22 Transition Metals Biological and Medical Applications RED COLOROF BLOOD the red ecioraf blood cxmaz fomthshame group, ‘amefecule contain a ning with feu tren stores that bin ts 2 central Fe" Lewis Acid or Lewis Base? le Chapter 22 wediseuss the bonding ard structure of eompounds ant complex ions formed by trane:tion matsle snd lea stout te presencia binlagical systems end theirapplictions te medicine, The compounds ‘shown hereare ameueris, koran, and water “+ raw the Lewis structure foreach compound. “+ Which compound} hasshave at least onelone pair of dlectrans cn the ceraral stern? ‘Which compound{e} can function 2: Lewis acid? Which ean function, sea Levis base? (Review Chapters 48, andt6 i you need help}ROW Us AU) ‘One Molecule, One Bond versus One Molecule, Two Bonds Here are two complex ions that contain metal cations bonded to different molecules, As you read Chapter 22, look for ideas that will help you answer these questions: + Two different molecules form coordinate bonds to Cu** and Ni?*in the figure to the right. Which element coordinates to the metal? + What molecule is bonded to the copper cation? How many of these molecules form coordinate bonds with the copper cation? * What molecule is bonded to the nickel cation? How many of these molecules form coordinate bonds with the nickel cation? Learning Outcomes LOT Recagnize complex ions and their counterions in chemical formulas ‘Sample Exercise 22.1 LOZ Interconvert the names and formulas of complex ions and coordination compounds Sample Exercise 22.2 LOS Explain the chelate effect and its importance Sample Exercise 22.3 LO4 Explain the origin of the colors af transition metal compounds by using the spectrochemical series LOS Describe the factors that lead ta high-spin or low-spin electronic states of ‘complex ions Sample Exercise 22.4 LOG Identify geometric, linkage, and optical isomers of coordination compounds Sample Exercise 22.5 LOT Describe several of the roles of transition metal complexes in biochemistry and how they are used as diagnostic or therapeutic compounds Sample Exercise 22.622.1 Transition Metals in Biology: Complex lons Many of the metallic elements in the periodic table are essential to good health. For example, copper, zine, and cobalt play key roles in protein function. Iron is needed to transport oxygen from our lungs to all the cells of our body. These and other essential metallic elements, several of which we discussed in Chapter 21, should be present either in our diets or in the supplements many of us rely on for balanced nutrition, Table 22.1 lists the wansition metals essential to our bodies im trace and ultratrace concentrations. However, the mere presence of these elements is insufficient—they must be in a form that our cells can use. Swallowing an 18-mg steel pellet would not be a good way for you to get your recommended dietary allowance (Table 21.4) of iron. If we are to benefit from consuming essential metals in food and nutritional supplements, the metals need to be in compounds, not free elements, and the compounds must be bioavailable to the body. All the metallic transition TABLE 22.1 Essential Transition Elements Found in the elements essential to human health occur in nature in ionic Human Body compounds, bur not all ionic a eee) forms are absorbed equally Sr well. For example, mast of the tron Chromium, iron in fish, poultry, and red Zine Cobalt meat is readily absorbed ‘copper because itis present in a form called heme iron. The iron in Manganese plants, however, is mostly Molyodenum nonheme and is not as readily Nickel absorbed. Eating a meal that Vanadium includes both meat and vegetables improves the absorption of the nonheme iron in the vegetables. Fruits, vegetables and other foods high in vitamin G increase the availability of iron, possibly by forming complex ions of the rype described in Section 16.6, All these dietary factors work together at the molecular level to provide us with the nutrients we need to survive.Interactions between transition metals and accompanying nonmetal ions and molecules influence the solubility of the metals, which is a key factor toward making them chemically reactive and biologically available to plants and animals. These interactions also influence other properties, including the wavelengths of visible light that the metals absorb and therefore the colors of their compounds and solutions. In this chapter we explore how the chemical environment of transition metal ions in solids and in solutions affects their physical, chemical, and biological properties. We answer questions such as why many, but not all, metal compounds have distinctive colors, and how, through the formation of complex ions with biomolecules, transition metals play key roles in many biological processes. ‘We begin by examining the interactions between transition metal ions and the other ions and molecules that surround them in solids and solutions. To understand these interactions, we need to review the definitions of Lewis acids and Lewis bases we first used in Section 16.5: » A Lewis base isa substance that donates a lone pair of electrons in a chemical reaction. * A Lewis acid is a substance that acespis a lone pair of electrons in a chemical reaction. CONNECTION Lewis's pioneering theories of the nature of covalent bonding were described in Chapter 8, and the formation of complex ions between metal ions (Lewis acids) and ligands (Lewis bases) was discussed in Section 16.6, In Section 10.3, we described how ions dissolved in water are hydrated, that is, surrounded by water molecules oriented with their positive dipoles directed toward anions and their negative dipoles directed toward cations (see Figure 10.6). When these ion-dipole interactions lead to the sharing of lone-pair electrons with empty valence-shell orbitals on the cations, they meet our definition of covalent bonds, and in this case are called coordinate covalent bonds, or simply coordinate bonds. Much of the chemistry of the transition metals is associated with their ability to form coordinate bonds with molecules or anions. Review Chapter 10 if you need help with these concepts.As we saw in Section 16.6, molecules or anions that function as Lewis bases and form coordinate bonds with metal cations are called ligands. The resulting species, which are composed of central metal ions and the surrounding ligands, are called complex ions or simply complexes. Direct bonding to a central cation means that the ligands in acomplex occupy the inner coordination sphere of the cation. Take another look at Sample Exercise 14.12, in which we discussed the equilibrium between two forms of cobalt(II), one pink and one blue (see Figure 14.11), in an aqueous solution of HCl (Figure 22.1). Both the pink and blue forms are complexes; the pink cobalt(II) species has six water ligands in its inner coordination sphere, whereas the blue species has four chloride ions. The charge on each complex ion is the sum of the charges of the metal ion and the ligands: 2+ for Co(H2O}a* because the charge of the cobalt ion is 2+ and water molecules are neutral, and 2- for CoCl,*> because the sum of the 2+ charge on the cobalt ion and four 1- charges on the chloride ions is 2-. me fami FIGURE 22.1 Equilibrium between two forms of cobalt in aqueous HCl solution.