometimes such complexes engage in agostic interactions with the

hydrocarbon framework of the bulky ligand. For example:

W(CO)3[P(C6H11)3]2 has 16 VE but has a short bonding contact

between one C-H bond and the W center.
Cp(PMe3)V(CHCMe3) (14 VE, diamagnetic) has a short V-H bond
with the 'alkylidene-H', so the description of the compound is
somewhere between Cp(PMe3)V(CHCMe3) and Cp(PMe3)V(H)
(CCMe3).

High-spin complexes[edit]
High-spin metal complexes have singly occupied orbitals and may
not have any empty orbitals into which ligands could donate electron
density. In general, there are few or no -acidic ligands in the
complex. These singly occupied orbitals can combine with the singly
occupied orbitals of radical ligands (e.g., oxygen), or addition of
a strong field ligand can cause electron-pairing, thus creating a vacant
orbital that it can donate into. Examples:

CrCl3(THF)3 (15 VE)

[Mn(H2O)6]2+ (17 VE)

[Cu(H2O)6]2+ (21 VE, see comments below)

Complexes containing strongly pi-donating ligands often violate the

18-electron rule. These ligands include fluoride (F), oxide (O2),
nitride (N3), alkoxide (RO), and imide (oxide (RN2). Examples:

[CrO4]2 (16 VE)

Mo(=NR)2Cl2 (12 VE)

In the latter case, there is substantial donation of the nitrogen lone

pairs to the Mo (so the compound could also be described as a 16 VE
compound). This can be seen from the short Mo-N bond length, and
from the angle Mo - N - C(R), which is nearly 180. Counterexamples:

trans-WO2(Me2PCH2CH2PMe2)2 (18 VE)

Cp*ReO3 (18 VE)

In these cases, the M=O bonds are "pure" double bonds (i.e., no
donation of the lone pairs of the oxygen to the metal), as reflected in
the relatively long bond distances.
Pi-donating ligands[edit]
Ligands where the coordinating atom bear nonbonding lone pairs
often stabilize unsaturated complexes. Metal amides and alkoxides
often violate the 18e rule.
Combinations of effects[edit]
The above factors can sometimes combine. Examples include

Cp*VOCl2 (14 VE)

TiCl4 (8 VE)

Higher electron counts[edit]

Some complexes have more than 18 electrons. Examples:

Cobaltocene (19 VE)

Nickelocene (20 VE)

The hexaaqua copper(II) ion [Cu(H2O)6]2+ (21 VE)

Often, cases where complexes have more than 18 valence electrons

are attributed to electrostatic forces - the metal attracts ligands to
itself to try to counterbalance its positive charge, and the number of
electrons it ends up with is unimportant. In the case of the
metallocenes, the chelating nature of the cyclopentadienyl ligand
stabilizes its bonding to the metal. Somewhat satisfying are the two
following observations: (i) cobaltocene is a strong electron donor,
readily forming the 18-electron cobaltocenium cation and (ii)
nickelocene tends to react with substrates to give 18-electron
complexes, e.g. CpNiCl(PR3) and free CpH.
In the case of nickelocene, the extra two electrons are in orbitals
which are weakly metal-carbon antibonding, this is why it often

participates in reactions where the M-C bonds are broken and the
electron count of the metal will change to 18. [4]

Electron counting is a formalism used for classifying compounds and

for explaining or predicting electronic structure and bonding.[1] Many
rules in chemistry rely on electron-counting:
Octet rule is used with Lewis structures for main group elements,
especially the lighter ones such as carbon, nitrogen, and oxygen,
Eighteen electron rule in inorganic chemistry and organometallic
chemistry of transition metals,

Polyhedral skeletal electron pair theory for cluster compounds,

including transition metals and main group elements such
as boron including Wade's rules for polyhedralcluster compounds,
including transition metals and main group elements and mixtures
thereof.

