Coordination Chemistry of Transition Metals

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This figure shows six containers. Each is filled with a different color liquid. The first appears to be clear; the second appears to be purple; the third appears to be red; the fourth appears to be teal; the fifth appears to be blue; and the sixth also appears to be clear.
Figure 1. Metal ions that contain partially filled d subshell usually form colored complex ions; ions with empty d subshell (d0) or with filled d subshells (d10) usually form colorless complexes. This figure shows, from left to right, solutions containing [M(H2O)6]n+ ions with M = Sc3+(d0), Cr3+(d3), Co2+(d7), Ni2+(d8), Cu2+(d9), and Zn2+(d10). (credit: Sahar Atwa)

Coordination Chemistry of Transition Metals (Openstax Chemistry 2e)

The hemoglobin in your blood, the chlorophyll in green plants, vitamin B-12, and the catalyst used in the manufacture of polyethylene all contain coordination compounds. Ions of the metals, especially the transition metals, are likely to form complexes. Many of these compounds are highly colored (Figure 1). In the remainder of this chapter, we will consider the structure and bonding of these remarkable compounds.

Remember that in most main group element compounds, the valence electrons of the isolated atoms combine to form chemical bonds that satisfy the octet rule. For instance, the four valence electrons of carbon overlap with electrons from four hydrogen atoms to form CH4. The one valence electron leaves sodium and adds to the seven valence electrons of chlorine to form the ionic formula unit NaCl (Figure 2). Transition metals do not normally bond in this fashion. They primarily form coordinate covalent bonds, a form of the Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in coordination complexes, often called a central metal ion (or atom), is often a transition metal or inner transition metal, although main group elements can also form coordination compounds. The Lewis base donors, called ligands, can be a wide variety of chemicals—atoms, molecules, or ions. The only requirement is that they have one or more electron pairs, which can be donated to the central metal. Most often, this involves a donor atom with a lone pair of electrons that can form a coordinate bond to the metal.

Three electron dot models are shown. To the left, a central C atom is shown with H atoms bonded above, below, to the left, and to the right. Between the C atom and each H atom are two electron dots, one red, and one black, next to each other in pairs between the atoms. The second structure to the right shows N superscript plus sign followed by a C l atom in brackets. This C l atom has pairs of electron dots above, below, left, and right of the element symbol. A single electron dot on the left side of the symbol is shown in red. All others are black. Outside the brackets to the right, a negative sign appears as a superscript. The third structure on the far right has a central S c atom. This atom is surrounded by six pairs of evenly-spaced electron dots. These pairs of dots are positioned between the S c atom and each of the O atoms from six H subscript 2 O molecules. This entire structure is within brackets to the right of which is the superscript 3 plus.
Figure 2. (a) Covalent bonds involve the sharing of electrons, and ionic bonds involve the transferring of electrons associated with each bonding atom, as indicated by the colored electrons. (b) However, coordinate covalent bonds involve electrons from a Lewis base being donated to a metal center. The lone pairs from six water molecules form bonds to the scandium ion to form an octahedral complex. (Only the donated pairs are shown.) Source: Openstax Chemistry 2e

The coordination sphere consists of the central metal ion or atom plus its attached ligands. Brackets in a formula enclose the coordination sphere; species outside the brackets are not part of the coordination sphere. The coordination number of the central metal ion or atom is the number of donor atoms bonded to it. The coordination number for the silver ion in [Ag(NH3)2]+ is two (Figure 3). For the copper(II) ion in [CuCl4]2−, the coordination number is four, whereas for the cobalt(II) ion in [Co(H2O)6]2+ the coordination number is six. Each of these ligands is monodentate, from the Greek for “one toothed,” meaning that they connect with the central metal through only one atom. In this case, the number of ligands and the coordination number are equal.

Three structures are shown. In a, a central A g atom has N atoms bonded to the left and right as indicated by line segments. Three H atoms are similarly bonded to each N atom extending out and up, out to the side, and out and below each N atom. The structure is enclosed in brackets with a superscript plus sign to the right of the brackets. In b, a C u atom is at the center of the structure. Line segments indicate bonds to two C l atoms, one above and the other below and to the left of the central atom. To the right, a dashed wedge, narrow toward the C u atom and widening toward a C l atom, is shown at the right side of the central C u atom. A solid wedge is similarly directed toward a C l atom below and slightly right of the central C u atom. This structure is enclosed in brackets with a superscript 2 negative sign present to the right of the brackets. In c, a structure is shown with a central C o atom. From the C o atom, line segments indicate bonds to H subscript 2 O molecules above and below the structure. Above and to both the right and left, dashed wedges indicate bonds to two H subscript 2 O molecules. Similarly, solid wedges below to both the right and left indicate bonds to two more H subscript 2 O molecules. Each bond in this structure is directed toward the O atom in each H subscript 2 O structure. This structure is enclosed in brackets. Outside the brackets to the right is a superscript 2 plus sign.
Figure 3. The complexes (a) [Ag(NH3)2]+, (b) [Cu(Cl)4]2−, and (c) [Co(H2O)6]2+ have coordination numbers of two, four, and six, respectively. The geometries of these complexes are the same as we have seen with VSEPR theory for main group elements: linear, tetrahedral, and octahedral. Source: Openstax Chemistry 2e

Many other ligands coordinate to the metal in more complex fashions. Bidentate ligands are those in which two atoms coordinate to the metal center. For example, ethylenediamine (en, H2NCH2CH2NH2) contains two nitrogen atoms, each of which has a lone pair and can serve as a Lewis base (Figure 4). Both of the atoms can coordinate to a single metal center. In the complex [Co(en)3]3+, there are three bidentate en ligands, and the coordination number of the cobalt(III) ion is six. The most common coordination numbers are two, four, and six, but examples of all coordination numbers from 1 to 15 are known.

