Intro 15
18 Electron "Rule"
Organic compounds, of course, follow the 8 electron rule: there can
only be a maximum of 8 valence electrons around a carbon center.
The vast majority of stable diamagnetic organometallic compounds
have 16 or 18 valence electrons due to the presence of the five d
orbitals which can hold 10 more electrons relative to C, O, N, etc.
Electron counting is the process of determining the number of
valence electrons about a metal center in a given transition metal
complex.
To determine the electron count for a metal complex:
1) Determine the oxidation state of the transition metal center(s)
and the metal centers resulting d-electron count. To do this one
must:
a) note any overall charge on the metal complex
b) know the charges of the ligands bound to the metal
center (ionic ligand method)
c) know the number of electrons being donated to the metal
center from each ligand (ionic ligand method)
2) Add up the electron counts for the metal center and ligands
Complexes with 18 e- counts are referred to as saturated, because
there are no empty low-lying orbitals to which another incoming
ligand can coordinate. Complexes with counts lower than 18e- are
called unsaturated and can electronically bind additional ligands.
Intro 16
Exceptions to the 18e “Rule”
Group 8 Metals
d3 d4 d5 d6 d7 d8 d9 d 10 d 10s 1
21 22 23 24 25 26 27 28 29
Sc Ti V Cr Mn Fe Co Ni Cu
Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper
39 40 41 42 43 44 45 46 47
Y Zr Nb Mo Tc Ru Rh Pd Ag
Yttrium Zirconium Niobium Molybdenum Technetium Ruthenum Rhodium Palladium Silver
57 72 73 74 75 76 77 78 79
La Hf Ta W Re Os Ir Pt Au
Lanthanum Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold
Early Transition Middle Transition Late Transition
Metals Metals Metals
16e and sub-16e 18e 16e and sub-16e
configurations configurations configurations
are common are common are common
Coordination Coordination Coordination
geometries geometries geometries
higher than 6 of 6 are common of 5 or lower
d6
Intro 17
Ligands, Bonding Types, Charges, and Electron Donor Numbers
Ligand Name Bonding Type Formal Electrons
Charge Donated
Molecular Hydrogen: H2 H 0 2
M
H
Hydride: H M-H -1 2
Hydride: H H -1 2
M M
Halide: X M-X -1 2
Halide: X X -1 4
bridging (2 to
M M each M)
Halide: X X -1 6
3 bridging (2 to
M M each M)
M
Alkoxide, thiolate: OR , SR M- OR -1 2 or 4
Alkoxide, thiolate: OR , SR R -1 4
bridging (2 to
O
each M)
M M
Alkoxide, thiolate: OR , SR R -1 6
3 bridging O (2 to
each M)
M M
M
Peroxide: O22 O -2 4
2
M
O
Peroxide: O22 O O M -2 4
O
2 bridging O (2 to
M M M
each M)
Intro 18
Oxide, sulfide: O2 , S2 M O -2 4
6
M O
Oxide, sulfide: O2 , S2 O -2 4
bridging (2 to
M M each M)
Oxide, sulfide: O2 , S2 O -2 6
3 bridging (2 to
M M each M)
M
Amine, phosphine, arsine: M-NR3 0 2
NR3, PR3, AsR3 M-PR3
Amide, phosphide:
M N R M P R
-1 2
NR2 , PR2
R R
R 4
M N R
Amide, phosphide: RR -1 4
NR2 , PR2 bridging: (2 to
P
each M)
M M
Imido: NR2 R -2 4 (bent)
M N
6 (linear)
M N R
Imido: NR2 R R -2 4 or 6
bridging (2 or 3 to
N N
each M)
M M M M
Imido: NR2 R -2 6
3 bridging N (2 to
each M)
M M
M
Nitride, phosphide: M N: -3 6
N3 , P3
Intro 19
Nitride, phosphide: N N -3 4 or 6
N3 , P3 , bridging (2 or 3 to
M M M M each M)
Nitride, phosphide: N -3 6
N3 , P3 , 3 bridging
M M
M
Nitrosyl: N O+ M N O +1 2
linear form
Nitrosyl: N O M N -1 2
bent form
O
Nitrosyl: N O+ O +1 1 to each
bridging metal
N
M M
Nitrosyl: N O+ O +1 1 to each
3 bridging metal
N
M M
M
Carbonyl: C O M C O 0 2
Carbonyl: C O O 0 2 to each
, 2 mode C metal
M M
Carbonyl: C O O 0 1 to each
bridging metal
C
M M
