Chem 310

Lecture Module 9

The 18-Electron Rule and

Organometallics
 Organometallic Chemistry
Organometallic compound: “one that possesses a metal-carbon bond”
Includes transition metal carbonyls,
carbonyls phosphines,
phosphines organoboron,
organoboron organosilicon
chemistry, but not cyano complexes. Best defined as chemistry of very
low-valent metal complexes (ie, close to zero).
Some compounds form useful catalysts for a few industrial reactions, tho
tho’ limited in scope

The 18-electron rule

•Originally
Originally based on concept from Lewis – ligands are L. bases, metals are L. acids.
Stability related to attaining noble gas configuration for metal. The sum of electrons on the
metal plus electrons donated to the metal was called the EAN.

•When
Wh EAN = 36 (Kr);
(K ) 54 (X
(Xe)) or 86 (R
(Rn)) th
the EAN rule
l iis said
id to
t be
b obeyed.
b d

•More easily stated: when the metal achieves an outershell configuration of ns2(n-1)d10np6,
there will be 18 electrons in the valence orbitals and a closed,, stable configuration.
g I.e.,, it
more simply refers to the total capacity of 9 orbitals (one set each of s, p and d)

•Rule of thumb is obeyed with high frequency for organometallic compounds, especially
those with carbonyl and nitrosyl (NO) ligands: Especially electron
electron-rich
rich metals (ie.,
(ie one in
low oxidation state), good π –acceptor ligands favor rule
 Reason for 18-Electron Rule – rooted in MO theory

For an octahedral complex, the most stable arrangement will be that in which all of
th b
the bonding
di orbitals
bit l ((a1g, t1u eg and
d t2g) are fully
f ll occupied;
i d and
d all
ll off the
th antibonding
tib di
orbitals are empty. .

E.g. [Co(NH3)6]3+: assign 18

electrons: 6 e- from Co3+, 6 x 2e-
= 12 e- from ligand.
Electrons fill 9 bonding orbitals,
antibonding MO
MO’ss are empty

Even though it isn’t an

organometallic complex, this
works
k partly
l because
b Δo is
i large.
l

Works also for Mo(CO)6: 12 e-

from 6 CO’s,, + 6 e- from Mo0
 Exceptions and Adherents to 18-Electron Rule – also rooted in MO theory

Complexes
p g Δo that makes occupation
will tend to 18 electron rule if theyy have large p of eg*
g
unfavorable, and for the same reason 2nd and 3rd row metals tend to adopt 18 ER.
May be fewer than 18 electrons if ligands do not provide stabilization of the t2g level by π –
bonding (remember: that lowers the energy of that orbital!)

MO diagram of d2 - ML6 with full π donor MO diagram of d2 - ML6 with empty π

ligand (e.g [CoF6]3-) p ligand
acceptor g ((CO,, PR3, SR2)

Examples are stable complexes [WCl6]2- (14 e-); [OsCl6]2- (16 e-); [PtF6]- (17 e-)
Ligands like CO and NO are high in spectrochemical series because they are excellent π –
2 orbitals Æ high Δo and increase in bonding energy. Most CO
acceptors, hence stabilize t2g
and NO compounds do obey rule
 Exceptions to 18-Electron Rule
If Δo is small (ie for 1st row TM) occupation of eg* does not come at such energy expense and
hence > 18 electron compounds often occur: Ni(en)32+ (20e-); [Zn(NH3)6]2+ (22 e-) etc.
TM metals on left hand side have few electrons to start with, and often can’t sterically
accommodate enough ligands to satisfy 18 ER – ie [Cr(NCS)6]3-
Tetrahedral exceptions to 18 ER common: the a1 and t2 levels are strongly bonding, housing 8
electrons (left). More e- go into e (non-bonding) and t2* (very weakly antibonding) but low
value of Δt means energy expenditure is low in any case.

Square planar d8 complexes a big exception – often obey “16

16 ER”
ER because of occupation of b1g
1 *
- th -
orbital – addition of 2e from 5 ligand converts complex to 5 CN 18e , marginally more stable
 The 16-Electron “Rule”

In the 0 oxidation states nickel is tetrahedral, palladium is

tetrahedral and square planar and platinum is square planar.

In the II oxidation state nickel has octahedral geometry,

geometry
while both palladium and platinum have square planar
geometries almost exclusively.

King,
g, B. R.,, Encyclopedia
y p off Inorganic
g Chemistry.
y Vol. 6,, pp 3023.
 An Example of the 16-Electron “Rule”

[Ir(CO)Cl(PPh3)2] (Vaska's compound)

Related to: [RhCl(PPh3)3] (Wilkinson's catalyst)

 Counting Electrons

Either use neutral atom or oxidation state approach

pp – neutral atom safer since oxidation state
assignment for metal isn’t required! Don’t mix them!
Determine how many electrons each ligand donates to metal and then add electrons from
metal, assuming the ox state is zero (unless the complex is charged), and that the (n+1)
electrons are simply added to the pot.
I.e, cyclopentadienyl (C5H5, or “Cp) donates 5e-; therefore ferrocene (Cp2Fe) is 10 + 8 = 18.
Note that Fe2+ is 3d6, but Feo is 3d6 4s2 = 8 electrons.
Carbonyl, phosphine, amine, dinitrogen, alkenes are all 2 electron donors; NO is 3, hydride
is 1; and metal-metal bonds count for two in the neutral atom method:
 Counting Electrons cont’d
Neutral and oxidation state method DO give the same answer
Neutral atom Oxidation state

Note CO can function as a terminal or bridging ligand but it doesn’t matter to the count
 Simple Carbonyl compounds:

•18 ER almost always obeyed: exception

is unstable 17e- V(CO)6, since if it
dimerized to give a metal-metal bond
(analogue to Mn2(CO)12), ie V2(CO)12 –>
each metal would have CN = 7.

Remember: IR spectroscopy can be used to characterize carbonyl complexes

b
because off connection
ti off symmetry,
t # carbonyl
b l groups and
d # stretches
t t h

•Only A2’’ and E’ are IR active (transform

as z and (x,y) respectively Î 2 modes

•Stretches for terminal CO groups are in region 1850 – 2200 cm-1

 Structures and Counting can be difficult for purely organic ligands:
•Ligands like allyl (C3H5), cyclopentadienyl (C5H5) and benzene can bind to a metal in more than
one way
way, the different modes are distinguished by # of carbon atoms participating in linkage
•Designated by symbol ηx symbol that refers to ligand “hapticity”; ie η5 –for typical Cp

•Hapticity can change to accommodate 18 ER! I.e, if

l was η5 on both
complex b th Cp,
C countt would
ld be 20 -
b 20e

•Lots of “sandwich metallocene compounds known: counting straightforward