‘The foundation of our understanding of the bonding and structure of complex ions comes from the pioneering research of Swiss chemist Alfred Werner (1866-1919), for which he was awarded the Nobel Prize in Chemistry in 1913. Some of Werner's research addressed the unusual behavior of different compounds formed by dissolving cobalt(II) chloride in aqueous ammonia and oxidizing it to cobalt(II) by bubbling air through the solution. One of the redox reactions produces an orange compound (Figure 22.2a) that contains 3 moles of Cl ions and 6 moles of ammonia for every | mole of Co™ ions. Another reaction produces a reddish purple compound (Figure 22.2b) that has the same proportions of Cl- and Co ions, but with only 5 moles of ammonia per mole of cobalt(III). Both compounds are water-soluble solids that react with aqueous solutions of AgNO, forming solid AgCl. However, 1 mole of the orange compound produces 3 moles of solid AgCl, whereas | mole of the reddish purple one produces only 2 moles of AgCl. Results like these inspired Werner to study the electrical conductivity of aqueous solutions of the two compounds. He found that the orange compound was the better conductor, indicating that it produced more ions in solution than the reddish purple one. CONNECTION We discussed in Chapter 4 how the electrical conductivity of aqueous solutions depends on the concentrations of dissolved ions in the solutions. () [ColNHQ,ICl, (b} [CoONH,)-CICL, FIGURE 222 ‘Two compounds of cobalt(III) chloride and ammonia.Werner concluded that the differences in the two compounds’ composition, in their capacities to react with Ag* ions, and in their electrolytic properties are all caused by the presence of two types of Co-Cl bonds inside them. He proposed that these bonds were all ionic in the orange compound, but that only two-thirds of them were ionic in the reddish purple compound. The remaining one-third are coordinate covalent bonds. Mi concert Test Si How would the electrical conductivity and freezing points of 0.010 m aqueous ‘solutions of the two compounds in Figure 22.2 differ? SHOW ANSWERS: This capacity to form two kinds of bonds means that Co and other transition metal ions have two kinds of bonding capacity, or valence. The first kind involves ionic bonds and is based on the number of electrons that a metal atom loses when it forms an ion. ‘This valence is equivalent to its oxidation number, which is +3 for cobalt in both the orange and reddish purple compounds. The second kind of valence is based on the capacity of metal ions to form coordinate bonds. This property corresponds to an ion’s coordination number, the number of sites around a central metal ion where bonds to ligands form. When the two compounds in Figure 22.22 and b dissolve in water, they form an orange and a reddish purple solution. The respective solutions contain the ions shown in Figure 22.3. The orange solution contains (Co(NH,)5|"" and three chloride ions, whereas the reddish purple solution contains [Co(NEH,);Cll?* and two chloride ions. Notice ‘how brackets in the formulas of these coordination compounds set off the complex ions fram the ionically bonded chieride counterions, which balance the charges on the complex ions: 3+ for the orange one (Figure 22.32), but only 2+ for the reddish purple one because it contains a negatively charged Cl- ion within its inner coordination sphere (Figure 22.36). The release of 3 moles of chloride ions from the orange compound, but only 2 from the reddish purple compound, explains the compounds’ chemical and electrolytic properties.‘Werner proposed, correctly, that the six ligands in the inner coordination sphere of cobalt(III) ions are arranged in an octahedral geometry, as shown in the structures in Figure 22.3. This geometry is consistent with the formation of six bonds to a central atom (or central ion in this case), as we learned in Chapter 9 (see Table 9.1). Many other transition metal ions form six coordinate bonds and octahedral complex ions. Some are listed in Table 22.2, as are complex ions that have only two or four ligands. Those with two have linear structures, whereas those with four may be tetrahedral or square planar. Both geometries occur in cobalt(II) ions: CoCl,*- is tetrahedral, whereas Co(CN},* is square planar. ab Coc FIGURE 223 Structures of cobalt(II) complex ions and counterions in aqueous solution. (il concert Test! In the coordination compound Naz[Fe(CN)¢]. which ions occupy the inner coordination sphere of the Fe®* ion and which ions are counterions? Of the four cobalt complexes: described in this section, which would have conductivity in aqueous selution similar to that of Nas[FefCN}e]? SHOW ANSWERSTABLE 22.2_ Common Coordination Numbers and Shapes of Complex lons Fe(Hz0}."* 6 6 Octahedral Ni( HO)?" GofH,0}.** 4 6 ‘Sepiara plana ses Prin)? 