The 18-electron rule and its exceptions (1) Octahedral complexes can be split into 3 categories: category A B C number

r of electrons 18 12-18 12-22 description 18-electron rule obeyed 18-electrons not exceeded 18-electron rule disobeyed

A. Those that obey the 18 electron rule Complexes with strong -acceptor ligands (e.g. [V(CO)6]-, [Cr(CO)6], [W(CO)6], [Mn(CO)6]+) - t2g strongly bonding filled - eg strongly antibonding (due to synergic bonding) empty
t 1u*

4p (t1u )

a1g*

strongly anti-bonding (empty)

4s (a1g )

t2g* e g*

* orbitals of CO (t2g)

3d (e g + t2g)

large O

strongly bonding (filled)

t2g (a1g + t1u + e g) eg

Cr

6 CO t1u a1g

- Complexes of strong -acceptor ligands tend to obey the 18-electron rule irrespective of their coordination number (e.g. [Fe(CO)5], [Fe(CO)4]2-, [Ni(PPh3)4]). - Note: d8 and d10 configurations are exceptions to this rule (see later).

B. Octahedral complexes with 12-18 electrons 2nd and 3 rd row TM complexes (high in the spectrochemical series of metal ions) with -donor or -donor ligands (low to medium in the spectrochemical series) - t2g non-bonding or weakly anti-bonding (because the ligands are either -donors or -donors) t2g can contain from 0 to 6 electrons - eg fairly strongly antibonding (because 2nd/3rd row TMs bond more effectively to the ligands)eg empty e.g. [ZrF6]2- (Zr4+, d0, 12 e), [PtF 6]2- (Pt4+, d6, 18 e), [OsCl6]2- (Os4+, d4, 16 e), [WMe6] (W6+, d0, 12 e), [Zr(OH2)6]3+ (Zr3+, d1, 13 e)

Octahedral, -donor ligands (e.g. [WMe6])

t1u*

4p (t1u)

a1g*

4s (a1g ) eg *

eg* is reasonably antibonding for a 2nd or 3rd row transition metal moderate o for 2nd or 3rd row transition metal O

3d (e g + t2g)

t 2g non-bonding t2g

(a 1g + t1u + eg) eg

t 1u a 1g

6 Me

C. Octahedral complexes with 12-22 electrons 1st row TM complexes (low in the spectrochemical series of metal ions) with -donor or -donor ligands (low to medium in the spectrochemical series) = 1st row transition metal coordination complexes {e.g. [TiF 6]2- (Ti4+, d0, 12 e), [Co(NH3)6]3+ (Co3+, d6, 18 e), [Cu(OH2)6]2+ (Cu2+, d9, 21 e)} - t2g non-bonding or weakly anti-bonding (because the ligands are either -donors or -donors) t2g can contain from 0 to 6 electrons - eg only weakly antibonding (because 1st row TMs dont bond as effectively to the ligands) eg can contain from 0 to 4 electrons

Octahedral, -donor ligands (e.g. [Cu(OH2)6]2+)

t1u*

4p (t1u )

a1g * eg* is only moderately antibonding for a 1st row transition metal eg* small o t2g only weakly anti-bonding

4s (a1g)

3d (eg + t 2g )

t2g *

orbitals (t2g )

t2g (a1g + t1u + eg) eg

Cu

t1u a1g

6 OH2

Tetrahedral Complexes Tetrahedral complexes cannot exceed 18 electrons because there are no low lying MOs that can be filled to obtain tetrahedral complexes with >18 electrons. In addition, a transition metal complex with the maximum of 10 d-electrons, will receive 8 electrons from the ligands a total of 18 electrons. t is small (~4/9 o), so there is no particular preference for the e or t2 orbitals to be filled (can have 8-18 electrons) similar to class C octahedral complexes.

