Theoretical models:

MO theory
Electron counting and Organometallic
chemistry

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 Ligand binding

Ligand: electron lone pair, nucleophilic

Metal: low-lying empty d-orbitals, electrophilic

Ligand: electron pair donor, Lewis base, σ base

Metal: electron pair acceptor, Lewis acid, σ acid

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 Basic MO theory

Metal ion A with one electron, and orbitals σ1 and

σ2; Ligand B with one orbital σL and two electrons.
1: A and B independent
2: MO theory.

σ1, σ2;
σL
A B
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 MO Theory for Acid—Base

anti-bonding

non-bonding
A B
bonding

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 Constructing an MO-scheme *

1. Choose metal orbitals (s,p,d) and define

Cartesian axes
2. Determine ligand orbitals for binding
3. Determine symmetry and interactions
• Keep same number of orbitals!
4. Estimate relative energies of filled and empty
orbitals
5. Determine which orbitals are bonding, anti-
bonding and non-bonding
6. Fill orbitals with available electrons
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 Metal complexes and symmetry for MO

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 Ligand binding ***
9 orbitals
 18 electrons
4p

4s
∆
3d

metal ligand
lone pairs
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 18 electron rule **
[Co(NH3)6]3+
4p

4s

3d

metal ligand
lone pairs
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 18 electron rule?
[Ni(NH3)6]2+
4p
20 electrons!
4s

3d

metal ligand
lone pairs
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 18 electron rule ***

• organometallic complexes have relatively covalent bonds

 the 18-electron rule quite often obeyed: the transition
metal aspires to have a total of 18 valence electrons
• d10s2p6 = configuration of next noble gas

• Not a very “hard” rule

• Especially NOT for coordination compounds

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 Electron counting: group numbers
***

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 Examples: carbonyl complexes ***

• Cr(CO)6 chromium(0) d6
– electrons: 6 + (6 x 2) = 18
• Fe(CO)5 iron(0) d8
– electrons: 8 + (5x2) = 18
• Ni(CO)4 nickel(0) d10
– electrons: 10 + (4x2) = 18

But how about metals with an odd number of

electrons?
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 Examples: carbonyl complexes ***
• manganese? Mn2(CO)10, Mn d7
– Mn(CO)5: 7 + (5x2) = 17e: radical! formation Mn-Mn bond: (CO)5Mn—
Mn(CO)5; compare: Cl• + Cl• → Cl2
– Mn(CO)6+ also exists, explain!
• cobalt? Co2(CO)8, Co d9
– Co(CO)4: 9 + (4x2) = 17 e  (CO)4Co—Co(CO)4
• vanadium? V(CO)6, V d5
– V(CO)6: 5 + (6x2) = 17e, this is a radical!
V-V bond not possible (crowded)
– [V(CO)6]– is stable
• message: 17e complex comparable with s2p5 halogen
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 Some ligands: counting ***

• CO, neutral, 2 e donor;

• PR3, neutral, 2 e donor
• CN, anionic: CN–, 2 e donor
• olefins, neutral, 2 e donor
• anionic 2 el donors are: F–, Cl–, Br–, I–, H–, CH3–, C6H5–
• RO–, RS– R2N– and R2P– are 2 e donors, but can bridge
between metals: then 4 or 6 e donors
• Potential 4 e donors: O2–, S2–
• 6 e donors: C5H5–, C6H6 (neutral)

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 Example counting CH3
R3P CO
Re
• no net charge PR3
• only CH3 is anionic CO
•  Re = Re+
• count: Re+ = d6,
2xPR3 = 4 e,
2xCO = 4 e,
CH3– = 2 e,
C2H4 = 2 e,
•  total = 18
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 Question
• What is the charge of the complex Mo(CNCH3)7?
• Answer:
– ligand is isocyanide: :C=N—CH3, 2e donor, neutral,  7x2 = 14e
– Mo is in group 6,  6 e
– To get a total of 18 e  Mo has to be Mo2+
– Charge of the complex must be 2+
– 7 coordination possible, Mo is large

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 Finding the charge… ***

Nomenclature anionic ligands:

• Ending with –o: chlorido, hydrido, bromido, acetato
 2 e donor, 1–
• Ending with –yl: methyl, phenyl, -dienyl, propyl,
 2 e donor, 1–
• Exception: carbonyl!

Rule of thumb: if you can find a compound as such in

a cupboard or cylinder, then it is neutral.
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 Nomenclature organic fragments

#e ending examples
2 -yl η1-alkyl, η1-alkenyl, η1-allyl
2 -ene; -yne η2-ethene, η2-ethyne
4 -enyl η3-alkenyl, η3-propenyl (η3-allyl)
4 -diene η4-butadiene, η4-cyclohexadiene
6 -dienyl η5-cyclopentadienyl, η5-heptadienyl
6 -triene η6-cycloheptatriene
8 -trienyl η7-cycloheptatrienyl

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 Counting: (C5H5)Fe(CO)2Cl
• dicarbonylchloridocyclopentadienyliron
– Cl–, Cp–
– FeII  = 6 e
– C5H5– = 6 e
– (CO) 2x2 = 4 e [Cu(NH3)3Br2]
– Cl- = 2 e
• 2x Br–  CuII
• total: 18 e • CuII =9e
• NH3 3x2 =6e
• Br– 2x2 =4e
• total: 19 e
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 Pi-donor and acceptor ligands ***

• Metal dxy, dyz, dzx  t2g set

– filled with metal electrons
– non-bonding for sigma-symmetry electron pairs of ligands
• Metal dxy, dyz, dzx  also called dπ
– correct symmetry for interaction with π-symmetry orbitals