4 4 Tetrahedral 2n(Ho0}7" 7" FIGURE 22.4 ‘The source of the blue color in The Great Wave aff Kanagawa, a woodblock print by the Japanese artist Hokusai, is the pigment Prussian blue.De SAMPLE EXERCISE Assigning Oxidation States in Lov 22.1 Coordination Compounds The frst modern synthetic color, Prussian blue, was made in 1704 in Berlin, Germany. It was heavily used in the 19th-century Japanese woodblock print The Great Wave off Kanagawa (Figure 22.4), and it continues to be popular with artists worldwide. The fornmula for the insoluble pigment is Fe,[Fe(CN)sJa. a. What is the formula of the complex ion in this compound and what is its charge if the counterion is Fe"? b, What is the oxidation state of iron in the complex ion? Collect, Organize, and Analyze We have the formula of a coordination compound and are asked to identify the complex ion and the counterion. The complex ion is contained in brackets, the four Fe counterions are outside the brackets, and the compound musi be electrically neutral. Solve a, The combined charge of four Fe is 12+. ‘To achieve clecwrical neutrality, the combined charge of the three complex anions must be 12- . ‘Therefore, the charge of each anion is (12- \/3 = 4- , and the formula for the anion is [Fe(CN),I*. b. Six cyanide ligands, CN-, occupy the inner coordination sphere for a total charge of 6- . ‘Therefore, the oxidation state of Fe must be 2+ for the charge on the complex ion to equal 4~ . Think About It Complex ions may have positive or negative charges. Correspondingly, coun:crions will have charges opposite to those of the complex ions to ensure electrical neutrality, Practice Exercise A coordination compound of ruthenium, [Ru(NH),Cly|Cl, has shown some activity against leukemia in animal studies. Identify the complex ion, determine the oxidation number of the metal, and identify the counterion. HIDE ANSWERS (Ru(NH),Cly) is the complex ion; Ru is present as Ru**; chloride is the counterion,22.2 Naming Complex lons and Coordination Compounds ‘The names of complex ions and coordination compounds tell us the identity and oxidation state of the central ion, the names and numbers of ligands, the charge in the case of complex ions, and the identity of counterions, To convey all this information, we need to follow some naming rules. Complex lons with a Positive Charge 1. Start with the identities of the ligand(s). Names of common ligands appear in Table 22.8. If there is more than one kind of ligand, list, the names alphabetically. 2. Use the usual prefixes) in front of the name(s) written in step 1 to indicate the number of each type of ligand (Table 22.4), 3. Write the name of the metal ion with a Roman numeral indicating its oxidation state: ‘TABLE 22.3 Names and Structures of Common Ligands ed Sd of Donor ee ed Cd lero I - 1 Bromo er oo Chloro cr oo Fluore F 4 Nitra - oo Hydroxide Hydroxo [0-H - oo ‘Water Agua 6. o 4 HOH Pyridine (ey) Pyridy! a 1 Ammonia Ammine NHs o 1 Ethylenediamine (same)? o 2 (en) HNN2,2? Bipyridine Bipyridy! 2 (bipy) 1,10- {same)* 2 Phenanthroline (phen) Cyanide? ‘Cyano _ eo [c=n] Carbon monoxide ® Carbonyl =o 0 1 TABLE 22.4 Common Prefixes Used in the Names of Complex lons 2 3 tri 4 tetra- 5 penta- 6 hexa-Mil, Og? Hexanquanickel(1]} CoqNHs)e" HexaemmineconaryIT} ‘CuiMHe(H 0,2 | Totranmminndinquacopper(tl) It may seem strange to have two a's together in these names, but it is consistent with current naming rules. Prefixes are ignored in determining alphabetical order, which is why ammine comes before aqua rather than di before tetra in tetraamminediaquacopperi(l). The ligands are all electrically neutral in these three examples. This makes determining the oxidation state of the central metal ion a simple task because the charge on the complex ion is the same as the charge on the metal ion, which is the oxidation state of the metal. When the ligands are anions, determining the oxidation state of the central metal ion requires us to account for these charges.Complex lons with a Negative Charge 1. Follow the steps for naming positively charged complexes. 2. Add -ate to the name of the central metal ion to indicate that the complex ion carries a negative charge (just as we use -ate to end the names of oxoanions). For some metals, the base name changes, too. ‘The two most common examples are iron, which becomes ferrate, and copper, which becomes cuprate. Examples: Fe(cn}.? Hexacyanoferate() [Fe JONCNI Aouapentacyanoferrate(Il) [MCLANF ha Dianinninetetiachion ovanedate(ILN) In the first two examples we must determine the oxidation state of Fe. ‘We start with the charge on the complex ion and then take into account the charges on the ligand anions to calculate the charge on the metal ion. For example, the overall charge of the aquapentacyanoferrate(II) ion is 3 . It contains five CN” ions. To reduce the combined charge of 5- from these cyanide ions to an overall charge of 3- , the charge on Fe must be 2+. The most common ionic charges for some transition metals are shown in Figure 22.5.2 13 14 15 16 17 B45 67 89 WHR cus VO gy Mn® Fe Co® NP Cur Beh TH ys. CO sgt Bel Cob Ne Cae 28 Yo tee Ag ca Hg} Hg FIGURE 225 Common ionic charges of some transition metals. concert Test What is the name of the complex anion with the formula PrCl.?-? ‘SHOW ANSWERS Coordination Compounds 1. If the counterion of the complex ion is a cation, the cation's name goes first, followed by the name of the anionic complex ion. 2. If the counterion of the complex ion is an anion, the name of the cationic complex ion goes first, followed by the name of the anion. Examples: Formula = NH, HN, | aN, ININH IE, Hexsamminenickel ll) Nn ails len chloride:KgFEIGN Potassium Ks hexeryanafortmottl) re HAN, NH ntaaramineag ace Ora (CoINH lH, O16; Pantagrmminoaquacabol( I} col" ey bromide HAN | SN, Ho Ackey to naming coordination compounds is to recognize from their formulas that they are coordination compounds. For help with this, Jook for formulas that have the atomic symbols of'a metallic element and one or more ligands, all in brackets, either followed by the atomic symbol of an anion, as in [Co(NH,);(H,0)]Br2, or preceded by the symbol of'a cation, as in Ks[Fe(CN)s]. SAMPLE EXERCISE — Naming Coordination Compounds Loz 22.2 Name the coordination compounds (a) Nay[Go(CN)¢] and (b) [Co(NHy)sCI(NOxbo. Collect and Organize We are asked to write a name for each compound that unambiguously identifies its composition. The formulas of the complex ions appear in brackets in both compounds, Because cobalt, the central metal ion in both, is a transition metal, we express its oxidation state by using Roman numerals, The names of common ligands are given in ‘Table 22.3 Analyze It is useful to take an inventory of the Hgands and counterions: ugaND compound ‘Gounterion Formula Name Number Prefix Nag{Oo(CN}.] Nat cn” cyano 6 Hexa: [Co(WH,),C(NO.), NOs NHs Amine 5 Penta: cr Chico 1 - The oxidation state of each cobalt ion can be calculated by seiting the sum of the charges on all the ions in both compounds equal to zero: a. Ions: (4 Na‘ ions) + (1 Ca¥ jon) + (6 GN” ions) Charges: dest 6- = 0 ramb. lons: (1. Cot ion) + (1 Cl’ ion) + (2 NOs" ions) (Charges:x+ 1- + 2- = 0 r=a Solve a. Because the