Tetrahedral - e.g. [Ni(PPh3)4] (Ni0, d10, 18-electron complex)

t2*

4p (t1u)

a1*

4s (a1g) t2*

t ~ 4/9 o

3d (eg + t2g) e

(a1g + t 1u + eg) a1

Ni

4 PPh3

t2

(2) Square Planar complexes (d8, 16 electrons) d8-metals with 4 ligands, so 16-electron complexes common with metals and ligands high in the spectrochemical series - Rh , Ir , Pd , Pt , Au almost always square planar All are very common oxidation states except AuIII which is quite oxidising.
I I II II III

d x2-y2 large E d xy d z2

d xz, d yz

- NiII can be square planar, but only with strong -acceptor ligands (because 1st row TMs are lower in the spectrochemical series than 2nd or 3rd row TMs). - CoI is almost never square planar because it is a first row transition metal in a low oxidation state (very low in the spectrochemical series for metals). - d8 CuIII and AgIII complexes are extremely rare and highly oxidising. - d8 Ru0 and Os 0 are not square planar (2nd or 3rd row TMs but low in the spectrochemical series of metal ions because their oxidation state is zero). - d9 complexes are sometimes square planar (e.g. [CuII(py)4]2+) this may be considered an extreme form of Jahn-Teller distortion.

EXAMPLES:
Ph3P Ph3P RhI PPh3 Cl

Ph 2 P P Ph 2

PtII

Cl Cl

NC NC

NiII

CN CN

2-

Ph3P OC

Ir I

CO Cl

Cl Cl

PtII

Cl Cl

2-

Cl Cl Cl Cl NiII

2-

CO OC Fe CO CO CO OC

CO Mn CO CO CO

CN NC OC CN Co I

2-

(3) Linear complexes (d10, 14 electrons) d -metals with 2 ligands, so 14-electron complexes
10

p small E s small E

Common for AgI, AuI and HgII Less common for Cu , Zn and Cd
I II II

Explanation: For d 10 complexes, there is a relatively small energy difference between the d, s and p orbitals (e.g. 5d, 6s and 6p for AuI). This permits extensive hybridization between the dz2, s and p z orbitals as shown below:

Step 1

Step 2

filled d z2

empty s

filled sd-hybrid

empty sd-hybrid

empty sd-hybrid

empty p

empty

empty

Overall:
filled dz2

empty s

empty p

filled sd-hybrid

empty

empty

orbitals suitable for forming a pair of linear covalent bonds

 More common for group 11 (Cu, Ag, Au) than group 12 (Zn, Cd, Hg) because the energy difference between the d, s and p-orbitals is smaller for group 11. More common for the heavier elements (AgI, AuI, HgII). Examples: [Ag(CN)2]-, [Ag(NH3)2]+, [Cu(NH3 )2]+, [(R3P)AuCl], [HgMe2 ], [CdMe2], [ZnMe2 ] However, there are also lots of tetrahedral complexes of AgI, AuI, CuI, ZnII, Cd II and HgII (e.g. 14 e- linear [(R3P)AuCl] + 2 PR3 18 e- tetrahedral [(R3P)3AuCl]).

Distribution of coordination numbers for crystallographically characterized CuI, AgI, and AuI compounds as found in the Cambridge Structural Database (2003). S. Alvarez et al. , JACS, 2004 , 1465-1477

(4) Steric Effects and Early Transition Metal Compounds Steric effects can produce low-coordinate (not many ligands) complexes which often have <18 electrons.
Me3Si Si Me3Si N N Me3Si ScIII SiMe3 N SiMe 3 SiMe3 Cl MII Si Me3Si M = Sc3+ d0 6 electrons M = Cr2+ M = Mn 2+ M = Fe2+ d4 d5 d6 SiMe3 SiMe 3 10 electrons 11 electrons 12 electrons SiMe 3 SiMe3

SiMe3

For early transition metals (e.g. with d0 metals) it is often not possible to fit the number of ligands necessary to reach 18 electrons around the metal.

Me Me Me WVI Me W6+ d0 12 electrons Me Me OC OC

CO V0 CO V0 d5 17 electrons Sc3+ d 0 16 electrons CO CO Sc III Cl PMe3

(5) Strong oxidants or reductants Many 18 electron complexes can be reduced or oxidised to give 17 or 19 electron complexes. Such compounds are often good oxidising or reducing agents (i.e. they want to get back to being 18-electron compounds).

- eFeII + eFeIII

FeII,

Ferrocene d6, 18 electrons

Ferrocenium cation FeIII, d5, 17 electrons Dark blue, paramagnetic Oxidant

Orange, diamagnetic Perfectly Happy !

+ eCoIII - eCoII

Cobaltocenium cation CoIII , d6, 18 electrons Yellow, diamagnetic Perfectly Happy !

Cobaltocene Co , d7, 19 electrons Dark purple, paramagnetic Strong Reductant

II