Nitrogen Compounds - Optical Isomerism

Isomers of a molecule that result from a difference in the arrangement of groups in 3-D space, and not in the type and/or position of covalent bonds, are known as stereoisomers. There are two types of stereoisomerism: geometrical (or E/Z) isomerism and optical isomersim. Geometrical isomerism results from a lack of rotation around a carbon-carbon -bond, and has already been discussed in AS Organic Chemistry : Alkenes. Optical isomerism occurs as a result of a molecule having two mirror images that are nonsuperimposable on each other. In Organic Chemistry that is usually the result of a carbon atom present having four different groups attached to it. Such a carbon atom is known as a chiral carbon atom:

Even though there is no chiral carbon atom present optical isomerism is also possible in Inorganic Chemistry, for example when a hexadentate transition metal complex ion is formed from three bidentate ligands:

{see the transition elements option in trends and patterns for more details} As shown above, all -amino acids, with the exception of glycine - H2NCH2COOH, have a carbon atom bonded to four different groups.

The two optical isomers are identical in virtually all respects. They will do the same general chemical reactions and will give the same results with I.R., N.M.R. and Mass Spectroscopy. Their physical properties are the same (for example, melting point, boiling point, refractive index), with the exception of their effect on plane-polarized light. When light that has been plane polarized, so that it travels in only one plane, is shone on an optical isomer and the isomer is rotated, at a particular angle the light is absorbed. The other optical isomer will absorb the light when rotated in the opposite direction. Amino acids present in living systems all block plane-polarized light when rotated in a positive (i.e. clockwise) direction. They are called D- isomers. {D- stands for dextrorotatory} A molecule that blocks plane-polarised light when rotated in a negative(i.e. anticlockwise) direction is called the L- isomer. {L- stands for laevorotatory}

When synthetic reactions are carried out that make compounds with the possibility of optical isomers, a 50:50 mixture of both isomers will be made. This is called a racemic mixture. Such a mixture will appear to have no effect on plane-polarized light, as the two isomers cancel out each others effect. For example, when turning ethanal into 2-hydroxypropanoic acid (lactic acid) the first stage is the nucleophilic addition of HCN to ethanal. The attack of the cyanide ion, -:CN, on the carbonyl group can occur either from above or beneath the molecule:

Each pathway is equally likely, so a 50:50 mixture of the two stereoisomers will be formed:

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