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Folie 05 2021 Ligands 02 Tambahan

This document discusses various types of ligands used in organometallic chemistry, including those with extended pi systems like ethylene and allyl ligands. It explains how donation and back-donation in ligands like ethylene cause the carbon-carbon bond to lengthen. Cyclopropene and other cyclic pi systems are also examined using molecular orbital theory. Ferrocene is presented as an example of a metallocene complex, following the 18 electron rule with its two cyclopentadienyl ligands.

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80 views97 pages

Folie 05 2021 Ligands 02 Tambahan

This document discusses various types of ligands used in organometallic chemistry, including those with extended pi systems like ethylene and allyl ligands. It explains how donation and back-donation in ligands like ethylene cause the carbon-carbon bond to lengthen. Cyclopropene and other cyclic pi systems are also examined using molecular orbital theory. Ferrocene is presented as an example of a metallocene complex, following the 18 electron rule with its two cyclopentadienyl ligands.

Uploaded by

Agil Aprianto
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Ligands in Organometallic

Chemistry
(2)
More Ligand Types
I. Ligands with Extended phi Systems
A. Linear phi Systems

1) Ethylene (C2H4)

a) Single phi-bond composed of two overlapping phi-orbitals


b) One bonding and one antibonding phi molecular orbital
Free ethylene has a C–C distance of 133.7 pm,
whereas the corresponding distance in the anion of
Zeise’s salt is 137.5 pm.

(Why?)
137.5 pm

CH2=CH2 (133.7 pm)


The lengthening of this bond can be explained by
a combination of the two factors involved in the
synergistic σ donor–π acceptor nature of the
ligand:
(a) Donation to the metal in a σ fashion reduces
the electron density in a filled π bonding
orbital within the ligand, weakening the C–C
bond;
(b) The back-donation from the metal to the π*
orbital of the ligand also reduces the C–C
bond strength by populating this antibonding
orbital.

The net effect weakens and hence lengthens the


C–C bond in the ligand.
ALLYL
Allyl Radical (C3H5.)

CH2 CH 2

HC HC

CH 2 CH2
Allyl Cation (C3H5+)
There are three 2p orbitals to be considered, one from each of
the carbon atoms participating in the π system. This situation
can be viewed using the group orbital approach.

The group orbitals here are derived from the parallel 2p


orbitals on the terminal carbon atoms.

CH2 CH

HC HC

CH CH2
CH2 CH

HC HC

CH CH2
Allyl Complex Preparation
1-C3H5?
1,3-Butadiene
3) 1,3-Butadiene
3) Other Extended ∏ Systems
CH2 CH2

HC HC

CH CH

HC HC

CH2 CH2

H2 C

CH

HC

CH

HC

CH2
H3+ as a Model
Cyclopropene
B. Cyclic p Systems
1) Cyclopropene

a) Similar construction of orbitals as in linear systems


b) Degenerate orbitals have the same number of nodes
2) Polygon Method for finding cyclic phi system
MO’s

Draw molecule as a polygon with vertex down

One MO per vertex gives energy ordering and


degeneracy

Number of nodes increases as energy increases


Ferrocene
Atomic and Molecular Orbitals
Three conditions are essential for overlap to lead
to bonding.

First, the symmetry of the orbitals must be such


that regions with the same sign of  overlap.

Second, the energies of the atomic orbitals must be


similar. When the energies differ by a large
amount, the change in energy on formation of the
molecular orbitals is small and the net reduction in
energy of the electrons is too small for significant
bonding.

Third, the distance between the atoms must be


short enough to provide good overlap of the
orbitals, but not so short that repulsive forces of
other electrons or the nuclei interfere.
Ferrocene
Ferrocene Synthesis
FeCl2 + 2 NaC5H5 (5-C5H5)2Fe + 2 NaCl

Called metallocene or sandwich complex

18-electron complex
Fe2+ = d6 and 2 Cp x 6 e-Bonding Group Orbitals of
2 eclipsed Cp rings
the zero-node orbitals
the interaction between the dyz orbital
of Fe and its appropriate group orbital
Matching with metal d-orbitals:
dyz orbital
MO Description
6 strongly bonding MO’s hold electrons from Cp
ligands

8 antibonding orbitals are empty

5 mid-range energy orbitals holding metal d-


electrons

Reactivity
Follows 18-electron rule, but not inert

Ligand reactions on Cp ring are most common


reactions
Other Metallocenes
Other metallocenes have
similar structures but do not
necessarily obey the
18-electron rule. For
example, cobaltocene, (η5–
C5H5)2Co, and nickelocene,
(η5–C5H5)2Ni, are
structurally similar 19- and
20-electron species
the trend
radii of transition metal atoms and ions are decrease from
Sc through Ni.

Why????
Why????
Why?????
Aromaticity
Hϋckel Rule:
The cyclic-conjugated polyenes were most
stable if there were (4n + 2) phi electrons
involved, where n is an integer.
Using the criteria for aromaticity, determine if the following
molecules are aromatic:
Answers
1. Aromatic - only 1 of S's lone pairs counts as π electrons, so
there are 6 π electrons, n=1
2. Not aromatic - not fully conjugated, top C is sp3 hybridized
3. Not aromatic - top C is sp2 hybridized, but there are 4 π
electrons, n=1/2
4. Aromatic - N is using its 1 p orbital for the electrons in the
double bond, so its lone pair of electrons are not π electrons,
there are 6 π electrons, n=1
5. Aromatic - there are 6 π electrons, n=1
6. Not aromatic - all atoms are sp2 hybridized, but only 1 of S's
lone pairs counts as π electrons, so there 8 π electrons, n=1.5
7. Not aromatic - there are 4 π electrons, n=1/2
8. Aromatic - only 1 of N's lone pairs counts as π electrons, so
there are 6 π electrons, n=1
9. Not aromatic - not fully conjugated, top C is sp3 hybridized
10. Aromatic - O is using its 1 p orbital for the elections in the
double bond, so its lone pair of electrons are not π electrons,
there are 6 π electrons, n=1
Home Work
to be continued …

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