Two possible interactions:

• with filled π-symmetry orbitals: π bonding
• with empty π* orbitals: π back bonding
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 MO diagram of CO *
pσ*
2π 2π C O LUMO
pπ*
p sσ* 5σ 5σ
s C O HOMO
pπ p 1π
1π
C O
pσ 4σ s 4σ
sσ 3σ C O
C C O O
HOMO of CO has carbon 2s and 2p LUMO has mainly carbon 2px and
character 2py character.
This orbital is donating into d-orbital Carbon is most important
MST - ANO
π-acceptor site. 21
 Metal—CO binding ***

σ-Bonding and π-back bonding

CO lone pair donates into d(x2-y2)

Electrons in d(xy) or d(xz) donate into π* CO

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 π-Back bonding ***

Ligand: low-lying empty π*-orbitals,

electron acceptor, π-acceptor, π-acid
Metal: filled dπ orbital
electron donor, π-donor, π-base

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 π-Back bonding ***

metal dσ (eg)

metal dπ (t2g)

Increase of ligand field stabilization

 18e preference

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 π-donor ligands ***

• Lone pairs on electronegative ligands: F–, Cl–, RO–

• Repulsion of M electrons: destabilization
• Strong bonds with electron-deficient metals (Ti4+, d0)

2e 4e 6e donating
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 π-donor ligands ***

metal dσ

metal dπ

Destabilization, smaller ligand field splitting

 18e rule not important
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π Donor & Acceptor Ligands
metal ligands π-acceptor ligands increase ∆O

metal ligands

π-donor ligands decrease ∆O

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 Spectrochemical series ***

Weak and strong-field ligands:

from π-donors
I– < Br– < S2– < SCN– < Cl– < NO2– < N3– < F– <
OH– < C2O42– < H2O < NCS– < CH3CN < py < NH3
< en < bpy < phen < NO2– < Pφ3 < CN– < CO
to π-acceptors

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 CO binding **

M—C bond stronger M—C bond stronger

C —O bond stronger C —O bond weaker

Question. In IR the CO vibration usually shifts

to lower energy upon coordination: Why?

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 CO binding **

IR free CO: 2143 cm–1

OCBH3: 2164 cm–1 σ donor only
Ni(CO)4 2060
[Co(CO)4]– 1890 Back bonding increases
[Fe(CO)4]2– 1790
Oxidation M  Mn+: Contraction d orbitals
Inefficient back bonding
Loss of CO ligands
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 Types of Bonding ***

Lone pair

π electrons

σ electrons

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 σ and π bonding electrons ***

σ Bonding electrons
H—H C—H Si—H B—H H—Cl M—H
π Bonding electrons

C=C (alkene); C≡C (alkyne); C=O (ketone)

Binding strength:
lone pair > π bonding e > σ bonding e
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 σ Bond electron donor ***
. H
M
H . H
M :
H
M L π back bonding
M L σ bonding into σ* orbital !

Weakens H—H bond Weakens H—H bond

H—H distance in H2 = 0.74 Å

in complexes: 0.8 – 1.5 Å
:H-

Extreme: oxidative addition M

:H- 33
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 Dihydrogen complexes
1984: [W(η2-H2)(CO)3(PCy3)2]

H—H 0.82 Å (neutron diffr); free H2 0.72 Å

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 “stretched” dihydrogen complex

Intermediate in
oxidative
addition?

[Os(en)2(H2)(OAc)](PF6)

MST - ANO H—H 1.25 Å (Xray) 35

 [Pt(Cl)(H)(P(pMe-Ph)3)2]

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 Metal carbonyl hydrides **

pKa compare to
HCo(CO)4 1 HCl
HCo(CO)3(PPh3) 7 H2S
HMn(CO)5 7.1
H2Fe(CO)4 4.4 HOAc
[HFe(CO)4]– 14 H2O
HWCp(CO)3 9.0 H3BO3

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 Binding of ethene ***

ML
σ donation
ML
π Back donation
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 Limitations of the 18e rule ***

MeTiCl3 8e Pt(PCy3)2 14e CoCp2 19e

Me2NbCl3 10e WMe6 12e NiCp2 20e
Steric restrictions and reactivity

[M(H2O)6]2+ V 15e; Cr 16e; Mn 17e; Fe 18e; Co 19e; Ni 20e

Weak field ligands: σ donor and π donor
Lowering of ligand field splitting ∆
t2g and eg comparable energy
Relatively easy to: add electrons to eg > 18e
MST - ANO
remove electrons from t2g < 18e 39
 “16-electron rule” ***

Group 8 – 11: d8 metals

8 Fe(0), Ru(0), Os(0) prefer 18e
9 Co(I), Rh(I), Ir(I) both 16e / 18e
10 Ni(II), Pd(II), Pt(II) prefer 16e
11 Cu(III), Au(III) rare

Square planar geometry, dx2–y2 high energy, dz2 filled

Difficult to add another ligand
16e  18e rehybridisation to TBP or Square pyramid

Examples: RhCl(L)3; IrCl(CO)L2; PdCl2L2; [PtCl4]2–; [AuMe4]–

MST - ANO 40
 Summary

• MO diagram
• Sigma/Pi donation; pi back bonding
• Sigma electrons, pi electrons, lone pair
• 18 electron rule; electron counting;
• 16 electron rule
• Alkene/alkyne binding, dihydrogen binding
• Organometallic compounds

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 Assignment
• Study § 20.1(c)
–p 520 - 521
• Study § 20.8 – 20.9
–p 544 – 547

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