Carbonyl: C O O 0 1 to each
3 bridging metal
C
M M
M
Intro 20
Isocyanide: C N-R M C N R 0 2
Isocyanide: C N-R R 0 1 to each
bridging N metal
C
M M
Alkene: R2C=CR2 R R 0 2
2 bonding mode R C C R
M
Alkyne: RC CR R C C R 0 2 or 4
2 bonding mode
M
Alkyne: RC CR R R 0 2 to each
bridging C C
metal
M M
Dienes: R2C=CH-CH=CR2 0 4
4 bonding mode
M
Dienes: R2C=CH-CH=CR2 0 2 to each
bridging metal
M M
Benzene: C6H6 0 6
6 bonding mode
M
Ketones, aldehydes: R 0 2
2 bonding mode R C O
M
Alkyl: CH3 , CH2R M CR 3 -1 2
1 bonding mode
Intro 21
Alkyl: CH3 , CH2R R R R -1 2
C (1 to
each M)
M M assuming no
agostic M-H
interactions
Aryl: C6H5 -1 2
1 terminal M
Alkenyl (vinyl), alkynyl: M R -1 2
CH=CH2 , C CH
1 terminal M
Alkenyl (vinyl): -1 4
CH=CH2 M
2 terminal
Alkenyl (vinyl), alkynyl: M -1 4
CH=CH2 , C CH (2 to
, 2 terminal M R each M)
M M
Cyclopropenyl: C3H3 +1 2
3 terminal
M
Allyl: C3H5 -1 4
3 terminal
M
Allyl: C3H5 M -1 2
1 terminal
Pentadienyl: C5H7 -1 6
5 terminal
M
Pentadienyl: C5H7 -1 4
3 terminal
M
Intro 22
Pentadienyl: C5H7 M -1 2
1 terminal
Cyclopentadienyl: C5H5 -1 6
5
M
M
Cyclopentadienyl: C5H5 -1 4
3
M
Carbene: =CYR R 0 2
where Y is a substituent M C
capable of interaction with
the carbene carbon atom Y
Alkylidene: =CR22 R -2 4
where no substituents capable M C
of bonding to the carbene
carbon atom are present R
Carbene: =CYR or =CR22 Y R -2 2 to each
bridging metal
C
M M
Carbyne or Alkyidyne: M C R -3 6
CR3
Carbyne or Alkyidyne: R -3 2 to each
CR3 3 bridging metal
C
M M
M
Intro 23
How do I Figure Out Ligand Charges & Donor #’s)??
(without memorizing that !#&!@%$* entire list)
First, you should know the charges and donor # for the common
ligands (this will significantly speed up your counting):
Cationic 2e- donor: NO (nitrosyl), cyclopropenium, C3H3+
Neutral 2e- donors: PR3 (phosphines), CO (carbonyl), R2C=CR2
(alkenes), RC CR (alkynes, can also donate
4 e-), N CR (nitriles)
Anionic 2e- donors: Cl (chloride), Br (bromide), I (iodide), CH3
(methyl), CR3 (alkyl), Ph (phenyl), H
(hydride)
The following can also donate 4 e- if needed, but
initially count them as 2e- donors (unless they
are acting as bridging ligands): OR (alkoxide),
SR (thiolate), NR2 (inorganic amide), PR2
(phosphide)
Anionic 4e- donors: C3H5 (allyl), O2 (oxide), S2 (sulfide), NR2
(imide), CR22 (alkylidene)
and from the previous list: OR (alkoxide), SR
(thiolate), NR2 (inorganic amide), PR2
Anionic 6e- donors: Cp (cyclopentadienyl), O2 (oxide)
Please note that we are using the Ionic Method of electron-counting.
95% of inorganic/organometallic chemists use the ionic method.
The ionic method assigns formal charges to the metal and ligands in
order to keep the ligands with an even # of electrons and (usually) a
filled valence shell. There is also the neutral method that considers
everything to be neutral. Synthetically, the ionic method generally
makes more sense and the one that we will use in this course.
Intro 24
Simple Example:
CH3
R 3P CO
Re
PR3
CO
1) There is no overall charge on the complex
2) There is one anionic ligand (CH3 , methyl group)
3) Since there is no overall charge on the complex (it is neutral),
and since we have one anionic ligand present, the Re metal atom
must have a +1 charge to compensate for the one negatively
charged ligand. The +1 charge on the metal is also its oxidation
state. So the Re is the in the +1 oxidation state. We denote this
in two different ways: Re(+1), Re(I), or ReI. I prefer the Re(+1)
nomenclature because it is clearer. Most chemistry journals,
however, prefer the Roman numeral notation in parenthesis
after the element.
