35 minutes
32

Chelation, Biological Effects

The transition metals are elements with partially filled d orbitals, located in the d-block of the periodic table. The reactivity of the transition elements varies widely from very active metals such as scandium and iron to almost inert elements, such as the platinum metals. The type of chemistry used in the isolation of the elements from their ores depends upon the concentration of the element in its ore and the difficulty of reducing ions of the elements to the metals. Metals that are more active are more difficult to reduce. Transition metals exhibit chemical behavior typical of metals. For example, they oxidize in air upon heating and react with elemental halogens to form halides. Those elements that lie above hydrogen in the activity series react with acids, producing salts and hydrogen gas. Oxides, hydroxides, and carbonates of transition metal compounds in low oxidation states are basic. Halides and other salts are generally stable in water, although oxygen must be excluded in some cases. Most transition metals form a variety of stable oxidation states, allowing them to demonstrate a wide range of chemical reactivity. The transition elements and main group elements can form coordination compounds, or complexes, in which a central metal atom or ion is bonded to one or more ligands by coordinate covalent bonds.

32.1 Occurrence, Preparation, and Properties of Transition Metals and Their Compounds

Transition metals are defined as those elements that have (or readily form) partially filled d orbitals. As shown in Figure 32.1, the d-block elements in groups 3–11 are transition elements. The f-block elements, also called inner transition metals (the lanthanides and actinides), also meet this criterion because the d orbital is partially occupied before the f orbitals. The d orbitals fill with the copper family (group 11); for this reason, the next family (group 12) are technically not transition elements. However, the group 12 elements do display some of the same chemical properties and are commonly included in discussions of transition metals. Some chemists do treat the group 12 elements as transition metals.

Figure 32.1

The transition metals are located in groups 3–11 of the periodic table. The inner transition metals are in the two rows below the body of the table.