counterion, sodium, is a cation, its name comes frst. ‘The complex ion is an anion. ‘To name it, we begin with the ligand cyano, to which we add the prefix hera- and write Aexacyano. This is followed by the name of the transition metal ion: hexacyanocobait. We add -ate to the ending of the name of the complex ion because it is an anion: hexacyanocobaltafe. We then add a Roman numeral to indicate the oxidation state of the cobalt: hexacyanocobaltate(). Putting it all together, we get sodium hexacyanocobaltate({D). ‘The complex ion is the cation in this compound, and we begin by naming the ligands directly attached to the metal ion in alphabetical order: ammine and chloro. We indicate the number (5} of NHy ligands with the appropriate prefix: pentaarnminechloro, We name the metal next and indicate its oxidation state with a Roman numeral: pentaamminechlorocobalt(I/D). Finally, we name the anionic counterion: nitrate. Putting it all together, we obtain the name: pentaamminechloracobali(I1!) nitrate. r The structures of the complex ions in the named coordination compounds are shown in Figure 22.6. Think About It Naming coordination compounds requires us to write a name for each compound that unambiguously identifies its composition. The names sodium hexacyanocobaltate(Il) and pentaamminechlorocobalt(II0) nitrate are unique to the compounds Nay[Co(CN)e] and [Co(NHq}sCl](NOu)s, respectively. Practice Exercise Identify the ligands and counterions in (a) [4n(NH},]Clz and (b) [Co(NHg),(H20)2](NOy)y, and name each [2n(NHg)JCl ci” NH, = ammine 4 tetra (chloride) [Co(NH;)4(H20)2] No.” NH ammine 4 tere Hy (NO), (nitrite) a. [2n(NHa):|Cle = tetraamminezine(1l) chloride b. [Co(NHq),(Hy0}4](NOs)y = tetraamminediaquacobalt(lI) nitrite(a) (b) FIGURE226 ‘The structures of the complex ions in (a) sodium hexacyanocobaltate{{!) and (b) pentaarnmminechlorocobale(Itl) nitrate:22.3 Polydentate Ligands and Chelation Ligands are electron-pair donors—that is, Lewis bases. Let's explore the strengths of several ligands as Lewis bases by considering their affinity for Ni?“(ag) ions. Suppose we dissolve crystals of nickel(LI) chloride hexahydrate, NiCly - 6 HO (Figure 22,7a), in water. The dot connecting the two halves of the formula and the prefix hexa indicate that each Ni* ion in crystals of nickel) chloride is surrounded by six water molecules. Lime green crystals of NiCly - 6 HyO form green aqueous solutions (Figure 22.7b). The solid and its solution have the same color, which tells us that the same arrangement of water molecules around Ni? ions occurs in both solid NiClz + 6 He and aqueaus solutions of Ni* ions. Thus, the Ni* ion in a solution of nickel(I]) chloride is most likely Ni{H0)¢"-. The hydrated ion Ni(},0);2* can also be expressed as Ni*(aq) ‘Now let's bubble colorless ammonia gas through a green solution of Ni(H;O); ions. As shown in the middle beaker in Figure 22.7b, the green solution turns blue. The color change means thar different ligands are bonded to the Ni” ions, We may conclude that NHy molecules have displaced at least some H,O molecules around the Ni ions. If all the molecules of HzO are displaced, the complex NNi(NH,),?* is formed. The following chemical equation describes this change: Ni( HO)" (ag) + 6 NH, ) + 61,00 Kj=5% 10" ‘This ligand displacement reaction illustrates that Ni?- ions have a greater affinity for molecules of NHs than for molecules of HyO. Many other transition metal ions also have a greater affinity for ammonia than for water. We may conclude that ammonia is inherently a better electron-pair donor and hence a stronger Lewis base than water. This conclusion is reasonable because we saw in Chapter 15 that ammonia was also a stronger Brensted-Lowry base than HO. ‘Next we add the compound ethylenediamine (see Table 22.8) to the blue solution of Ni(NHle** ions. The solution changes color again, from blue to purple (Figure 22.7b), indicating yet another change in the ligands surrounding the Ni? ions. Molecules of ethylenediamine displace ammonia molecules from the inner coordination sphere of Ni? ions. This affinity of Ni? ions for ethylenediamine molecules is reflected in the large formation constant for Ni(en),?" (where “en” represents ethylenediamine):Na(HO}2 lagh | 3 entag) = Nilen}? ay) 6 H,O() Ke = 1.41 x 100 FIGURE 227 Structures of the cormplex ions in solid and dissolved nickel) chloride. (a) Solid nickel(1)) chloride hexahydrate. (b) When it dissolves in water, the resulting solution has the same green color, indicating that each Ni2* ion (gold sphere) must be surrounded by Hy molecules both in the solid and in the solution. When armmonia gas is bubbled through a solution of Ni{HsO),"", the color changes to blue as NH replaces HO in the Ni? ion's inner coordination sphere. When ethylenediarnine (en) is added ta a solution of Ni(NHylp®", the color turns from blue to purple as the ethylenediamine displaces the ammonia ligands and the Nilen)s2> complex forms. This value is more than 10° times the Kyvalue for Ni(NHie?. Why should the affinity of Ni** ions for ethylenediamine be so much greater than their affinity for ammonia? After all, in both ligands the coordinate bonds are formed by lone pairs of electrons on N atoms. To answer this question, we need to look at the differences between ligands such as ammonia, which occupy only one site on a metal ion, and ligands such as ethylenediamine, which occupy two or more sites.4. FIGURE 228 (a) The bidentate ligand ethylenediamine has two N atoms that can each donate a pair of electrons to empty orbitals of adjacent octahedral bonding sites on the same Ni (aq) ion (gold sphere), displacing two molecules of water. (b) Three ethylenediamine molecules occupy all six ‘octahedral coordination sites of a Ni" jon. ‘Many ligands in Table 22.3 can donate only one pair of electrons to a single metal ion. Even atoms with more than one lone pair usually donate only one pair at a time toa given metal ion because the other lone pair or pairs are oriented away from the metal ion. Because these ligands have effectively only one donor group, they are called monodentate ligands, which literally means “single-toothed.” ‘Certain molecules larger than ammonia and water may be able to donate more than one lone pair of electrons and therefore form more than one coordinate bond to a central metal ion. Ligands in this category are called polydentate ligands, or more specifically bidentate, tridentate, and so on, One group of polydentate ligands is the polyamines, which include ethylenediamine, a bidentate ligand that has the structure: H a NH, H,C—CH, ‘The lone pairs on the two -NH, groups are separated from each other by two —CHy- groups. This combination means thata molecule of ethylenediamine can partially encircle a metal ion so that both lone pairs can bond to the same metal ion.The structure of an ethylenediamine complex of Ni?