7.3.8.

Stereochemistry of Substitution Reactions in Octahedral Complexes

• Consider the hydrolysis of cis/trans-[CoAX(en)2]+:

Stereochemistry of A X Percentage of
starting complex cis in product
cis OH- Cl- 100
Cl- Cl- 100
NCS- Cl- 100
Cl- Br- 100
trans NO2- Cl- 0
NCS- Cl- 50-70
Cl- Cl- 35
OH- Cl- 75

• Two pathways for the substitution are possible: either through square-pyramidal or
trigonal-bipyramidal intermediates:

(Shriver & Atkins, Inorganic Chemistry, 3rd Ed., Freeman, 1999)

• The pathway through the square-pyramidal intermediate leads to retention of the

stereochemistry. The pathway through the trigonal-bipyramid can lead to
isomerization.

• A good π-donor trans to the leaving group leads to isomerization because it stabilizes
the trigonal bipyramid. We can rationalize this point based on MO considerations:

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(Source: Purcell + Kotz, “Inorganic Chemistry”, Holt-Saunders, 1977)

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