The Periodic Table of Elements is shown. The 18 columns are labeled “Group” and the 7 rows are labeled “Period.” Below the table to the right is a box labeled “Color Code” with different colors for metals, metalloids, and nonmetals, as well as solids, liquids, and gases. To the left of this box is an enlarged picture of the upper-left most box on the table. The number 1 is in its upper-left hand corner and is labeled “Atomic number.” The letter “H” is in the middle in red indicating that it is a gas. It is labeled “Symbol.” Below that is the number 1.008 which is labeled “Atomic Mass.” Below that is the word hydrogen which is labeled “name.” The color of the box indicates that it is a nonmetal. Each element will be described in this order: atomic number; name; symbol; whether it is a metal, metalloid, or nonmetal; whether it is a solid, liquid, or gas; and atomic mass. Beginning at the top left of the table, or period 1, group 1, is a box containing “1; hydrogen; H; nonmetal; gas; and 1.008.” There is only one other element box in period 1, group 18, which contains “2; helium; H e; nonmetal; gas; and 4.003.” Period 2, group 1 contains “3; lithium; L i; metal; solid; and 6.94” Group 2 contains “4; beryllium; B e; metal; solid; and 9.012.” Groups 3 through 12 are skipped and group 13 contains “5; boron; B; metalloid; solid; 10.81.” Group 14 contains “6; carbon; C; nonmetal; solid; and 12.01.” Group 15 contains “7; nitrogen; N; nonmetal; gas; and 14.01.” Group 16 contains “8; oxygen; O; nonmetal; gas; and 16.00.” Group 17 contains “9; fluorine; F; nonmetal; gas; and 19.00.” Group 18 contains “10; neon; N e; nonmetal; gas; and 20.18.” Period 3, group 1 contains “11; sodium; N a; metal; solid; and 22.99.” Group 2 contains “12; magnesium; M g; metal; solid; and 24.31.” Groups 3 through 12 are skipped again in period 3 and group 13 contains “13; aluminum; A l; metal; solid; and 26.98.” Group 14 contains “14; silicon; S i; metalloid; solid; and 28.09.” Group 15 contains “15; phosphorous; P; nonmetal; solid; and 30.97.” Group 16 contains “16; sulfur; S; nonmetal; solid; and 32.06.” Group 17 contains “17; chlorine; C l; nonmetal; gas; and 35.45.” Group 18 contains “18; argon; A r; nonmetal; gas; and 39.95.” Period 4, group 1 contains “19; potassium; K; metal; solid; and 39.10.” Group 2 contains “20; calcium; C a; metal; solid; and 40.08.” Group 3 contains “21; scandium; S c; metal; solid; and 44.96.” Group 4 contains “22; titanium; T i; metal; solid; and 47.87.” Group 5 contains “23; vanadium; V; metal; solid; and 50.94.” Group 6 contains “24; chromium; C r; metal; solid; and 52.00.” Group 7 contains “25; manganese; M n; metal; solid; and 54.94.” Group 8 contains “26; iron; F e; metal; solid; and 55.85.” Group 9 contains “27; cobalt; C o; metal; solid; and 58.93.” Group 10 contains “28; nickel; N i; metal; solid; and 58.69.” Group 11 contains “29; copper; C u; metal; solid; and 63.55.” Group 12 contains “30; zinc; Z n; metal; solid; and 65.38.” Group 13 contains “31; gallium; G a; metal; solid; and 69.72.” Group 14 contains “32; germanium; G e; metalloid; solid; and 72.63.” Group 15 contains “33; arsenic; A s; metalloid; solid; and 74.92.” Group 16 contains “34; selenium; S e; nonmetal; solid; and 78.97.” Group 17 contains “35; bromine; B r; nonmetal; liquid; and 79.90.” Group 18 contains “36; krypton; K r; nonmetal; gas; and 83.80.” Period 5, group 1 contains “37; rubidium; R b; metal; solid; and 85.47.” Group 2 contains “38; strontium; S r; metal; solid; and 87.62.” Group 3 contains “39; yttrium; Y; metal; solid; and 88.91.” Group 4 contains “40; zirconium; Z r; metal; solid; and 91.22.” Group 5 contains “41; niobium; N b; metal; solid; and 92.91.” Group 6 contains “42; molybdenum; M o; metal; solid; and 95.95.” Group 7 contains “43; technetium; T c; metal; solid; and 97.” Group 8 contains “44; ruthenium; R u; metal; solid; and 101.1.” Group 9 contains “45; rhodium; R h; metal; solid; and 102.9.” Group 10 contains “46; palladium; P d; metal; solid; and 106.4.” Group 11 contains “47; silver; A g; metal; solid; and 107.9.” Group 12 contains “48; cadmium; C d; metal; solid; and 112.4.” Group 13 contains “49; indium; I n; metal; solid; and 114.8.” Group 14 contains “50; tin; S n; metal; solid; and 118.7.” Group 15 contains “51; antimony; S b; metalloid; solid; and 121.8.” Group 16 contains “52; tellurium; T e; metalloid; solid; and 127.6.” Group 17 contains “53; iodine; I; nonmetal; solid; and 126.9.” Group 18 contains “54; xenon; X e; nonmetal; gas; and 131.3.” Period 6, group 1 contains “55; cesium; C s; metal; solid; and 132.9.” Group 2 contains “56; barium; B a; metal; solid; and 137.3.” Group 3 breaks the pattern. The box has a large arrow pointing to a row of elements below the table with atomic numbers ranging from 57-71. In sequential order by atomic number, the first box in this row contains “57; lanthanum; L a; metal; solid; and 138.9.” To its right, the next is “58; cerium; C e; metal; solid; and 140.1.” Next is “59; praseodymium; P r; metal; solid; and 140.9.” Next is “60; neodymium; N d; metal; solid; and 144.2.” Next is “61; promethium; P m; metal; solid; and 145.” Next is “62; samarium; S m; metal; solid; and 150.4.” Next is “63; europium; E u; metal; solid; and 152.0.” Next is “64; gadolinium; G d; metal; solid; and 157.3.” Next is “65; terbium; T b; metal; solid; and 158.9.” Next is “66; dysprosium; D y; metal; solid; and 162.5.” Next is “67; holmium; H o; metal; solid; and 164.9.” Next is “68; erbium; E r; metal; solid; and 167.3.” Next is “69; thulium; T m; metal; solid; and 168.9.” Next is “70; ytterbium; Y b; metal; solid; and 173.1.” The last in this special row is “71; lutetium; L u; metal; solid; and 175.0.” Continuing in period 6, group 4 contains “72; hafnium; H f; metal; solid; and 178.5.” Group 5 contains “73; tantalum; T a; metal; solid; and 180.9.” Group 6 contains “74; tungsten; W; metal; solid; and 183.8.” Group 7 contains “75; rhenium; R e; metal; solid; and 186.2.” Group 8 contains “76; osmium; O s; metal; solid; and 190.2.” Group 9 contains “77; iridium; I r; metal; solid; and 192.2.” Group 10 contains “78; platinum; P t; metal; solid; and 195.1.” Group 11 contains “79; gold; A u; metal; solid; and 197.0.” Group 12 contains “80; mercury; H g; metal; liquid; and 200.6.” Group 13 contains “81; thallium; T l; metal; solid; and 204.4.” Group 14 contains “82; lead; P b; metal; solid; and 207.2.” Group 15 contains “83; bismuth; B i; metal; solid; and 209.0.” Group 16 contains “84; polonium; P o; metal; solid; and 209.” Group 17 contains “85; astatine; A t; metalloid; solid; and 210.” Group 18 contains “86; radon; R n; nonmetal; gas; and 222.” Period 7, group 1 contains “87; francium; F r; metal; solid; and 223.” Group 2 contains “88; radium; R a; metal; solid; and 226.” Group 3 breaks the pattern much like what occurs in period 6. A large arrow points from the box in period 7, group 3 to a special row containing the elements with atomic numbers ranging from 89-103, just below the row which contains atomic numbers 57-71. In sequential order by atomic number, the first box in this row contains “89; actinium; A c; metal; solid; and 227.” To its right, the next is “90; thorium; T h; metal; solid; and 232.0.” Next is “91; protactinium; P a; metal; solid; and 231.0.” Next is “92; uranium; U; metal; solid; and 238.0.” Next is “93; neptunium; N p; metal; solid; and N p.” Next is “94; plutonium; P u; metal; solid; and 244.” Next is “95; americium; A m; metal; solid; and 243.” Next is “96; curium; C m; metal; solid; and 247.” Next is “97; berkelium; B k; metal; solid; and 247.” Next is “98; californium; C f; metal; solid; and 251.” Next is “99; einsteinium; E s; metal; solid; and 252.” Next is “100; fermium; F m; metal; solid; and 257.” Next is “101; mendelevium; M d; metal; solid; and 258.” Next is “102; nobelium; N o; metal; solid; and 259.” The last in this special row is “103; lawrencium; L r; metal; solid; and 262.” Continuing in period 7, group 4 contains “104; rutherfordium; R f; metal; solid; and 267.” Group 5 contains “105; dubnium; D b; metal; solid; and 270.” Group 6 contains “106; seaborgium; S g; metal; solid; and 271.” Group 7 contains “107; bohrium; B h; metal; solid; and 270.” Group 8 contains “108; hassium; H s; metal; solid; and 277.” Group 9 contains “109; meitnerium; M t; not indicated; solid; and 276.” Group 10 contains “110; darmstadtium; D s; not indicated; solid; and 281.” Group 11 contains “111; roentgenium; R g; not indicated; solid; and 282.” Group 12 contains “112; copernicium; C n; metal; liquid; and 285.” Group 13 contains “113; ununtrium; U u t; not indicated; solid; and 285.” Group 14 contains “114; flerovium; F l; not indicated; solid; and 289.” Group 15 contains “115; ununpentium; U u p; not indicated; solid; and 288.” Group 16 contains “116; livermorium; L v; not indicated; solid; and 293.” Group 17 contains “117; ununseptium; U u s; not indicated; solid; and 294.” Group 18 contains “118; ununoctium; U u o; not indicated; solid; and 294.”