Two structures are shown. In a, H subscript 2 N appears at the left end of the structure. A short line segment extends up and to the right from the N atom to a C atom in a C H subscript 2 group. A short line segment extends down and to the right to another C atom in a C H subscript 2 group. A final short line segment extends from this C H subscript 2 group up and to the right to the N atom of an N H subscript 2 group. Each N atom in the structure has a pair of electron dots at its top. In b, a central C o atom has six N H subscript 2 groups attached with single bonds. These bonds are indicated with line segments extending above and below, dashed wedges extending up and to the left and right, and solid wedges extending below and to the left and right. The bonds to these groups are all directed toward the N atoms. The N H subscript 2 groups are each connected to C atoms of C H subscript 2 groups extending outward from the central C o atom. These C H subscript 2 groups are connected in pairs with bonds indicated by short line segments, forming 3 rings in the structure. This entire structure is enclosed in brackets. Outside the brackets to the right is a superscript 3 plus sign.

Figure 4. (a) The ethylenediamine (en) ligand contains two atoms with lone pairs that can coordinate to the metal center. (b) The cobalt(III) complex [Co(en)3]3+ contains three of these ligands, each forming two bonds to the cobalt ion. Source: Openstax Chemistry 2e

Any ligand that bonds to a central metal ion by more than one donor atom is a polydentate ligand (or “many teeth”) because it can bite into the metal center with more than one bond. The term chelate (pronounced “KEY-late”) from the Greek for “claw” is also used to describe this type of interaction. Many polydentate ligands are chelating ligands, and a complex consisting of one or more of these ligands and a central metal is a chelate. A chelating ligand is also known as a chelating agent. A chelating ligand holds the metal ion rather like a crab’s claw would hold a marble. Figure 4 showed one example of a chelate. The heme complex in hemoglobin is another important example (Figure 5). It contains a polydentate ligand with four donor atoms that coordinate to iron.

A structure is shown for the single ligand heme. At the center of this structure is an F e atom. From this atom, four single bonds extend up and to the right and left and below and to the right and left to four N atoms which are shown in red. Each N atom is a component of a 5 member ring with four C atoms. Each of these rings has a double bond between the C atoms that are not bonded to the N atom. The C atoms that are bonded to N atoms are connected to C atoms that serve as links between the 5-member rings. The bond to the C atom clockwise from the 5-member ring in each case is a double bond. The bond to the C atom counterclockwise from the 5-member ring in each case is a single bond. To the left of the structure, two of the C atoms in the 5-member rings that are not bonded to N are bonded to C H subscript 3 groups. The other carbons in these rings that are not bonded to N atoms are bonded to groups above and below. Above is a C H group double bonded to a C H subscript 2 group. Below is a C H subscript 2 group bonded to another C H subscript 2 group, which is bonded to a C O subscript 2 H group. At the right side of the structure, the C atoms in the 5-member rings that are not bonded to N atoms are bonded to additional structures. The C atom at to the right in the 5-member ring at the upper right is bonded to a C H group which is in turn double bonded to a C H subscript 2 group. Similarly, the right most C atom from the 5-member ring in the lower right is bonded to a C H subscript 3 group. The C atom from the 5-member ring not bonded to an N atom in the upper right region of the structure is bonded to a C H subscript 3 group above. Similarly, the C atom on the 5-member ring not bonded to an N atom in the lower right region of the structure is bonded to a C H subscript 2 group that is bonded to another C H subscript 2 group, which is bonded to a C O subscript 2 H group below.
Figure 5. The single ligand heme contains four nitrogen atoms that coordinate to iron in hemoglobin to form a chelate. Source: Openstax Chemistry 2e

Polydentate ligands are sometimes identified with prefixes that indicate the number of donor atoms in the ligand. As we have seen, ligands with one donor atom, such as NH3, Cl, and H2O, are monodentate ligands. Ligands with two donor groups are bidentate ligands. Ethylenediamine, H2NCH2CH2NH2, and the anion of the acid glycine, NH2CH2CO2− (Figure 6) are examples of bidentate ligands. Tridentate ligands, tetradentate ligands, pentadentate ligands, and hexadentate ligands contain three, four, five, and six donor atoms, respectively. The ligand in heme (Figure 5) is a tetradentate ligand.

A structure is shown. At the center of this structure is an P t atom. From this atom, two single bonds extend up and to the right and below and to the left to two O atoms which are shown in red. Similarly, two bonds extend up and to the left and down and to the right to N atoms in N H subscript 2 groups. The N atoms in these groups are in red. The N atoms are bonded to C H subscript 2 groups, which in turn are bonded to C atoms. These C atoms have doubly bonded O atoms bonded and oriented toward the outside of the structure. They are also singly bonded to the O atoms in the structure forming two rings connected by the central P t atom.
Figure 6. Each of the anionic ligands shown attaches in a bidentate fashion to platinum(II), with both a nitrogen and oxygen atom coordinating to the metal. Source: Openstax Chemistry 2e

Source:

Flowers, P., Theopold, K., Langley, R., & Robinson, W. R. (2019, February 14). Chemistry 2e. Houston, Texas: OpenStax. Access for free at: https://openstax.org/books/chemistry-2e

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