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Absolute Configuration of Chelate Complexes From ORD and CD

1) Absolute configuration of chelate complexes can be determined using optical rotatory dispersion (ORD) and circular dichroism (CD) spectroscopy. 2) ORD and CD curves indicate whether a complex is left- or right-handed based on the direction of maximum absorption and presence of a positive or negative Cotton effect. 3) Complexes that produce ORD and CD curves of the same sign, such as several tris(chelate) cobalt(III) complexes, are known to have the same absolute configuration based on X-ray crystallography data.

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862 views4 pages

Absolute Configuration of Chelate Complexes From ORD and CD

1) Absolute configuration of chelate complexes can be determined using optical rotatory dispersion (ORD) and circular dichroism (CD) spectroscopy. 2) ORD and CD curves indicate whether a complex is left- or right-handed based on the direction of maximum absorption and presence of a positive or negative Cotton effect. 3) Complexes that produce ORD and CD curves of the same sign, such as several tris(chelate) cobalt(III) complexes, are known to have the same absolute configuration based on X-ray crystallography data.

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Absolute Configuration of Chelate Complexes from ORD and CD

 It is not possible to assign the absolute configuration simply on the basis of

the direction of rotation of the plane of polarized light.

 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.

 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)

 ORD and CD are two phenomena associated with d-d transitions 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.


(A) Positive cotton effect

The maximum absorption values

For ORD : 0 (Zero), See green colour curve

For CD : λmax , See violet colour curve

Two graphs represent two enantiomers

(B) Negative cotton effect

Assignment of Absolute Configuration using Optical Rotatory Dispersion (ORD)

 ORD involves measuring the variation of optical rotation with wavelength.

There is a sudden reversal of rotation in the vicinity of absorption band.

 If the complex is laevorotatory, the ORD curve falls to a minimum, rises

rapidly to a maximum, and then slowly falls.

 If the complex is dextrorotatory, the effect is reversed with ORD curve rising

first to a maximum, then falling.

 ORD curves are useful in the assignment of absolute configurations.

 For example, the configurations of the enantiomers of

1. tris(ethylenediamine)cobalt(III)

2. Tris(alaninato)cobalt(III)

3. Bis(ethylenediamine)glutamatocobalt(III)

are known from X-ray diffraction technique. It is found that three Λ-(+)-

enantiomers or Λ-(D)-enantiomers of these complexes have similar ORD spectra.

 The ORD spectra of Λ-[Co(en)3]3+, Λ-[Co(S-ala)3]3+ and Λ-[Co(en)2(S-glu)]3+ are

shown in below,
(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)]3+)

 All these complexes represent positive Cotton effect (All of these complexes have Λ or

D configuration).

Assignment of Absolute Configuration using Circular Dichroism (CD)

 The circular dichroism (CD) refers to differential absorption of left and right

circularly polarized light, εL-εR.

 Complexes having the same sign of CD for a given absorption band will have the same

absolute configuration.

 The absorption and CD spectrum of [Co(en)3]3+ is shown in below,

 The CD spectrum of [Co(en)3]3+ suggest that, Λ-[Co(en)3]3+ isomer shows

positive deflections, however Λ-[Co(en)3]3+ isomer shows negative deflections

in CD spectrum which also corresponds to the sign of Cotton effect.


 The fac isomers give rise to similar UV-visible spectra; similarly mer isomers

also give similar UV-visible spectra.

 The absorption and CD spectra for the four diastereomers of [Co(S-

alaninate)3] are shown below,

 The positive sign of the Cotton effect for the lowest energy CD band of the fac-

(+) and mer-(+) isomers suggests that these complexes (Co(S-alaninate)3 and Λ-

(+)-[Co(en)3]3+) have the same absolute configuration,Λ.

 The negative sign of the Cotton effect for the lowest energy CD band of the

fac-(-) and mer-(-) isomers suggests that these complexes have the same

absolute configuration, Δ.

 The observed results show that, the CD curves for (+) and (-) isomers are not

mirror images of one another.

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