The d-block elements are divided into the first transition series (the elements Sc through Cu), the second transition series (the elements Y through Ag), and the third transition series (the element La and the elements Hf through Au). Actinium, Ac, is the first member of the fourth transition series, which also includes Rf through Rg.

The f-block elements are the elements Ce through Lu, which constitute the lanthanide series (or lanthanoid series), and the elements Th through Lr, which constitute the actinide series (or actinoid series). Because lanthanum behaves very much like the lanthanide elements, it is considered a lanthanide element, even though its electron configuration makes it the first member of the third transition series. Similarly, the behavior of actinium means it is part of the actinide series, although its electron configuration makes it the first member of the fourth transition series.

EXAMPLE 32.1.1

Valence Electrons in Transition Metals

Review how to write electron configurations, covered in the chapter on electronic structure and periodic properties of elements. Recall that for the transition and inner transition metals, it is necessary to remove the s electrons before the d or f electrons. Then, for each ion, give the electron configuration:

(a) cerium(III)

(b) lead(II)

(c) Ti2+

(d) Am3+

(e) Pd2+

For the examples that are transition metals, determine to which series they belong.

Solution

For ions, the s-valence electrons are lost prior to the d or f electrons.

(a) Ce3+[Xe]4f1; Ce3+ is an inner transition element in the lanthanide series.

(b) Pb2+[Xe]6s25d104f14; the electrons are lost from the p orbital. This is a main group element.
(c) titanium(II) [Ar]3d2; first transition series

(d) americium(III) [Rn]5f6; actinide

(e) palladium(II) [Kr]4d8; second transition series

Check Your Learning

Give an example of an ion from the first transition series with no d electrons.

V5+ is one possibility. Other examples include Sc3+, Ti4+, Cr6+, and Mn7+.

32.1.2 CHEMISTRY IN EVERYDAY LIFE

Uses of Lanthanides in Devices

Lanthanides (elements 57–71) are fairly abundant in the earth’s crust, despite their historic characterization as rare earth elements. Thulium, the rarest naturally occurring lanthanoid, is more common in the earth’s crust than silver (4.5 ×× 10−5% versus 0.79 ×× 10−5% by mass). There are 17 rare earth elements, consisting of the 15 lanthanoids plus scandium and yttrium. They are called rare because they were once difficult to extract economically, so it was rare to have a pure sample; due to similar chemical properties, it is difficult to separate any one lanthanide from the others. However, newer separation methods, such as ion exchange resins similar to those found in home water softeners, make the separation of these elements easier and more economical. Most ores that contain these elements have low concentrations of all the rare earth elements mixed together.

The commercial applications of lanthanides are growing rapidly. For example, europium is important in flat screen displays found in computer monitors, cell phones, and televisions. Neodymium is useful in laptop hard drives and in the processes that convert crude oil into gasoline (Figure 32.2). Holmium is found in dental and medical equipment. In addition, many alternative energy technologies rely heavily on lanthanoids. Neodymium and dysprosium are key components of hybrid vehicle engines and the magnets used in wind turbines.

Figure 32.2

(a) Europium is used in display screens for televisions, computer monitors, and cell phones. (b) Neodymium magnets are commonly found in computer hard drives. (credit b: modification of work by “KUERT Datenrettung”/Flickr)

This figure contains two images. Figure a shows a background with approximately half of the background to the upper right covered by a dark blue quarter circle. The remainder of the background is red. On top of this surface are 15 vertical columns of light blue dots, which are evenly spaced with gaps between them approximately equal to the width of the columns. In figure b, a computer hard drive is shown. It consists of a thin black plastic rectangular frame on which a thin disk with a metallic appearance is placed. A curved grey shape lies outside of this disk in the rectangular frame and is circled in red. This curved shape has a thin, pointed extension that reaches to the surface of the metallic disk.

As the demand for lanthanide materials has increased faster than supply, prices have also increased. In 2008, dysprosium cost $110/kg; by 2014, the price had increased to $470/kg. Increasing the supply of lanthanoid elements is one of the most significant challenges facing the industries that rely on the optical and magnetic properties of these materials.

