Common Organic Ligands

H
H
H

H H
H H

H
H H
H H

Carbon Monoxide (CO) is also an important ligand

 Terminology: Hapticity
h x
“eta-x” was originally developed to indicate how many contiguous donor atoms of a
p-system were coordinated to a metal center. Hapticity is another word used to describe the
bonding mode of a ligand to a metal center. An h5-cyclopentadienyl ligand, for example, has
all five carbons of the ring bonding to the transition metal center.
hx values for all-carbon based ligands where the x value is odd usually
indicate anionic carbon ligands (e.g., h5-Cp, h1-CH3, h1-allyl or h3-allyl, h1-
CH=CH2). The # of electrons donated (ionic method of electron counting) by the
ligand is usually equal to x + 1. Even hx values usually indicate neutral carbon p-
system ligands (e.g., h6-C6H6, h2-CH2=CH2, h4-butadiene, h4-cyclooctadiene).
The # of electrons donated by the ligand in the even (neutral) case is usually just
equal to x.
 Common Ligands and Electrons Contributed
q Electron Counting

a) Common organometallic ligands

are assigned an electron count
and charge; those that are
commonly ions are treated as
such

b) The overall charge on the complex

must equal the total charge on
ligands plus the charge on the
metal; this helps determine d-
electron count of metal

c) Add up all electrons from metal d

orbitals and ligands to find total e-
count
 Varying Hapticity = Varying Electron Contribution
q Consider the cyclopentadienyl anion.

q How do we get the cyclopentadienyl anion? How to understand its structure?

Varying Hapticity = Varying Electron Contribution

2 electron donor

4 electron donor

6 electron donor
The allyl anion has similar attributes

A molecule can have the

Same ligand in different
hapticities.

4 electron donor 2 electron donor

Dewar-Chatt-Duncanson Model for Metal-Alkene Bonding

s-component: p-component:
C-C p → empty metal orbital occupied metal d → empty C-C p*

Note the similarity to CO ligands...

s-component: donation of C lone pair

p-component: backbonding into CO p*

3I3-7
 Metal-Carbonyl Complexes
q The carbonyl ligand forms a huge number of complexes with metal ions,
most commonly in low oxidation states, where it binds to the metal
through its C-donor, as in the complexes below, where all the metal ions
are zero-valent:

[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]

 Metal-Carbonyl Complexes: 18 Electron Rule
q Why in the above complexes Ni(0) has four C≡O groups attached to it,
Fe(0) five C≡O, and Cr(0) six C≡O?

q The eighteen electron rule allows us to explain this observation.

q The charge on the complexes is zero. Since CO is a neutral molecule, the

metals are in the zero oxidation state.

[Ni(CO)4] [Fe(CO)5] [Cr(CO)6]

Ni(0) = d10 Fe(0) = d8 Cr(0) = d6

4 x CO = 8 5 x CO =10 6 x CO = 12
18 e 18e 18e
 Example: A Simple Case

CH3 1) There is no overall charge on the complex

2) There is one anionic ligand (CH3-, methyl
R3P CO group)
Re 3) The Re metal atom must have a +1 charge to
compensate for the one negatively charged
PR3 ligand. So the Re is the in the +1 oxidation
CO state. We denote this three different ways:
Re(+1), Re(I), or ReI.

Re(+1) d6
2 PR3 4e-
2 CO 4e-
CH3- 2e-
CH2=CH2 2e-
Total: 18e-
Example: Simple Case with Somewhat Unusual Ligand

1) There is a +2 charge on the

CNCH3 2+ complex
H3CNC
CNCH3 2) The CNCH3 (methyl isocyanide)
H3CNC Mo ligand is neutral, but lets check the
Lewis Dot structure to make sure
H3CNC CNCH3 that is correct:
CNCH3
C NCH3
3) Because there is a +2 charge on the
complex and all neutral ligands
Mo(+2) d4 present, the Mo has a +2 charge &
oxidation state.
7 CNCH3 14e-
Total: 18e-
 Example: Somewhat Tricky!
Me 1) There is no overall charge on the complex
2) There is one anionic ligand (C3H5-, allyl)

Rh
3) The top ligand is NOT a MeCp-!
PPh3 It is a neutral diene that has a H
attached to the methyl-
substituted ring carbon. This is
a neutral 4e- donor.

4) Because the complex is neutral and there is one Rh(+1) d8

anionic ligand present, the Rh atom must have a +1 PR3 2e-
charge to compensate for the one negatively
charged ligand. So the Rh atom is in the +1 h4-C5H5Me 4e-
oxidation state. h3-C3H5- 4e-
Total: 18e-
 18 Electron Rule Explains Some Observations
q The compound Mn2(CO)10 exists but Mn(CO)5 does not.
q A species such as [Mn(CO)5] would have only 17 e.
q Each Mn contributes one electron to the valence shell of the other Mn,
giving the metal-metal bonded species [(CO)5Mn-Mn(CO)5]. To check on
the 18e rule, we look at one metal at a time:

Mn-Mn Mn(0) = d7
bond 5 C≡O = 10
Mn Mn-Mn = 1
Mn

18 e
[Mn2(CO)10]
 Bridging Carbonyl Ligands
bridging
carbonyls
q Carbonyls may form bridges between
two metals, where they donate one
electron to each metal in working out
Co Co the 18 electron rule.
q In [Co2(CO)8] , each Co has three
terminal CO’s, two bridging CO’s, and a
Co-Co bond:

Co-Co
bond Co(0) = d9
[Co2(CO)8] 3 CO’s = 6
2 bridge CO’s = 2
Co-Co bond = 1
18 e
 Terminolgy for Bridging Ligands
µx “mu-x” is the nomenclature used to indicate the presence of a
bridging ligand between two or more metal centers. The x refers to the
number of metal centers being bridged by the ligand. Usually most authors
omit x = 2 and just use µ to indicate that the ligand is bridging the simplest
case of two metals.

(CO)3Co(μ-CO)2Co(CO)3