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Unit 4: Ord and CD: M.Sc. Semester II

1) Complexes with three rings formed by chelating ligands, such as [Co(en)3]3+, can be treated like three-bladed propellers and their handedness determined by viewing down the three-fold axis. 2) Optical rotation dispersion (ORD) and circular dichroism (CD) measurements of d-d transitions are useful for assigning absolute configurations of metal complexes. ORD curves indicate the sign of Cotton effects which can determine handedness. 3) Complexes that show the same sign of Cotton effects in their corresponding electronic transitions have the same absolute configuration. The configurations of several cobalt complexes have been determined using ORD and CD data.

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501 views

Unit 4: Ord and CD: M.Sc. Semester II

1) Complexes with three rings formed by chelating ligands, such as [Co(en)3]3+, can be treated like three-bladed propellers and their handedness determined by viewing down the three-fold axis. 2) Optical rotation dispersion (ORD) and circular dichroism (CD) measurements of d-d transitions are useful for assigning absolute configurations of metal complexes. ORD curves indicate the sign of Cotton effects which can determine handedness. 3) Complexes that show the same sign of Cotton effects in their corresponding electronic transitions have the same absolute configuration. The configurations of several cobalt complexes have been determined using ORD and CD data.

Uploaded by

Ayushi Kapoor
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UNIT 4: ORD and CD

Part IV: Application of ORD & CD in determining


absolute configuration of metal complexes
M.Sc. Semester II

Dr Anil Kumar Singh


Department of Chemistry
Mahatma Gandhi Central University
Absolute configuration of Complexes
• It is not possible to assign the absolute configuration simply on the basis of the
direction of rotation of the plane of polarized light.

Assignment of configuration

• Complexes with three rings formed via chelating ligands, such as [Co(en)3]3+, can
be treated like three-bladed propellers by looking at the molecule down a
threefold axis.

Picture Credit: Inorganic Chemistry, 5th Edition, Miessler & Tarr, Chapter 9.
Absolute configuration of Complexes
To decide the handedness one should view, for example, tris(chelate) down the three fold
rotational axis. If the helix thus viewed is right-handed, the isomer is the Δ-isomer, and its
mirror image is the Λ-isomer.

Λ or D isomer Δ or L isomer
Absolute configuration of Complexes

• ORD and CD are two phenomena associated with d-d transitions that that are
useful in assigning absolute configurations.
• A general rule is- If, in analogous compounds, corresponding electronic transitions
shown Cotton effects of the same sign, the compounds have the same optical
configuration.
• ORD involves measuring the variation of optical rotation with wavelength. There is
an abrupt reversal of rotation in the vicinity of absorption band (See Cotton effect,
part III).
• If the complex is initially laevorotatory, the ORD curve falls to a minimum, rises
rapidly to a maximum, and then slowly falls. If the complex was initially
dextrorotatory, the effect is reversed with ORD curve rising first to a maximum, then
falling. These represents positive and negative Cotton effects, respectively.
λmax
(A)

...…………………………………………………………….
+ CD curve ORD curve +
(A) Positive cotton effect
[] 0 Δɛ

- -
The maximum absorption values
For ORD: 0 (Zero), See green colour curve
For CD : λmax , See violet colour curve ORD curve
(B)
Two graphs represent two enantiomers
+ +

(B) Negative cotton effect [] 0 Δɛ


CD curve
- -

λ
Absolute configuration of Complexes

➢ ORD curves are useful in the assignment of absolute configurations. For example,
the configurations of the enantiomers of
o tris(ethylenediamine)cobalt(III)
o Tris(alaninato)cobalt(III), and
o Bis(ethylenediamine)glutamatocobalt(III)
are known from X-Ray investigations, and it is found that the three Λ-(D)-
configuration could have been assigned to any of these in the absence of x-ray
data simply on the basis of the similarity of the ORD spectra to one of the known
configuration.

➢ Complexes having the same sign of CD for a given absorption band will have the
same absolute configuration.
Picture Credit: Inorganic Chemistry: Principles of
Structure and Reactivity James Huheey, Medhi
The absolute configurations and ORD spectra of (a) Λ-[Co(en)3]3+; (b) Λ-[Co(S-alanine)3];
(c) Λ-[Co(en)2(S-glu)]+. All of these complexes have Λ or D configuration
CD data for some Λ-(D)- and Λ-(L)-tris(chelate) complexes of cobalt(III)*

*Data adopted from Inorganic Chemistry: Principles of Structure and Reactivity, 4th Ed. James Huheey, Medhi
End of Chapter 4: ORD & CD

THANK YOU

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