*(ag} is shown in Figure 22.82. The two orbitals that share the lone pairs of electrons from a molecule of ethylenediamine must be on the same side of the Ni* ion. However, two more ethylenediamine molecules can bond to other pairs of bonding sites, displacing additional pairs of water molecules and forming a complex in which the Ni** ion is surrounded ‘by three bidentate ethylenediamine molecules, as shown in Figure 22.8b. Each ethylenediamine molecule forms a five-atom ring with the metal ion. If the ring were a regular pentagon (meaning all bond lengths and bond angles were exactly the same), each of its bond angles would be 108°. These pentagons are not perfect, but each ring’s preferred octahedral bond angles of 90° for the N-Ni-N bond, and of 107° to 109° for all the other bonds, are accommodated with only a little strain on the ideal bond angles. The compound in Figure 22.8b is also chiral, a topic we address in Section 22.6. i au: ML HN chi, cht, CH, ‘NH, (a) ib) FIGURE 229 ‘Tridentate chelation. (a) The three amine groups in the tridentate ligand diethylenetriamine are all potential electron-pair donor groups. (b) When these groups donate their lone pairs of electrons to a Ni** (ag) ion (gold sphere), they occupy three of the six coordination sites on the ion.An even larger ligand, diethylenetriamine (HgNCHyCHyNHCHyCH,NHg) is shown in Figure 22.9a. The lone pairs of electrons on its three nitrogen atoms give diethylenetriamine the capacity to form three coordinate bonds to a metal ion, meaning this is a tridentate ligand (Figure 22.9b). ‘The interaction of a metal ion with a ligand having multiple donor atoms is called chelation (pronounced key-LAY-shun). The word comes from the Greek chele, meaning “claw.” The polydentate ligands that take part in these interactions are called chelating agents. ‘When we added ethylenediamine to the blue solution of Ni(NHq),? ions in Figure 22.7b, molecules of ethylenediamine (en) displaced ammonia molecules from the inner coardination sphere of Nit+ ions as described in the following chemical equation: The color change tells us that this reaction as written is spontaneous. As we Ni(NH)2" (ag) + 3 enlag) = Nifends?* (ag) + 6 NHylag) (22.1) discussed in Chapter 17, spontaneous reactions are those in which free energy decreases (ie., AG < 0). Furthermore, under standard conditions the change in free energy AG" is related to the changes in enthalpy and entropy that accompany the reaction: AG = AN - TAS: ‘The displacement of NHs by ethylenediamine is exothermic, but only slightly (AZT = -12 kJ/mol), More important, AS’ = +185 J/mol - K. At 25°C, then, Iss} 1 iS = 298 TM Kx TT = 55.1 kl/mol mol « There is such a large increase in entropy because there are 4 moles of reactants but 7 moles of products in Equation 22.1. Nearly doubling the number of moles of aqueous products aver reactants translates into a large gain in entropy. It is this positive AS", more than the negative AH’ value, that drives the reaction and makes it spontaneous. Entropy gains drive many complexation reactions that involve polydentate ligands. The entropy-driven affinity of metal ions for polydentate ligands is called the chelate effect. CONNECTION The molecule nonactin in Figure 21.6 acts as chelating ligand when it forms a complex ion with K”.Many chelating agents have more than one kind af electron-pair— donating group. Aminocarborylic acids represent one family of such compounds. The most important of them is ethylenediaminetetraacetic acid (EDTA), which is shown in Figure 22.102, One molecule of EDTA contains two amine (nitragen- containing) groups and four carboxylic acid (- COOH) groups. When the acid groups release their H” ions, they form four carboxylate anions, -COQ*, in which either of the © atoms can donate a pair of electrons to a central metal ion. When O atoms on all four groups do. so and the two amine groups do as well, six octahedral bonding sites around the metal ion ean be occupied, as shown in Figure 22.10b. FIGURE 22.10 (a) In the hexadentate ligand EDTA, the six donor groups are the two amine groups and the four carboxylic acid groups. The acid groups ionize to form carboxylate anions. (b) All six Lewis base groups in ionized EDTA can form a coordinate bond with the same metal ion, such as Co™ {the gold sphere) shown here. In the process they form four S-membered rings. EDTA forms very stable complex ions and is used as a metal ion. sequestering agent—that is, a8 a chelating agent that binds metal ions so tightly that they are “sequestered” and prevented from reacting with other substances. For example, EDTA is used as a preservative in many beverages and prepared foods because it sequesters iran, copper, zine, manganese, and other transition metal ions often present in these foods that can catalyze the degradation of ingredients in the foods. ‘Many foods are fortified with ascorbic acid (vitamin C), which is particularly vulnerable to metal-catalyzed degradation because it is also a polydentate ligand and is more likely to be oxidized when chelated to one of the alsove metal ions. EDTA effectively shields vitamin C from these ions. EDTA is also a common additive to shampoos because it can remove metal cations from hard water. CONNECTION Hard water is discussed in Section 11.5.SAMPLE EXERCISE Identifying the Potential Electron-Pair— Loz 22.3 Donor Groups in a Molecule How many donor groups does nitrilotiacetic acid (NTA) have? HO Collect, Organize, and Analyze We need to examine the molecular structure of this polydentate ligand to find electron pairs that can be donated. Because there are three single bonds around the N atorn, the atom’ fourth sp? orbital must contain a lone pair of electrons, When all three carboxylic acid groups are ionized, there are three carboxylate groups in the molecule, and each carboxylate group can donate one nonbonding pair of electrons from one of its oxygen atoms to a metal atom. Solve The central N atom and an O atom from each of the three carboxylate groups form a total of four coordinate bonds. Therefore, NTA js potentially a tetradentate ligand with four donor groups. [f we also consider the lone pairs on the oxygen atoms of the C—O group, NYAcould coordinate atotal of six exygens te a transition metal cation, making NTA a hexadentate ligand. If we coordinate the nitrogen in NTA through its lone pair, one can imagine a seven- coordinate, heptadentate NTA ligand. The three carboxylate groups, though, are all bonded to a single N through a CHy group, so the bond. distances and bond angles in NTA may prevent coordination numbers greater than four. Think About It ‘The tetradentate capacity of NTAis reasonable because, like EDTA, it is an aminocarboxylic acid. It has one fewer amino group and one fewer carboxylic acid group than the hexadentate EDTA. Practice Exercise How many potential donor groups are there in citric acid, a component of citrus fruits and a widely used preservative in the food industry? 