Created by Burke Scott Williams (swilliams@jsd.claremont.edu) and posted on VIPEr on 01/10/2009.

This
work is licensed under the Creative Commons Attribution Non-commercial Share Alike License in 2009.
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An 18 Electron Guideline Worksheet

Use what you learned in the primmer and the hints below to count electrons
by both the Closed Shell (CS) and Neutral Ligand (NL) Methods.

1. First let’s figure out how to deal with charged complexes. Remember that each of
the complexes, unless specified otherwise, is an 18 e- species.

[Fe(CO)4]2-

L or X e- (CS) e- (NL)
Fe n/a

CO
(x4, remember!)
2- charge n/a

TOTAL n/a 18 18

Explain below in one sentence each (a) how we deal with overall charges on the
complex in the two methods and (b) how this can be rationalized.

2. Now let’s look at a complex which is unusual in two ways. Zeise’s Salt (first
synthesized in 1825!) is a square planar complex. Square planar complexes are
almost invariably d8, 16 e- species. You’ll learn why this is later. The second
interesting feature is that it’s a -complex (remember the Dewar-Chatt-Duncanson
model?)
-
- Cl Cl
[Pt(C2H4)Cl3]
Pt
-
L or X e (CS) e (NL) - Cl
Pt n/a

C2H4

Cl

1- charge n/a

TOTAL n/a 16 16
Created by Burke Scott Williams (swilliams@jsd.claremont.edu) and posted on VIPEr on 01/10/2009. This
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3. The first organometallic compound most students encounter is ferrocene.

Each of the rings of the “sandwich” is a cyclopentadienide anion (Cp-,
C5H5-) . This is an 18 e- compound.
Fe

L or X e- (CS) e- (NL)
FeCp2 Fe n/a

Cp Leave H
Blank
TOTAL n/a 18 18 : H
H

Obviously, we can’t class Cp- as “X” or “L” given your above answer. H H
Cp- is a composite ligand. It is possible for a ligand to act as an “L2”
ligand (ethylene diamine, en, H2NCH2CH2NH2, is a good example), or an XL ligand
(such as acetate, which can coordinate through both the anionic oxygen (X) and the
neutral oxygen (L) at the same time). Many other such LmXn ligands are possible.
Given your electron counts above, give a classification to Cp- and justify your choice
on the basis of the Cp- structure at right.

Nota Bene: All n-membered all-sp2 rings of this type donate n electrons in the neutral
ligand method or either n (even values of n) or n+1 (odd values of n) for the closed
shell method.

4. Now let’s try a dimeric species. Obviously, when you have two metals, each of
the metals should go to 18. You can either count to 36 for the metals together, or,
as we’ll do it here, divide the molecule in half, trying to share any bridging
ligands equally. Note that “” indicates a ligand bridging two metals.
L or X e- (CS) e- (NL)
[CoCp(CO)(-CO)]2 Co n/a

O Cp
O
CO
C
Co Co
-CO
C C
O TOTAL n/a 18 18
O
Created by Burke Scott Williams (swilliams@jsd.claremont.edu) and posted on VIPEr on 01/10/2009. This
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5. One kind of bonding we have yet to deal with is metal-metal bonding. Let’s try a
couple of metal-metal bonded complexes that are each 18 e-.

L or X e- (CS) e- (NL)
[FeCp(CO)(-CO)]2
Fe n/a
O
O Cp
C CO
Fe Fe
C C -CO
O
O Fe-Fe
bond
TOTAL n/a 18 18

6. We can also use the 18 electron guideline to predict the bond order (number of
bonds) between two metals in a dimer. For this one forget everything you know
about what kind of bonding is possible between two atoms (yes, this is a real
molecule).

[Cr(OH2)(-OAc)2]2
L or X e- (CS) e- (NL)
Cr n/a

H2O
O O O O
-OAc*
H2O Cr ? Cr OH2
(anion)
O O O O -OAc*
(neutral)
Cr-Cr
bond
TOTAL n/a 18 18

* Note that there are “two ends” to each acetate (see

text of #3). Make sure each Cr gets an equal share!

In case this mode of bonding is new to you, it involves , , and -bonding!

Created by Burke Scott Williams (swilliams@jsd.claremont.edu) and posted on VIPEr on 01/10/2009. This
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7. We dealt with -complexes back in #2, now let’s do a -complex. It’s pretty
similar. In this case, the metal is bound to the -bond of dihydrogen.

trans-mer-
W(CO)3(PCy3)2(H2) L or X e- (CS) e- (NL)
W n/a
PCy3
O
PCy3
C H
CO
O C W
H 
C
O PCy3
TOTAL n/a 18 18

8. Now let’s do a bridging halide.

[Rh(COD)Cl]2
L or X e- (CS) e- (NL)
Rh n/a

Cl COD
Rh Rh -Cl
Cl (mode 1)
-Cl
(mode 2)
TOTAL n/a 16 16
(sq. pl.)

Hint: See OAc in #6 for the “two kinds” of bonding

here

Provide a brief explanation for why chlorine is able to bond in both modes here:
Created by Burke Scott Williams (swilliams@jsd.claremont.edu) and posted on VIPEr on 01/10/2009. This
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9. A final common ligand is allyl, C3H3-. Figure out the totals for yourself (I suggest
counting the metals together, and think
about whether you’d expect these to be L or X e- (CS) e- (NL)
16 e- or 18 e- metals)! Ni n/a

[Ni(allyl)(-OH)]2 -OH
H C3H5
O
Ni Ni TOTAL n/a
O
H

There are two ligand types that we have not dealt with here. One of them is metal-
ligand multiple bonded ligands (carbenes, carbynes, imides, nitrides, and oxides), and
the other is nitrosyl ligands (NO). Different chemists and different textbooks treat
them slightly differently, and we have concentrated here on the “core cases” for
which the electron counting is straightforward and (relatively) non-controversial.