The transition elements have many properties in common with other metals. They are almost all hard, high-melting solids that conduct heat and electricity well. They readily form alloys and lose electrons to form stable cations. In addition, transition metals form a wide variety of stable coordination compounds, in which the central metal atom or ion acts as a Lewis acid and accepts one or more pairs of electrons. Many different molecules and ions can donate lone pairs to the metal center, serving as Lewis bases. In this chapter, we shall focus primarily on the chemical behavior of the elements of the first transition series.

32.1.3 Properties of the Transition Elements

Transition metals demonstrate a wide range of chemical behaviors. As can be seen from their reduction potentials (see Appendix H), some transition metals are strong reducing agents, whereas others have very low reactivity. For example, the lanthanides all form stable 3+ aqueous cations. The driving force for such oxidations is similar to that of alkaline earth metals such as Be or Mg, forming Be2+ and Mg2+. On the other hand, materials like platinum and gold have much higher reduction potentials. Their ability to resist oxidation makes them useful materials for constructing circuits and jewelry.

Ions of the lighter d-block elements, such as Cr3+, Fe3+, and Co2+, form colorful hydrated ions that are stable in water. However, ions in the period just below these (Mo3+, Ru3+, and Ir2+) are unstable and react readily with oxygen from the air. The majority of simple, water-stable ions formed by the heavier d-block elements are oxyanions such as MoO42−MoO42− and ReO4.ReO4.

Ruthenium, osmium, rhodium, iridium, palladium, and platinum are the platinum metals. With difficulty, they form simple cations that are stable in water, and, unlike the earlier elements in the second and third transition series, they do not form stable oxyanions.

Both the d- and f-block elements react with nonmetals to form binary compounds; heating is often required. These elements react with halogens to form a variety of halides ranging in oxidation state from 1+ to 6+. On heating, oxygen reacts with all of the transition elements except palladium, platinum, silver, and gold. The oxides of these latter metals can be formed using other reactants, but they decompose upon heating. The f-block elements, the elements of group 3, and the elements of the first transition series except copper react with aqueous solutions of acids, forming hydrogen gas and solutions of the corresponding salts.

Transition metals can form compounds with a wide range of oxidation states. Some of the observed oxidation states of the elements of the first transition series are shown in Figure 32.3. As we move from left to right across the first transition series, we see that the number of common oxidation states increases at first to a maximum towards the middle of the table, then decreases. The values in the table are typical values; there are other known values, and it is possible to synthesize new additions. For example, in 2014, researchers were successful in synthesizing a new oxidation state of iridium (9+).

Figure 32.3

Transition metals of the first transition series can form compounds with varying oxidation states.

A table is shown with 10 columns and 8 rows. The first row is the header, which shows element symbols with atomic numbers as superscripts to the upper left of the element symbols. The following element symbols and numbers are shown in this manner; S c 21, T i 22, V 23, C r 24, M n 25, F e 26, C o 27, N i 28, C u 29, and Z n 30. The second row shows the value 1 plus under C u. The third row shows the value 2 plus under V, C r, M n, F e, C o, N i, C u, and Z n. The fourth row shows the value 3 plus under S c, T i, V, C r, M n, F e, C o, N i, and C u. The fifth row shows the value 4 plus under T I, V, C r, and M n. The sixth row shows the value 5 plus only under V. The seventh row shows the value 6 plus under C r, M n, and F e. The eighth row shows the value 7 plus under Mn.

For the elements scandium through manganese (the first half of the first transition series), the highest oxidation state corresponds to the loss of all of the electrons in both the s and d orbitals of their valence shells. The titanium(IV) ion, for example, is formed when the titanium atom loses its two 3d and two 4s electrons. These highest oxidation states are the most stable forms of scandium, titanium, and vanadium. However, it is not possible to continue to remove all of the valence electrons from metals as we continue through the series. Iron is known to form oxidation states from 2+ to 6+, with iron(II) and iron(III) being the most common. Most of the elements of the first transition series form ions with a charge of 2+ or 3+ that are stable in water, although those of the early members of the series can be readily oxidized by air.

The elements of the second and third transition series generally are more stable in higher oxidation states than are the elements of the first series. In general, the atomic radius increases down a group, which leads to the ions of the second and third series being larger than are those in the first series. Removing electrons from orbitals that are located farther from the nucleus is easier than removing electrons close to the nucleus. For example, molybdenum and tungsten, members of group 6, are limited mostly to an oxidation state of 6+ in aqueous solution. Chromium, the lightest member of the group, forms stable Cr3+ ions in water and, in the absence of air, less stable Cr2+ ions. The sulfide with the highest oxidation state for chromium is Cr2S3, which contains the Cr3+ ion. Molybdenum and tungsten form sulfides in which the metals exhibit oxidation states of 4+ and 6+.

EXAMPLE 32.1.4

Activity of the Transition Metals

Which is the strongest oxidizing agent in acidic solution: dichromate ion, which contains chromium(VI), permanganate ion, which contains manganese(VII), or titanium dioxide, which contains titanium(IV)?

Solution

First, we need to look up the reduction half reactions (in Appendix L) for each oxide in the specified oxidation state:
Cr2O72−+14H++6e2Cr3++7H2O+1.33 VCr2O72−+14H++6e2Cr3++7H2O+1.33 V
MnO4+8H++5eMn2++H2O+1.51 VMnO4+8H++5eMn2++H2O+1.51 V
TiO2+4H++2eTi2++2H2O−0.50 VTiO2+4H++2eTi2++2H2O−0.50 V

A larger reduction potential means that it is easier to reduce the reactant. Permanganate, with the largest reduction potential, is the strongest oxidizer under these conditions. Dichromate is next, followed by titanium dioxide as the weakest oxidizing agent (the hardest to reduce) of this set.

