Several isomers of the complex [Co(R-picpn)-(ala)]2+ have been synthesized, where R-picpn is 2,5-diaza-3R-methyl-1,6,-di(2-pyridyl)hexane, and ala is the anion of R- or S-alanine. The isomers have been studied using circular dichroism and high resolution 1H nmr techniques. Of the 40 possible isomers accessible in this system only 5 are observed to form in aqueous solution from Λ-α-[Co(R-picpn)Cl2]+. Two contain R-ala, and three contain S-ala. Four of the isomers (or their mirror images) correspond to those which have been previously characterized using X-ray crystallographic methods. Several diastereomers are found to cocrystallize. Λ-α-[Co(R-picpn)Cl2]+ reacts with 1,2-diaminoethane to form one main isomer which has also been characterized spectroscopically. Extensive rearrangement of the Co(III) coordination sphere is found to take place in all reactions.