ADVANCED INORGANIC CHEMISTRY

(CHM4301)

ALKENES AND ALKYNES

GROUP MEMBERS:
1) MUHAMMAD KHAIRUL SYAFIQ BIN AZMI
2) NUR ‘AISYAH BINTI NORDIN
3) RAJA FARAH IZZATY BINTI RAJA IDZHAR
4) CYNTHIA MONA ANAK RENANG
5) ASILAH BINTI AHMAD

LECTURER: DR HASLINA BINTI AHMAD

 INTRODUCTION
ALKENES
Alkenes usually bond side-on to a metal
atom with both carbon atoms

This is called the Dewar-Chatt-Duncanson model

ƞ2-alkenes are considered to be two-electron
neutral ligand
• Electron-donor and –acceptor seems balanced in most ethene complexes of
the d-metals, but the degree of donation and backdonation can be altered by
substituents on the metal and on the alkene

• When the π backbonding from the metal atom increases, the strength of the
C=C bond decreases as the electron density is located in the C=C antibonding
orbital and the structure tends to be like singly bonded structure,
metallocyclopropane
ALKYNES
• Alkynes behave similar to alkenes, but being more electronegative, they tend to
encourage backdonation and bind more strongly.
• Alkynes have two π bonds and hence potentially be four-electron donors.
• When strongly electron-withdrawing groups are attached to an alkyne, the ligand
can become an excellent π acceptor and displace other ligands such as phosphines
BONDING MODE PROPERTIES
CONTAINING ALKENE & ALKYNE LIGAND
Alkene ligand
Based on Dewar-Chatt-Duncanson model

σ bond
- Electron density of C=C bond donated to an empty orbital on the metal
atom

π bond
- A filled d orbital donate electron density back to the empty π* orbital

Synergic bonding

Both σ-donation and π-acceptance weakens the CC bond

The greater the π back bonding from metal atoms, the greater the
reduction in the C=C bond order
Alkyne ligand
Synergic bonding

Alkynes tend to be more electronegative

- bind more tightly to a transition metal than
alkenes
- alkynes will often displace alkenes

Alkyne can act as either 2 or 4 electrons donor

Alkynes have two sets of mutually orthogonal pi bonds

-Can bind one of the sets, A & B as in alkene

-Another orthogonal set can also bind in a pi-

type fashion using an orthogonal metal d-
orbital (C)

-Back-donation to the antibonding orbital (D)

produced a delta-bond
- The degree of overlap is quite small

-Two orbitals meet side-to-side

rather than engaging in direct
overlap.

-Therefore, the contribution of D to

the bonding of alkynes is minimal at
best.

-Alkynes are usually non-linear when

coordinated to a transition metal
complex due to additional of pi-
donation
 Several resonance structures that depict the bonding of an alkyne :

I is the metallacyclopropene resonance form

III generally does not contribute to the bonding of alkyne complexes.

SPECIAL CHARACTERISTICS
OF ALKENE & ALKYNE
ALKENES
Ligand substitution
• Provide important method for synthesis the metal complexes

Insertion to give alkyls

• Wacker process: alkene oxidized by external nucleophilic reagents to give acetaldehyde;
synthesis of acetic acid

Transition metal-catalysed reaction

• Proceed via an alkene complex intermediate
• Alkene play parts as cheap raw materials – polymerization, hydrogenation.
ALKYNES
Has second occupied orbital perpendicular to the equatorial plane (diff from alkenes)
• Engage in transition-metal alkyne bonding

Stronger acceptor ligand than alkenes

• Bind more tightly to transition metals
• Can bridge two metals providing two electrons to each metal
SYNTHESIS OF COMPLEXES
CONTAINING ALKENE & ALKYNE LIGAND
 SYNTHESIS (ALKENE)
The alkene complexes are usually obtained by :-
1. Substitution in a low-valent metal:

Reversible binding of alkenes to Ag+ is used to separate different alkenes chromatographically

on silver-doped gas chromatography columns

Less hindered alkenes usually bind more strongly

ethylene > propylene > cis-2-butene > trans-2-butene
 SYNTHESIS (ALKENE)
2. Reduction of a higher valent metal in the presence of an alkene

The ligand acts as well as reducing agent (cod = cyclooctadiene)

The solvent ethanol acts as the reducing agent (a common occurrence in inorganic synthesis)
 SYNTHESIS (ALKENE)
3. From alkyls and related species

Protonate an allyl complex

Abstract H– from an alkyl complex

Fp = cyclopentadienyl iron dicarbonyl radical, FeCp(CO)2 –

Me = methyl, CH3
Ph = phenyl, C6H5 –
 SYNTHESIS (ALKYNE)
Transition metal alkyne complexes are often formed by:-
1. The displacement of labile ligands by the alkyne
Co2(CO)8 + R2C2 → Co2(C2R2)(CO)6 + 2 CO
Cobalt-alkyne complexes formed by reaction of the alkyne with dicobalt octacarbonyl

2. Reduction of metal halides

Cp2TiCl2 + C2R2 + Mg → Cp2Ti(C2R2) + MgCl2

Titanocene dichloride and in the presence of the alkyne

 SUMMARY
• Alkenes is any of the series of unsaturated hydrocarbons containing a double bond, C=C while
alkynes is an unsaturated hydrocarbon containing at least one carbon—carbon triple bond.
• The special characteristics of alkenes and alkynes also had been discovered and discussed.
• The binding mode properties of alkenes and alkynes ligand had been explained in detail based on
Dewar-Chatt-Duncanson model.
• The alkenes complexes could be synthesised by three methods:
1) Substitution in a low-valent metal.
2) Reduction of a higher valent metal in the presence of an alkene.
3) From alkyls and related species
• The alkynes complexes could be synthesised by two methods:
1) The displacement of labile ligands by the alkyne.
2) Reduction of metal halides.
 REFERENCES
• Crabtree, R. H. (2009). The organometallic chemistry of the transition metals. John
Wiley & Sons.
• Astruc, D. (2007). Organometallic chemistry and catalysis (Vol. 291). Berlin:
Springer.
• Trost, B. M., & Verhoeven, T. R. (1982). Comprehensive Organometallic Chemistry.
by G. Wilkinson, FGA Stone, and EW Abel, Pergamon Press, Oxford, 8, 799-938.
• T.L., Overton, J.P. Rouke, M.T. Weller and F.A. Armstrong (2014). Inorganic
Chemistry 6th edition, Oxford University Press.