Check Your Learning

Predict what reaction (if any) will occur between HCl and Co(s), and between HBr and Pt(s). You will need to use the standard reduction potentials from Appendix L.

Answer

Co(s)+2HClH2+CoCl2(aq);Co(s)+2HClH2+CoCl2(aq); no reaction because Pt(s) will not be oxidized by H+

32.1.5 Preparation of the Transition Elements

Ancient civilizations knew about iron, copper, silver, and gold. The time periods in human history known as the Bronze Age and Iron Age mark the advancements in which societies learned to isolate certain metals and use them to make tools and goods. Naturally occurring ores of copper, silver, and gold can contain high concentrations of these metals in elemental form (Figure 32.4). Iron, on the other hand, occurs on earth almost exclusively in oxidized forms, such as rust (Fe2O3). The earliest known iron implements were made from iron meteorites. Surviving iron artifacts dating from approximately 4000 to 2500 BC are rare, but all known examples contain specific alloys of iron and nickel that occur only in extraterrestrial objects, not on earth. It took thousands of years of technological advances before civilizations developed iron smelting, the ability to extract a pure element from its naturally occurring ores and for iron tools to become common.

Figure 32.4

Transition metals occur in nature in various forms. Examples include (a) a nugget of copper, (b) a deposit of gold, and (c) an ore containing oxidized iron. (credit a: modification of work by http://images-of-elements.com/copper-2.jpg; credit c: modification of work by http://images-of-elements.com/iron-ore.jpg)

Three images are provided. In a, a smooth chunk of a copper-colored metal with an uneven surface is shown. In b, a dull gold chunk of a metal is shown. This chunk has a rough surface to which smaller chunks appear to be attached. In c, a rust colored chunk of a solid material with a dull surface is shown.

Generally, the transition elements are extracted from minerals found in a variety of ores. However, the ease of their recovery varies widely, depending on the concentration of the element in the ore, the identity of the other elements present, and the difficulty of reducing the element to the free metal.

In general, it is not difficult to reduce ions of the d-block elements to the free element. Carbon is a sufficiently strong reducing agent in most cases. However, like the ions of the more active main group metals, ions of the f-block elements must be isolated by electrolysis or by reduction with an active metal such as calcium.

We shall discuss the processes used for the isolation of iron, copper, and silver because these three processes illustrate the principal means of isolating most of the d-block metals. In general, each of these processes involves three principal steps: preliminary treatment, smelting, and refining.

  1. Preliminary treatment. In general, there is an initial treatment of the ores to make them suitable for the extraction of the metals. This usually involves crushing or grinding the ore, concentrating the metal-bearing components, and sometimes treating these substances chemically to convert them into compounds that are easier to reduce to the metal.
  2. Smelting. The next step is the extraction of the metal in the molten state, a process called smelting, which includes reduction of the metallic compound to the metal. Impurities may be removed by the addition of a compound that forms a slag—a substance with a low melting point that can be readily separated from the molten metal.
  3. Refining. The final step in the recovery of a metal is refining the metal. Low boiling metals such as zinc and mercury can be refined by distillation. When fused on an inclined table, low melting metals like tin flow away from higher-melting impurities. Electrolysis is another common method for refining metals.

32.1.6 Isolation of Iron

The early application of iron to the manufacture of tools and weapons was possible because of the wide distribution of iron ores and the ease with which iron compounds in the ores could be reduced by carbon. For a long time, charcoal was the form of carbon used in the reduction process. The production and use of iron became much more widespread about 1620, when coke was introduced as the reducing agent. Coke is a form of carbon formed by heating coal in the absence of air to remove impurities.

The first step in the metallurgy of iron is usually roasting the ore (heating the ore in air) to remove water, decomposing carbonates into oxides, and converting sulfides into oxides. The oxides are then reduced in a blast furnace that is 80–100 feet high and about 25 feet in diameter (Figure 32.5) in which the roasted ore, coke, and limestone (impure CaCO3) are introduced continuously into the top. Molten iron and slag are withdrawn at the bottom. The entire stock in a furnace may weigh several hundred tons.

Figure 32.5

Within a blast furnace, different reactions occur in different temperature zones. Carbon monoxide is generated in the hotter bottom regions and rises upward to reduce the iron oxides to pure iron through a series of reactions that take place in the upper regions.

