Spectroscopic Methods for

determination of Absolute
Configuration of Coordination
Complexes
Octahedral complexes of Co(|||) ion show lowest d-d transition as
1A1g1T1g like in hexaminecobalt(III) and [Co(en)3]
3+ complex ion.

There are two spectroscopic methods for the

determination of the absolute configuration.
(i) Optical Rotatory Dispersion (ORD)
(ii) Circular Dichroism (CD)

These are based on cotton effect

 Optical Rotatory Dispersion (ORD)

The rate of change of specific rotation with respect to wavelength is known as optical rotatory
dispersion (ORD).

Optical Rotatory Dispersion (ORD) curves

ORD curve is plotted between change in the optical rotation and wavelength.
1. Plain curves
2. Anomalous/Cotton effect curves
Usually two types of plain curves are observed

(i) Plain positive ORD: Graph A represents a

plain positive ORD curve. Plain positive ORD
curves are obtained when specific rotation
increases with decreasing wavelength. In other
words, clockwise rotation is plotted positively.
(ii) Plain negative ORD: Graph B represents
plain negative ORD curve. Plain negative ORD
curves are obtained when specific rotation
decreases with decreasing wavelength. In other
words, counter clockwise rotation is plotted
negatively.
 Anomalous/Cotton effect curves

In ORD we measure the variation of optical rotation with wavelength. There is abrupt reversal of rotation in the
vicinity of the absorption band .
In case of Laevorotatory complex, the ORD curve fall to minimum then rises to maximum and then slowly falls .
On the other hand for Dextrorotatory complexes , it is reverse i.e, first ORD curve rises to maximum then fall
rapidly to minimum and then slowly rises .
These Represent Negative and Postive cotton effect.
 Circular Dichroism (CD)

The differential absorption of left and right

circularly polarized light is referred to
Circular dichroism (CD). Optically active
compounds possess this special property of
absorption of the left-handed circularly
polarized light to a different extent than the
right-handed circularly polarized light. This
phenomenon is called the circular dichroism
Thus absolute configuration of complexes may be assigned by ORD curves.
Although at one time ORD was used extensively for determination of
absolute configuration due to simpler instrument but nowadays CD is much
used .
Complexes having same sign of CD for given absorption band will have the
same absolute configuration .