Atoms that do not obey their rule are called "electron-deficient" when
they have too few electrons to achieve a noble gas configuration, or
"hypervalent" when they have too many electrons. Since these
compounds tend to be more reactive than compounds that obey their
rule, electron counting is an important tool for identifying the reactivity
of molecules.
Contents
[hide]

o
o

1 Counting rules
1.1 Neutral counting
1.2 Ionic counting
2 Electrons donated by common fragments

2.1 "Special cases"

3 Examples of electron counting

4 See also

5 References
Counting rules[edit]
Two methods of electron counting are popular and both give the same
result.

The neutral counting approach assumes the molecule or fragment

being studied consists of purely covalent bonds. It was popularized
by M.L.H. Green along with the L and X ligand notation.[2][3] It is
usually considered easier especially for low-valent transition metals.
[citation needed]

The "ionic counting" approach assumes purely ionic bonds

between atoms. It rewards the user with a knowledge of oxidation
states, which can be valuable.[peacock term] One can check one's
calculation by employing both approaches, though it is important to
be aware that most chemical species exist between the purely
covalent and ionic extremes.

Neutral counting[edit]

This method begins with locating the central atom on the periodic
table and determining the number of its valence electrons. One counts
valence electrons for main group elements differently from transition
metals.
E.g. in period 2: B, C, N, O, and F have 3, 4, 5, 6, and 7 valence
electrons, respectively.
E.g. in period 4: K, Ca, Sc, Ti, V, Cr, Fe, Ni have 1, 2, 3, 4, 5, 6, 8,
10 valence electrons respectively.

One is added for every halide or other anionic ligand which

binds to the central atom through a sigma bond.
Two is added for every lone pair bonding to the metal (e.g. each
Lewis base binds with a lone pair). Unsaturated hydrocarbons
such as alkenes and alkynes are considered Lewis bases.
Similarly Lewis and Bronsted acids (protons) contribute
nothing.

One is added for each homoelement bond.

One is added for each negative charge, and one is subtracted for
each positive charge.

Ionic counting[edit]

This method begins by calculating the number of electrons of

the element, assuming an oxidation state

e.g. for a Fe2+ has 6 electrons

S2 has 8 electrons

Two is added for every halide or other anionic ligand

which binds to the metal through a sigma bond.
Two is added for every lone pair bonding to the metal
(e.g. each phosphine ligand can bind with a lone pair).
Similarly Lewis and Bronsted acids (protons) contribute
nothing.
For unsaturated ligands such as alkenes, one electron is
added for each carbon atom binding to the metal.

Electrons donated by common fragments[edit]

Ligand

Electrons
Electrons
contributed
contributed
(neutral counting) (ionic counting)

2 (X; X = F, Cl, Br, I)

2 (H)

0 (H+)

4(O2)

6 (N3)

NR3

2 (NR3; R = H, alkyl,
aryl)

CR2

4 (CR22)

Ethylene

2 (C2H4)

cyclopentadienyl 5

6(C5H5)

benzene

6 (C6H6)

"Special cases"[edit]
The numbers of electrons "donated" by some ligands
depends on the geometry of the metal-ligand ensemble.
Perhaps the most famous example of this complication is the
M-NO entity .[peacock term] When this grouping is linear, the NO
ligand is considered to be a three-electron ligand. When the
M-NO subunit is strongly bent at N, the NO is treated as a

pseudohalide and is thus a one electron (in the neutral

counting approach). The situation is not very different from
the -3 vs. -1 allyl. Another unusual ligand from the
electron counting perspective is sulfur dioxide.
Examples of electron counting[edit]

CH4, for the central C

neutral counting: C contributes 4 electrons, each H radical

contributes one each: 4+4(1) = 8 valence electrons
ionic counting: C4 contributes 8 electrons, each proton contributes
0 each: 8 + 4(0) = 8 electrons.
Similar for H:
neutral counting: H contributes 1 electron, the C contributes 1
electron (the other 3 electrons of C are for the other 3 hydrogens in
the molecule): 1 + 1(1) = 2 valence electrons.
ionic counting: H contributes 0 electrons (H+), C4 contributes 2
electrons (per H), 0 + 1(2) = 2 valence electrons
conclusion: Methane follows the octet-rule for carbon, and the duet
rule for hydrogen, and hence is expected to be a stable molecule
(as we see from daily life)

H2S, for the central S

neutral counting: S contributes 6 electrons, each hydrogen radical

contributes one each: 6+2(1) = 8 valence electrons
ionic counting: S2 contributes 8 electrons, each proton contributes
0: 8+2(0) = 8 valence electrons
conclusion: with an octet electron count (on sulfur), we can
anticipate that H2S would be pseudotetrahedral if one considers the
two lone pairs.