A diagram of a blast furnace is shown. The furnace has a cylindrical shape that is oriented vertically. A pipe at the lower left side of the figure is shaded yellow and is labeled “Slag.” It connects to an interior chamber. Situated at a level just below this piping on the right side of the figure is another pipe that is shaded orange. It opens at the lower right side of the figure. The orange-shaded substance at the bottom of the chamber that matches the contents of the pipe to its right is labeled “Molten iron.” The pipe has an arrow exiting to the right pointing to the label “Outlet.” Just above the slag and molten iron regions is narrower tubing on both the left and right sides of the chamber which lead slightly up and out from the central chamber to small oval shapes. These shapes are labeled, “Preheated air.” The region just above the points of entry of these two pipes or tubes into the chamber is a white region in which small rust-colored chunks of material appear suspended. This region tapers slightly to the bottom of the furnace. The region above has an orange background in which small rust-colored chunks are similarly suspended. This region fills nearly half of the interior of the furnace. Above this region is a grey shaded region. At the very top of the furnace, black line segments indicate directed openings through which small rust-colored chunks of material appear to be entering the furnace from the top. This material is labeled, “Roasted ore, coke, limestone.” Exiting the grey shaded interior region to the right is a pipe. An arrow points right exiting the pipe pointing to the label “C O, C O subscript 2, N subscript 2.” At the right side of the figure, furnace heights are labeled in order of increasing height between the outlet pipes, followed by temperatures and associated chemical reactions. Just above the pipe labeled, “Outlet,” no chemical equation appears right of, “5 f t, 1510 degrees C.” To the right of, “15 f t, 1300 degrees C,” is the equation, “C plus O subscript 2 right pointing arrow C O subscript 2.” To the right of, “25 f t, 1125 degrees C,” are the two equations, “C a O plus S i O subscript 2 right pointing arrow C a S i O subscript 3” and “C plus C O subscript 2 right pointing arrow 2 C O.” To the right of, “35 f t, 945 degrees C,” are the two equations, “C a C O subscript 3 right pointing arrow C a O plus C O subscript 2,” and, “C plus C O subscript 2 right pointing arrow 2 C O.” To the right of, “45 f t, 865 degrees C,” is the equation, “C plus C O subscript 2 right pointing arrow 2 C O.” To the right of, “55 f t, 525 degrees C,” is the equation “F e O plus C O right pointing arrow F e plus C O subscript 2.” To the right of, “65 f t, 410 degrees C,” is the equation, “F e subscript 3 O subscript 4 plus C O right pointing arrow 3 F e O plus C O subscript 2.” To the right of “75 f t, 230 degrees C,” is the equation, “3 F e subscript 2 O subscript 3 plus C O right pointing arrow 2 F e subscript 3 O subscript 4 plus C O subscript 2.”

Near the bottom of a furnace are nozzles through which preheated air is blown into the furnace. As soon as the air enters, the coke in the region of the nozzles is oxidized to carbon dioxide with the liberation of a great deal of heat. The hot carbon dioxide passes upward through the overlying layer of white-hot coke, where it is reduced to carbon monoxide:

CO2(g)+C(s)2CO(g)CO2(g)+C(s)2CO(g)

The carbon monoxide serves as the reducing agent in the upper regions of the furnace. The individual reactions are indicated in Figure 32.5.

The iron oxides are reduced in the upper region of the furnace. In the middle region, limestone (calcium carbonate) decomposes, and the resulting calcium oxide combines with silica and silicates in the ore to form slag. The slag is mostly calcium silicate and contains most of the commercially unimportant components of the ore:

CaO(s)+SiO2(s)CaSiO3(l)CaO(s)+SiO2(s)CaSiO3(l)

Just below the middle of the furnace, the temperature is high enough to melt both the iron and the slag. They collect in layers at the bottom of the furnace; the less dense slag floats on the iron and protects it from oxidation. Several times a day, the slag and molten iron are withdrawn from the furnace. The iron is transferred to casting machines or to a steelmaking plant (Figure 32.6).

Figure 32.6

Molten iron is shown being cast as steel. (credit: Clint Budd)

This figure shows a photo of molten iron. A bright yellow-orange glow appears just left of center in the figure. Smoke appears to be rising toward the top center of the figure. Just below and to the right, sparks appear to be falling.

Much of the iron produced is refined and converted into steel. Steel is made from iron by removing impurities and adding substances such as manganese, chromium, nickel, tungsten, molybdenum, and vanadium to produce alloys with properties that make the material suitable for specific uses. Most steels also contain small but definite percentages of carbon (0.04%–2.5%). However, a large part of the carbon contained in iron must be removed in the manufacture of steel; otherwise, the excess carbon would make the iron brittle.

32.1.7 Isolation of Copper

The most important ores of copper contain copper sulfides (such as covellite, CuS), although copper oxides (such as tenorite, CuO) and copper hydroxycarbonates [such as malachite, Cu2(OH)2CO3] are sometimes found. In the production of copper metal, the concentrated sulfide ore is roasted to remove part of the sulfur as sulfur dioxide. The remaining mixture, which consists of Cu2S, FeS, FeO, and SiO2, is mixed with limestone, which serves as a flux (a material that aids in the removal of impurities), and heated. Molten slag forms as the iron and silica are removed by Lewis acid-base reactions:

CaCO3(s)+SiO2(s)CaSiO3(l)+CO2(g)CaCO3(s)+SiO2(s)CaSiO3(l)+CO2(g)
FeO(s)+SiO2(s)FeSiO3(l)FeO(s)+SiO2(s)FeSiO3(l)

In these reactions, the silicon dioxide behaves as a Lewis acid, which accepts a pair of electrons from the Lewis base (the oxide ion).

Reduction of the Cu2S that remains after smelting is accomplished by blowing air through the molten material. The air converts part of the Cu2S into Cu2O. As soon as copper(I) oxide is formed, it is reduced by the remaining copper(I) sulfide to metallic copper:

2Cu2S(l)+3O2(g)2Cu2O(l)+2SO2(g)2Cu2S(l)+3O2(g)2Cu2O(l)+2SO2(g)
2Cu2O(l)+Cu2S(l)6Cu(l)+SO2(g)2Cu2O(l)+Cu2S(l)6Cu(l)+SO2(g)

The copper obtained in this way is called blister copper because of its characteristic appearance, which is due to the air blisters it contains (Figure 32.7). This impure copper is cast into large plates, which are used as anodes in the electrolytic refining of the metal (which is described in the chapter on electrochemistry).