0. IH or 8 ll Be US HO~ “ch, fi, ch OH HIDE ANSWERS Six, if we count the six oxygens in the ~CO,~ groups or three if we consider each ~CO,~as one group.CONNECTION In Section 7.3 we first used the equation E = hy = Ac/A when discussing the energy of light in the electromagnetic spectrum (Figure 7.7).22.4 Crystal Field Theory Why does the formation of complex ions change the color of solutions of transition metals? The mo colors of transition metal 5 compounds and ions in solution. result from transitions of d-orbital electrons. Let's explore these transitions by using Cr as our ey model transition metal ion (Figure 22.11). ACr* jon has the electron configuration [Ar]8dyin the gas phase. When a Cr“ ion (or any atom or ion) is in the gas phase, all the orbitals in a given subshell have the same energy (Figure FIGURE22.11 When 22.122). However, when a Cr ion chromjumi{ll) nitrate dissolves is in an aqueous solution and in water, the resulting solution surrounded by an octahedral array has a distinctive violet color of water molecules in CriHyQ)."", caused by the presence of the energies of its 3d orbitals are Cr(Hy0)* ions. no longer all the same. The 3d. 3d,,, and 3d,, orbitals experience some increase in energy, but the energies of the 8d,?-,2and 3d,“orbitals increase even more (Figure 22.12b) because the lobes of the 3d,*-,*and 3 d7orbitals point directly toward the HyOQ molecules’ oxygen atoms at the corners of the octahedron formed by the ligands and are repelled by the electrons on those O atoms (Figure 22.12c). The energies of the 3d,,, 3d,., and 3d,. orbitals are not raised as much because the lobes of these three orbitals do not point directly toward the corners of the octahedron, so the electron repulsion they experience is weaker.UR FIGURE 22:12 Getahedral erystal feld splitting. (a) In an atom or ion in the ‘gas phase, all orbitals in a subshell are degenerate, as shown here for the five dd orbitals. (b) When an ion is part of a complex ion in a compound or solution, repulsions between electrons in the ion’s d orbitals and ligand electrons raise the energy of the orbitals, as shown here for an ectahedral field. (¢) The greatest repulsion is experienced by electrons in the doy? and d,2 orbitals because the lobes of these orbitals are directed toward the corners of the octahedron and so are closest to the lone pairs on the ligands (L). The lobes of the lower-energy dy, dz, and dz orbitals are directed soward points that lie between the corners of the octahedron, so electrons in them experience less repulsion. This process of changing degenerate (equal-energy) d orbitals into orbitals with different energies is known as crystal field splitting, and the difference in energy created by crystal field splitting is called crystal field splitting energy (4). The name was originally used 10 describe splitting of d-orbital energies in minerals, but the theory is also routinely applied to species in aqueous solutions. doy do 4 dap ds A, 4 by dye dee dy dye deg (a) Ground-state Cr** — (b) Excited-state Cr’* FIGURE 22:13 A Cr°* ion, [Arad ®, in an octahedral field can absorb a phoion of light that has energy (hv) equal to A,. This energy raises a Sd electron from (a) one of the lower-energy d orbitals to (b) one of the higher-energy d orbitals. EnergyIna Cr{H,Ol.** ion, three electrons are distributed among five dd orbitals. According to Hund’s rule, each of the three electrons should occupy one of the three lower-energy orbitals, leaving the two higher- energy orbitals unoccupied, as shown in Figure 22.18a. The energy difference between the two subsets of orbitals is symbolized by A,, where the subscript “o” indicates that the energy split was caused by an octahedral array of electron repulsions. Whar if an aqueous Cr ion absorbs a photon whose energy is exactly equal to A,? As the photon is absorbed, a 3d electron moves from a lower-energy orbital to a higher-energy orbital (Figure 22.13b). The wavelength | of the absorbed photon is related to the energy difference between the two groups of orbitals—in other words, to the crystal field splitting energy—as follows: ke t= = 2 E rn A, (22.2) The energy and wavelength of a photon are inversely proportional to each other (see Equation 7.3 in Section 7.3). Therefore, the larger the crystal field splitting in a complex ion, the shorter the wavelength of the photons the ion absorbs. CONNECTION Crystal field theoryis an example of molecular orbital theary, which was introduced in Section 9.6.‘The size of the energy gap between split d orbitals often ‘corresponds to radiation in the visible region of the electromagnetic spectrum. This means that the colors of solutions of metal complexes depend on the strengths of metal-ligand interactions that affect 4., ‘When white light (which contains all colors of visible light) passes ‘through a solution containing complex ions, the ions may absorb energy corresponding to one or more colors. So, the light leaving the solution and reaching our eyes is missing some colors. ‘The color we perceive for any transparent abject is not the color it absorbs but rather the color(s} that it transmits. To relate the color of asolution to the wavelengths of light it absorbs, we need to consider complementary colors as defined by a simple color wheel (Figure 22.14), For example, red and green are complementary colors, saa solution that absorbs green light appears red to us. Aqueous solutions of Cu? (Figure 18.1) are blue because ‘Cu(H,O)s** absorbs orange light, the color that is complementary to blue. A solution of Cu{NHy),2 ions also has a distinctive deep blue Red po Violet ax Orange FIGURE 2214 A color wheel. Golors on opposite sides af the wheel are complementary to each other. When we look at a solution or object that absorbs light corresponding to a given color, we see the complementary color. Wavelengths are in nanometers. color (Figure 22.15). The spectrum of a solution containing ‘Cu(NH,)," features a rather broad absorption band between 580 and 590 nm that spans yellow, orange, and red wavelengths. Once again, the complementary color is in the blue-violet region. If more than ‘one color is absorbed, then our brain processes the bands of transmitted colors and signals to us as the average of these colors. The violet color of the solution containing Cr!