SCl2, for the central S

neutral counting: S contributes 6 electrons, each chlorine radical

contributes one each: 6+2(1) = 8 valence electrons
ionic counting: S2+ contributes 4 electrons, each chloride anion
contributes 2: 4+2(2) = 8 valence electrons
conclusion: see discussion for H2S above. Notice that both
SCl2 and H2S follow the octet rule - the behavior of these
molecules is however quite different.

SF6, for the central S

neutral counting: S contributes 6 electrons, each fluorine radical

contributes one each: 6+6(1) = 12 valence electrons
ionic counting: S6+ contributes 0 electrons, each fluoride anion
contributes 2: 0+6(2) = 12 valence electrons
conclusion: ionic counting indicates a molecule lacking lone pairs
of electrons, therefore its structure will be octahedral, as predicted
by VSEPR. One might conclude that this molecule would be
highly reactive - but the opposite is true: SF 6 is inert, and it is
widely used in industry because of this property.

TiCl4, for the

central Ti

neutral counting: Ti contributes 4 electrons, each chlorine radical

contributes one each: 4+4(1) = 8 valence electrons
ionic counting: Ti4+ contributes 0 electrons, each chloride anion
contributes two each: 0+4(2) = 8 valence electrons
conclusion: Having only 8e (vs. 18 possible), we can anticipate
that TiCl4 will be a good Lewis acid. Indeed, it reacts (in some
cases violently) with water, alcohols, ethers, amines.

Fe(
CO
)5

neutral counting: Fe contributes 8 electrons, each CO contributes 2

each: 8 + 2(5) = 18 valence electrons
ionic counting: Fe(0) contributes 8 electrons, each CO contributes
2 each: 8 + 2(5) = 18 valence electrons
conclusions: this is a special case, where ionic counting is the same
as neutral counting, all fragments being neutral. Since this is an 18electron complex, it is expected to be isolable compound.
Ferrocene, (C5H5)2Fe, for the central Fe:
neutral
counting:
Fe
contributes
8
electrons,
the
2 cyclopentadienyl-rings contribute 5 each: 8 + 2(5) = 18 electrons
ionic counting: Fe2+ contributes 6 electrons, the two aromatic
cyclopentadienyl rings contribute 6 each: 6 + 2(6) = 18 valence
electrons on iron.
conclusion: Ferrocene is expected to be an isolable compound.
These examples show the methods of electron counting, they are
a formalism, and don't have anything to do with real life chemical
transformations. Most of the 'fragments' mentioned above do not exist as
such; they cannot be kept in a bottle: e.g. the neutral C, the tetraanionic
C, the neutral Ti, and the tetracationic Ti are not free species, they are
always bound to something, for neutral C, it is commonly found in
graphite, charcoal, diamond (sharing electrons with the neighboring
carbons), as for Ti which can be found as its metal (where it shares its
electrons with neighboring Ti atoms!), C4 and Ti4+ 'exist' only with
appropriate counterions (with which they probably share electrons). So
these formalisms are only used to predict stabilities or properties of
compounds!

Square Planar Complexes

In a square planar, there are four ligands as well. However, the difference is that the electrons of the ligands are only
attracted to the \(xy\) plane. Any orbital in the xy plane has a higher energy level. There are four different energy
levels for the square planar (from the highest energy level to the lowest energy level): dx -y , dxy, dz , and both dxz and dyz.
2

Figure 6: Splitting of the degenerate d-orbitals (without a ligand field) due to an square planar ligand field.

The splitting energy (from highest orbital to lowest orbital) is \(\Delta_{sp}\) and tends to be larger then \(\Delta_{o}\)
\[\Delta_{sp} = 1.74\,\Delta_o \tag{2}\]
Moreover, \(\Delta_{sp}\) is also larger than the pairing energy, so the square planar complexes are usually low
spin complexes.