Figure 32.7

Blister copper is obtained during the conversion of copper-containing ore into pure copper. (credit: “Tortie tude”/Wikimedia Commons)

This figure shows a large, dull, black, lumpy mass with small, metallic flecks displayed on a clear, colorless rectangular solid base.

32.1.8 Isolation of Silver

Silver sometimes occurs in large nuggets (Figure 32.8) but more frequently in veins and related deposits. At one time, panning was an effective method of isolating both silver and gold nuggets. Due to their low reactivity, these metals, and a few others, occur in deposits as nuggets. The discovery of platinum was due to Spanish explorers in Central America mistaking platinum nuggets for silver. When the metal is not in the form of nuggets, it often useful to employ a process called hydrometallurgy to separate silver from its ores. Hydrology involves the separation of a metal from a mixture by first converting it into soluble ions and then extracting and reducing them to precipitate the pure metal. In the presence of air, alkali metal cyanides readily form the soluble dicyanoargentate(I) ion, [Ag(CN)2],[Ag(CN)2], from silver metal or silver-containing compounds such as Ag2S and AgCl. Representative equations are:

4Ag(s)+8CN(aq)+O2(g)+2H2O(l)4[Ag(CN)2](aq)+4OH(aq)4Ag(s)+8CN(aq)+O2(g)+2H2O(l)4[Ag(CN)2](aq)+4OH(aq)
2Ag2S(s)+8CN(aq)+O2(g)+2H2O(l)4[Ag(CN)2](aq)+2S(s)+4OH(aq)2Ag2S(s)+8CN(aq)+O2(g)+2H2O(l)4[Ag(CN)2](aq)+2S(s)+4OH(aq)
AgCl(s)+2CN(aq)[Ag(CN)2](aq)+Cl(aq)AgCl(s)+2CN(aq)[Ag(CN)2](aq)+Cl(aq)

Figure 32.8

Naturally occurring free silver may be found as nuggets (a) or in veins (b). (credit a: modification of work by “Teravolt”/Wikimedia Commons; credit b: modification of work by James St. John)

This figure contains two images. The first is of a small clump of bronze-colored metal with a very rough, irregular surface. The second shows a layer-like region of silver metal embedded in rock.

The silver is precipitated from the cyanide solution by the addition of either zinc or iron(II) ions, which serves as the reducing agent:

2[Ag(CN)2](aq)+Zn(s)2Ag(s)+[Zn(CN)4]2−(aq)2[Ag(CN)2](aq)+Zn(s)2Ag(s)+[Zn(CN)4]2−(aq)

EXAMPLE 32.1.9

Refining Redox

One of the steps for refining silver involves converting silver into dicyanoargenate(I) ions:
4Ag(s)+8CN(aq)+O2(g)+2H2O(l)4[Ag(CN)2](aq)+4OH(aq)4Ag(s)+8CN(aq)+O2(g)+2H2O(l)4[Ag(CN)2](aq)+4OH(aq)

Explain why oxygen must be present to carry out the reaction. Why does the reaction not occur as:

4Ag(s)+8CN(aq)4[Ag(CN)2](aq)?4Ag(s)+8CN(aq)4[Ag(CN)2](aq)?

Solution

The charges, as well as the atoms, must balance in reactions. The silver atom is being oxidized from the 0 oxidation state to the 1+ state. Whenever something loses electrons, something must also gain electrons (be reduced) to balance the equation. Oxygen is a good oxidizing agent for these reactions because it can gain electrons to go from the 0 oxidation state to the 2− state.

Check Your Learning

During the refining of iron, carbon must be present in the blast furnace. Why is carbon necessary to convert iron oxide into iron?

The carbon is converted into CO, which is the reducing agent that accepts electrons so that iron(III) can be reduced to iron(0).

32.1.10 Transition Metal Compounds

The bonding in the simple compounds of the transition elements ranges from ionic to covalent. In their lower oxidation states, the transition elements form ionic compounds; in their higher oxidation states, they form covalent compounds or polyatomic ions. The variation in oxidation states exhibited by the transition elements gives these compounds a metal-based, oxidation-reduction chemistry. The chemistry of several classes of compounds containing elements of the transition series follows.

32.1.10.1 Halides

Anhydrous halides of each of the transition elements can be prepared by the direct reaction of the metal with halogens. For example:

2Fe(s)+3Cl2(g)2FeCl3(s)2Fe(s)+3Cl2(g)2FeCl3(s)

Heating a metal halide with additional metal can be used to form a halide of the metal with a lower oxidation state:

Fe(s)+2FeCl3(s)3FeCl2(s)Fe(s)+2FeCl3(s)3FeCl2(s)

The stoichiometry of the metal halide that results from the reaction of the metal with a halogen is determined by the relative amounts of metal and halogen and by the strength of the halogen as an oxidizing agent. Generally, fluorine forms fluoride-containing metals in their highest oxidation states. The other halogens may not form analogous compounds.

