General Chemistry Principles, Patterns, and Applications, 2011

Consequently, most microorganisms synthesize and secrete organic molecules calledsiderophores to
increase the total concentration of available iron in the surrounding medium. Siderophores are generally
cyclic compounds that use bidentate ligands, such as the hydroxamate and catecholate groups shown
here, to bind Fe 3+ in an octahedral arrangement. Typical siderophores are ferrichrome, a cyclic peptide
produced by fungi, and enterobactin, a cyclic ester produced by bacteria (Figure 23.18 "Siderophores").
Attaching the three iron ligands to a cyclic framework greatly increases the stability of the resulting
Fe 3+ complex due to the chelate effect described in Section 23.4 "Coordination Compounds". The
formation constants for the Fe 3+ complexes of ferrichrome and enterobactin are about 10 32 and 10 40 ,
respectively, which are high enough to allow them to dissolve almost any Fe(III) compound.
Figure 23.18 Siderophores
Ferrichrome (a) and enterobactin (b) are siderophores that use hydroxamate and catecholate ligands, respectively,
to bind Fe 3+ . The “wrapped” drawing of enterobactin (c) shows how the cyclic ester framework places the three
catecholate ligands in the correct orientation to bind to a single Fe 3+ ion, which is an application of the chelate effect.
The actual structure of ferrichrome is similar to that of enterobactin, with the three hydroxamate ligands adjacent
to one another for optimal binding of Fe 3+ . Note: For clarity, most or all hydrogen atoms have been omitted in this
and the following structures.
Siderophores increase the [Fe 3+ ] in solution, providing the bacterium that synthesized them (as well as any
competitors) with a supply of iron. In addition, siderophores neutralize the positive charge on the metal
ion and provide a hydrophobic “wrapping” that enables the Fe 3+ –siderophore complex to be recognized by
a specific protein that transports it into the interior of a cell. Once it is inside a cell, the iron is reduced to
Fe 2+ , which has a much lower affinity for the siderophore and spontaneously dissociates.
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