Now we can do our electron counting:
Re(+1) d6
2 PR3 4e-
2 CO 4e-
CH3 2e-
CH2=CH2 2e-
Total: 18e-
Intro 25
Next Electron-Counting Example:
CNCH3 2+
H3CNC
CNCH3
H3CNC Mo
H3CNC CNCH3
CNCH3
1) There is a +2 charge on the complex
2) The CNCH3 (methyl isocyanide) ligand is neutral, but lets check
the Lewis Dot structure to make sure that is correct:
C NCH3
Nitrogen is normally trivalent, that is, it wants to have 3
chemical bonds to it. When it has 4 bonds, one more than usual,
the nitrogen atom is assigned a formal positive charge. Carbon,
on the other hand, is tetravalent and almost always wants 4
bonds. In isocyanides, however, we only have 3 bonds to the C.
To keep an even number of electrons around the C we add an
extra electron and the carbon gains a formal negative charge.
3) Since there is a +2 charge on the complex, and since we have all
neutral ligands present, the Mo has a +2 charge & oxidation
state.
Now we can do our electron counting:
Mo(+2) d4
7 CNCH3 14e-
Total: 18e-
Intro 26
More Complicated Ligand Analysis:
H2C M
R2P
H2C M
How do we figure out the charge and electron donor ability of this
weird ligand??
1) Remove the metal atoms and examine the ligand by itself:
H
H
H2C M C
R2P R2P
H2C M H
C
H
Phosphorus is trivalent and since it has four bonds to it, there is a
formal positive charge assigned to the atom. Each carbon is
currently neutral and has an odd electron.
Intro 27
2) We always want the ligand in the ionic method of ligand electron
counting to have an even # of electrons. IF the ligand atom has an
odd # of electrons, add enough electrons to get to an even # (and
usually a filled valence shell). This usually means adding one
electron. In this specific case we have two carbon atoms each which
needs an additional electron to give a lone pair that can donate to
the metal center:
H H
H H
C C
+2e-
R2P R2P
C H
C
H
H H
Adding two electrons to this ligand generates two anionic carbon
donor centers. But remember that we have a positive charge on the
phosphorus atom, which although not involved in bonding to the
metal, is part of the overall charge of the ligand. So two negative
charges and one positive charge (on the phosphorus) yields a net
negative charge on this ligand. Each carbon can donate 2 e- to each
metal center.
This strange ligand is called a phosphorus di-ylide and is a strongly
donating ligand for bridging two metal centers.
Intro 28
More Complicated Metal Compound Analysis:
Me
Rh
PPh3
1) There is no overall charge on the complex
2) There is one anionic ligand ( 3-C3H5 , allyl).
H H
H H +e- H H
H H H H H
H H
H H
H H
H H +e- H H
H H H H
Rule of Thumb: -based carbon ligands that have odd number
attachments to the metal center are usually anionic (except for CO
and CNR [isocyanide] ligands) and donate one more electron than
the number of carbons bonded to the metal center. So our 3-
C3H5 , allyl ligand is anionic and donates 4e- to the metal center.
Intro 29
The C5H5Me ligand is NOT a simple anionic cyclopentadienyl
ligand. It is a neutral ligand with two alkenes that each act as
neutral 2e- donors to the metal:
Me
H
If you work out the Lewis Dot structure for this ligand you get an
even # of electrons so there is no need to add an electron to get an
anionic ligand. Note that it is EASY to forget that there is a H on
the Cp carbon that has the methyl group attached if you are not
thinking about organic line notation.
3) Since there is no overall charge on the complex (it is neutral),
and since we have one anionic ligand present, the Rh atom must
have a +1 charge to compensate for the one negatively charged
ligand. So the Rh atom is the in the +1 oxidation state.
Now we can electron-count:
Rh(+1) d8
PR3 2e-
4-C H Me 4e-
5 5
3-C H 4e-
3 5
Total: 18e-
Intro 30
Problems in Electron Counting
Re(+1) d6
6
-benzene 6
Re 5 Mo
-Cp 6
(MeO)3P
18 (Me O) 3P
PMe 3
Cl Ta Ni
Cl
PMe 3
O O
N N
Me 2 N NMe 2
Cr
Mo
N
NMe 2 N O
Me 2N O
PMe 3
Br CO
Ti OC W CO
Br
OC
PMe 3
Intro 31
Pd Ni
N
O
Mo Mn
C Ph3P
C O
N O C
O O OMe
Co
Sc OMe Me 3 P PMe 3
Me 3 P
R
PMe 3
C
CO H Ph2
Cr W CH 2t-Bu
OC C P
OC OR P CH
PMe 3 Ph2
Intro 32
R
C C R O O
O O O C C O
C C C C
Fe ? Fe Fe ? Fe
OC CO
C
C O C
O O
O O
OC C C
CO
O
C
Os
OC
O
C
O
C Co ? Co
CO
Os ? Os C
H H O
C C
O O
Br
Au Au
P ? P P ? P
Au Au
CH 3
OR
RO OR
O
Mo Rh
O O
? O R
Mo
R ? R
RO OR R O Rh
O
O
OR O