{ag) in Figure 22.11 is the ‘result of color averaging, as are the colors of the aqueous Ni*, Ni{NHq)s2>, and Ni(en),2* solutions in Figure 22.7, The nickel(11) and chromium(III) complexes we have examined up to this point were octahedral, and their central ions had a coordination number of 6. In the solution of Cu(NH,),2", however, the copper(I) ion has a coordination number of 4. This means that the deep blue calor of this complex ion is caused by a different crystal field.of teins FIGURE2215 The visible light transmitted by a solution of Cu(NHs)2° tons is missing much of the yellow, orange, and red portions of the visible spectrum because of a broad absorption band centered at $90 nm. Qur eyes and brain perceive the transmitted colors as navy blue. Four ligands around a central metal have either a tetrahedral arrangement ora square planar arrangement (Table 22.2). Square planar geometries tend to be limited to the transition metal ions with nearly filled valence-shell d orbitals, particularly thse with dor @ electron configurations. Cu®* has the electron configuration [Ar]3d®, and the Cu(NH),?> complex is square planar—which means that the strongest interactions occur between the 3d orbitals on the central ian. and the nitrogen atom lone pairs at the four corners of the equatorial plane of the octahedron, as shown in Figure 22.16. The d,?-,7orbital has the strongest interactions and the highest energy because its lobes are oriented directly at the four corners of the plane. The d,, orbital hhas slightly less energy because its lobes, although in the zy plane, are directed 45° away from the corners. Electrons in the three d orbitals with most of their electron density out of the zy plane (ie., d.?.d,., and d,.) interact even less with the lone pairs of the ligand and thus have even lower energies. Finally, let's consider the d orbital crystal field splitting that occurs in a tetrahedral complex (Figure 22.17a), In this geometry, the greatest electron-electron repulsions are experienced in the d., dye, and dz orbitals because the lobes of these orbitals are oriented most directly to the corners of the tetrahedron, which are occupied by ligand electron pairs (Figure 22.17b). The two other d orbitals (d."-,%and d.*) are less affected because their lobes do nat point toward the corners. ‘The difference in energy between the wo subsets of d orbitals in a tetrahedral geometry is labeled 4,.| apliming energies = Foe dtochitas in fe atom orion FIGURE2216 Square planar crystal field splitting. The d orbitals of a transition metal ion in a square planar feld are split into several energy levels depending on the relative orientations of the metal orbitals and ligand electrons at the four comers of the square. The d_2,? orbital has the highest energy because its lobes are directed right at the four corners of the square plane. Before ending this discussion on the colors of transition metal ions, let's revisit the color changes we saw in Figure 22.7, when first ammonia and then ethylenediamine were added to a solution of Ni (ag) ions. A green solution of Ni#‘(ag) ions absorbs at red light (725 nm) as shown in Table 22.5, Similarly, a blue solution of Ni(NHy).2" or a violet solution of Ni(en};® absorbs yellow light (570 nm) or green light (645 nm), respectively, Notice how the colors these three solutions absorb run from longest to shortest wavelength. Radiant energy is inversely proportional to wavelength (Equation 22.2); therefore, the crystal field splitting of the d orbitals of Ni? ions is en > NHy> Hy. ‘Table 22.4 summarizes the observed colors of these Ni ion complexes and the meaning we can infer from their colors.FIGURE 22.17 {aj In a tetrahedral complex ion, such as Zn{NH3),”, the d orbitals of the metal ion are split by a tetrahedral crystal feld. The tetrahedral ion fits inside a cube so that NHz molecules occupy opposite corners on the top and bottom face of the cube, The NHa ligands lie between the x, y, and z axes. (b) The lobes of the higher-energy orbitals (dz, dyz, and des) are closer to the ligands at the four corners of the tetrahedron than the lobes of the lower-energy orbitals (d222 and dy?) are, (One of the four corners of the tetrahedron is hidden in these drawings.) Chemists use the parameter field strength to describe the relative magnitude of the split in the energies of the d orbitals in metal ions, ranking ligands in what is called a spectrochemical series. Table 22.6 contains one such series. As the field strength of the ligand increases from the bottom to the top of Table 22.6, the crystal field splitting energy (4) increases. Consequently, high-field-strength ligands form complexes that absorb short-wavelength, high-energy light, whereas complexes of low-field-strength ligands absorb long-wavelength, low- energy light. The refinements of crystal field theory that have been made to better explain the spectrochemical series are beyond the scope of this book.TABLE 22.5 Light Transmitted and Absorbed by Three Ni2* Complexes witjoj2* NYa, i285 itend,2* eed TABLE 22.6 Spectrochemical Series of Some Common Ligands oN NO, en Py = NH EDTAY 4,0 e arHi concert Test Sis Figure 22.18 shows the absorption spectrum of a complex found in nature. What color is this complex ion? HIDE ANSWERS Green Absorption 400 500 600 700 Wavelength (nm) FIGURE 2218 Absorption spectrum.22.5 Magnetism and Spin States In addition to contributing to the color of transition metal ions, crystal field splitting influences their magnetic proper properties depend on the number of unpaired electrons in the valence shell d orbitals. The more unpaired electrons, the