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This structure shows a metal atom, represented by M in red. Single bonds extending from the M are also shown in red. Bonds are indicated with O atoms by line segments extending above and below. Dashed wedges extend up and to the left to an N atom and up and to the right to an O atom, and solid wedges extend below and to the left to an N atom and below and to the right to an O atom. The O atoms bonded to the M atom each have a negative sign associated with them and they are each bonded to a C atom which is in turn double bonded to an O atom and single bonded to a C atom in a C H subscript 2 group. This last C atom in each case is single bonded to one of the N atoms, resulting in two five-member rings of which the M atom is a part. To the left of each N atom, are single bonds to the C in C H subscript 2 groups, which in turn are connected with a single bond, forming another five-member ring with the two N atoms and the M atom. Extending up and to the left of the upper N atom is a bond to the C atom of another C H subscript 2 group. This group is in turn bonded to a C atom which is double bonded to an O atom and single bonded to the O atom that is bonded to the M atom at the top of the structure, again forming a five-member ring. The same bonding structure repeats at the bottom of the structure extending from the N atom bonded at the lower left of the M atom. All single bonded O atoms in this structure have negative charges associated with them.
The ligand EDTA binds tightly to a variety of metal ions by forming hexadentate complexes.

Complexing agents that tie up metal ions are also used as drugs. British Anti-Lewisite (BAL), HSCH 2 CH(SH)CH 2 OH, is a drug developed during World War I as an antidote for the arsenic-based war gas Lewisite. BAL is now used to treat poisoning by heavy metals, such as arsenic, mercury, thallium, and chromium. The drug is a ligand and functions by making a water-soluble chelate of the metal; the kidneys eliminate this metal chelate ( [link] ). Another polydentate ligand, enterobactin, which is isolated from certain bacteria, is used to form complexes of iron and thereby to control the severe iron buildup found in patients suffering from blood diseases such as Cooley’s anemia, who require frequent transfusions. As the transfused blood breaks down, the usual metabolic processes that remove iron are overloaded, and excess iron can build up to fatal levels. Enterobactin forms a water-soluble complex with excess iron, and the body can safely eliminate this complex.

This figure includes two structures. In a, a five member ring is shown with an S atom at the top with additional atoms single bonded in the following order clockwise around the pentagonal ring; M atom, S atom, C atom of a C H subscript 2 group, followed by a C atom of a C H group. The final C atom is bonded to the original S atom completing the ring. The C in the C H group is at the upper left of the structure. This C has a C H subscript 2 group bonded above to which an O H group is bonded to the right. In b, a complex structure is shown. It has an open central region and multiple ring structures. A single F e atom is included, appearing to be bonded to six O atoms. Fifteen total O atoms are bonded into the structure along with three N atoms and multiple C atoms and H atoms. Nine O atoms are single bonded and are incorporated into rings and six are double bonded, extending outward from ring structures.
Coordination complexes are used as drugs. (a) British Anti-Lewisite is used to treat heavy metal poisoning by coordinating metals (M), and enterobactin (b) allows excess iron in the blood to be removed.

Chelation therapy

Ligands like BAL and enterobactin are important in medical treatments for heavy metal poisoning. However, chelation therapies can disrupt the normal concentration of ions in the body, leading to serious side effects, so researchers are searching for new chelation drugs. One drug that has been developed is dimercaptosuccinic acid (DMSA), shown in [link] . Identify which atoms in this molecule could act as donor atoms.

A structure is shown that has an H atom on the far left which is single bonded to an O atom to its right. This atom is bonded to a C atom just below and to the right. This C atom has a double bonded O atom below and is bonded to the C atom of a C H group. Above this C atom, a solid wedge extends upward to the S atom of an S H group. A bond extends from this last C atom to another C atom of a second C H group below and to the right. A dashed wedge extends from this C atom to the S of an S H group below. A single bond extends up and to the right of the C atom to another C atom. This last C atom has a double bonded O atom above. A single bond extends to a second O atom below and to the right. To the right of this O atom, an H atom is connected with a single bond. All S and O atoms in the structure are shown with two unshared pairs of electron dots.
Dimercaptosuccinic acid is used to treat heavy metal poisoning.

Solution

All of the oxygen and sulfur atoms have lone pairs of electrons that can be used to coordinate to a metal center, so there are six possible donor atoms. Geometrically, only two of these atoms can be coordinated to a metal at once. The most common binding mode involves the coordination of one sulfur atom and one oxygen atom, forming a five-member ring with the metal.

Check your learning

Some alternative medicine practitioners recommend chelation treatments for ailments that are not clearly related to heavy metals, such as cancer and autism, although the practice is discouraged by many scientific organizations. National Council against Health Fraud, NCAHF Policy Statement on Chelation Therapy , (Peabody, MA, 2002). Identify at least two biologically important metals that could be disrupted by chelation therapy.

Answer:

Ca, Fe, Zn, and Cu

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Ligands are also used in the electroplating industry. When metal ions are reduced to produce thin metal coatings, metals can clump together to form clusters and nanoparticles. When metal coordination complexes are used, the ligands keep the metal atoms isolated from each other. It has been found that many metals plate out as a smoother, more uniform, better-looking, and more adherent surface when plated from a bath containing the metal as a complex ion. Thus, complexes such as [Ag(CN) 2 ] and [Au(CN) 2 ] are used extensively in the electroplating industry.

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Source:  OpenStax, Chemistry. OpenStax CNX. May 20, 2015 Download for free at http://legacy.cnx.org/content/col11760/1.9
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