more paramagnetic the ion. For example, an Fe ion has five &d electrons (Figure 22.19). In an octahedral field there are two ways to distribute the five 3d. electrons among these orbitals. One arrangement conforms to Hund’s rule and has a single electron in each orbital, leaving them all unpaired (Figure 22.19b) and giving rise to the green color in aquamarine (Figure 22.19d). However, when A. is large, as shown in Figure 22.19c, all five electrons occupy the three lawer-energy orbitals. This pattern of electron distribution occurs when the energy of repulsion between two electrons in the same orbital is less than the energy needed to promote an electron to a higher-energy orbital. In this configuration, only one electron is unpaired. because these CONNECTION Weintroduced the magnetic behavior of matter in Section 9.6 in our iscussion of molecular orbital theory. ‘The configuration with all five electrons unpaired is called the Aigh- spin state because the spin on all five electrons is in the same direction, resulting in the maximum magnetic field produced by the spins. The configuration with only one electron unpaired is called the low-spin state. Both configurations are paramagnetic because both have at least one unpaired electron, but material containing high-spin iron dll) ions. would be more strongly attracted to an external magnet than a ‘material containing low-spin iron(1II) ions. FIGURE2219 Low-spin and high-spin complexes. (a) ‘The ground state of a free Fe® ion has a degenerate, half-flled set of 3d orbitals, (b) A weak octahedral feld (A, < clectron-pairing energy) produces the high-spin state: five unpaired electrons, each in its own orbital. (¢) Ina strong octahedral field (A, > electron-pairing energy), the energies of the orbitals are split enough to produce the low-spin state: two sets of paired electrons, one unpaired electron, and two empty, higher-enezgy orbitals. d) The Fe ions incrystals of aquamarine are high spin.‘Not all transition metal ions can have both high-spin and low-spin states. A Cr ion in an octahedral field, for instance, has only three 3d electrons (Figure 22.13), so each electron is unpaired whether the orbital energies are splita lot or only a liule. Therefore, Cr ions and any ion with less than four d electrons will have only one spin state. ‘Metal ions with eight or more electrons in d orbitals also have only ‘one spin state because there cannot be more than one or two unpaired electrons in these orbitals no matter how the electrons are distributed. = =! Mm CLD © AL! ggg | TE wi ib 3 FIGURE 22.20 Options for electron distribution. ay Energy al" SAMPLE EXERCISE Predicting Spin States. Los 24 Determine which of the following ions can have high-spin and low- spin configurations when surrounded by six Lewis bases in an octahedral complex: (a) Mn‘; (b} Mn; (¢) Gu®. Collect and Organize Mn and Gu are in groups 7 and I of the periodic table, so their atoms have 7 and 11 valence electrons, respectively. In an octahedral feld, a set of five d orbitals splits into a low-energy subset of three orbitals and a high-energy subset of two orbitals, Analyze ‘To determine whether high-spin and low-spin states are possible, we need to determine the number of d electrons in each ion. Then we need to distribute them among sets of d orbitals split by an octahedral field to see whether it is possible for the ions to have different spin states. The electron configurations for manganese and copper atoms are [ArJad “4s “for Mn and [Ar]8d !45!, respectively. When the transition metals Mn and Cu form cations, their atoms lose their 4s electrons first and then their dd electrons. Therefore, the numbers of d electrons in the ions are 3.in Mn‘, 5 in Mn, and 9 in. Gut, Itis likely that the ion with the fewest d electrons (Mn) and the one with nearly the most d electrons possible (Cu*+) will each have only one spin stateSolve a. Mn‘: Following Hund’s rule and putting three electrons inte the lowest-energy dd orbitals available and keeping them as unpaired as possible gives this orbital distribution of electrons (Figure 22.203). ‘There is only one spin state for Mn* b. Mn®: There are two options for distributing 5 electrons among the five 3d orbitals (Figure 22.206), Thus, Mn® can have a high-spin (on the lefi) or a low-spin (on the right) configuration in an octahedral field. c. Cu®: The # 8d electrons fill the lower-energy orbitals and nearly fill the higher-energy ones. Only one arrangement is possible, so Cu? has only one spin state (Figure 22.20c). Think About It In an octahedral Seld, metal ions with 4, 5,6, or 7d electrons can exist in high-spin and low-spin states. Those ions with 3 or fewer d electrons have only one spin state, in which all the electrons are unpaired and in the lower-energy set of orbitals. Jons with 8 or more d electrons have only one spin state because their lower-energy_ set of orbitals is Glled. The magnitude of the crystal field splitting energy, do, determines which spin state an ion with 4, 5, 6,0r7 electrons occupies. Practice Exercise Which of the following ions can have high-spin and low-spin configurations when part of an octahedral complex: (a) V%; (b) Cr+; (@) Ni? Are any of the possible spin configurations diamagnetic? HIDE ANSWERS ‘Ni** can have either a high-spin or a low-spin configuration; none of the ions is diamagnetic. ‘Ifthe energy needed to promote an electron toa higher-energy orbital (4.,) is greater than the energy from the repulsion experienced by two electrons sharing the same lower-energy orbital, a low spin state is observed. If 4, is less than the energy of repulsion, a high spin state is observed. Several factors affect the size of Ay. We have already discussed a major one in the context of the spectrochemical series shown in Table 22.6: the different field strengths of different ligands. Because molecules containing nitrogen atoms with lone pairs of electrons are stronger field-splitting ligands than HyO molecules, hydrated metal ions (small 4.) are more likely to be in high-spin states, and metals surrounded by nitrogen-containing ligands (large Ao) are more likely to be in low-spin states. Another factor affecting spin state is the oxidation state of the metal ion. The higher the oxidation number (and ionic charge), the stronger the attraction of the electron pairs on the ligands for the ion. Greater attraction leads to more ligand-d arbital interaction and therefore to a larger Ay.