In general, the preparation of stable water solutions of the halides of the metals of the first transition series is by the addition of a hydrohalic acid to carbonates, hydroxides, oxides, or other compounds that contain basic anions. Sample reactions are:

NiCO3(s)+2HF(aq)NiF2(aq)+H2O(l)+CO2(g)NiCO3(s)+2HF(aq)NiF2(aq)+H2O(l)+CO2(g)
Co(OH)2(s)+2HBr(aq)CoBr2(aq)+2H2O(l)Co(OH)2(s)+2HBr(aq)CoBr2(aq)+2H2O(l)

Most of the first transition series metals also dissolve in acids, forming a solution of the salt and hydrogen gas. For example:

Cr(s)+2HCl(aq)CrCl2(aq)+H2(g)Cr(s)+2HCl(aq)CrCl2(aq)+H2(g)

The polarity of bonds with transition metals varies based not only upon the electronegativities of the atoms involved but also upon the oxidation state of the transition metal. Remember that bond polarity is a continuous spectrum with electrons being shared evenly (covalent bonds) at one extreme and electrons being transferred completely (ionic bonds) at the other. No bond is ever 100% ionic, and the degree to which the electrons are evenly distributed determines many properties of the compound. Transition metal halides with low oxidation numbers form more ionic bonds. For example, titanium(II) chloride and titanium(III) chloride (TiCl2 and TiCl3) have high melting points that are characteristic of ionic compounds, but titanium(IV) chloride (TiCl4) is a volatile liquid, consistent with having covalent titanium-chlorine bonds. All halides of the heavier d-block elements have significant covalent characteristics.

The covalent behavior of the transition metals with higher oxidation states is exemplified by the reaction of the metal tetrahalides with water. Like covalent silicon tetrachloride, both the titanium and vanadium tetrahalides react with water to give solutions containing the corresponding hydrohalic acids and the metal oxides:

SiCl4(l)+2H2O(l)SiO2(s)+4HCl(aq)SiCl4(l)+2H2O(l)SiO2(s)+4HCl(aq)
TiCl4(l)+2H2O(l)TiO2(s)+4HCl(aq)TiCl4(l)+2H2O(l)TiO2(s)+4HCl(aq)

32.1.10.2 Oxides

As with the halides, the nature of bonding in oxides of the transition elements is determined by the oxidation state of the metal. Oxides with low oxidation states tend to be more ionic, whereas those with higher oxidation states are more covalent. These variations in bonding are because the electronegativities of the elements are not fixed values. The electronegativity of an element increases with increasing oxidation state. Transition metals in low oxidation states have lower electronegativity values than oxygen; therefore, these metal oxides are ionic. Transition metals in very high oxidation states have electronegativity values close to that of oxygen, which leads to these oxides being covalent.

The oxides of the first transition series can be prepared by heating the metals in air. These oxides are Sc2O3, TiO2, V2O5, Cr2O3, Mn3O4, Fe3O4, Co3O4, NiO, and CuO.

Alternatively, these oxides and other oxides (with the metals in different oxidation states) can be produced by heating the corresponding hydroxides, carbonates, or oxalates in an inert atmosphere. Iron(II) oxide can be prepared by heating iron(II) oxalate, and cobalt(II) oxide is produced by heating cobalt(II) hydroxide:

FeC2O4(s)FeO(s)+CO(g)+CO2(g)FeC2O4(s)FeO(s)+CO(g)+CO2(g)
Co(OH)2(s)CoO(s)+H2O(g)Co(OH)2(s)CoO(s)+H2O(g)

With the exception of CrO3 and Mn2O7, transition metal oxides are not soluble in water. They can react with acids and, in a few cases, with bases. Overall, oxides of transition metals with the lowest oxidation states are basic (and react with acids), the intermediate ones are amphoteric, and the highest oxidation states are primarily acidic. Basic metal oxides at a low oxidation state react with aqueous acids to form solutions of salts and water. Examples include the reaction of cobalt(II) oxide accepting protons from nitric acid, and scandium(III) oxide accepting protons from hydrochloric acid:

CoO(s)+2HNO3(aq)Co(NO3)2(aq)+H2O(l)CoO(s)+2HNO3(aq)Co(NO3)2(aq)+H2O(l)
Sc2O3(s)+6HCl(aq)2ScCl3(aq)+3H2O(l)Sc2O3(s)+6HCl(aq)2ScCl3(aq)+3H2O(l)

The oxides of metals with oxidation states of 4+ are amphoteric, and most are not soluble in either acids or bases. Vanadium(V) oxide, chromium(VI) oxide, and manganese(VII) oxide are acidic. They react with solutions of hydroxides to form salts of the oxyanions VO43−,VO43−, CrO42−,CrO42−, and MnO4.MnO4. For example, the complete ionic equation for the reaction of chromium(VI) oxide with a strong base is given by:

CrO3(s)+2Na+(aq)+2OH(aq)2Na+(aq)+CrO42−(aq)+H2O(l)CrO3(s)+2Na+(aq)+2OH(aq)2Na+(aq)+CrO42−(aq)+H2O(l)

Chromium(VI) oxide and manganese(VII) oxide react with water to form the acids H2CrO4 and HMnO4, respectively.

32.1.10.3 Hydroxides

When a soluble hydroxide is added to an aqueous solution of a salt of a transition metal of the first transition series, a gelatinous precipitate forms. For example, adding a solution of sodium hydroxide to a solution of cobalt sulfate produces a gelatinous pink or blue precipitate of cobalt(II) hydroxide. The net ionic equation is:

Co2+(aq)+2OH(aq)Co(OH)2(s)Co2+(aq)+2OH(aq)Co(OH)2(s)

In this and many other cases, these precipitates are hydroxides containing the transition metal ion, hydroxide ions, and water coordinated to the transition metal. In other cases, the precipitates are hydrated oxides composed of the metal ion, oxide ions, and water of hydration:

4Fe3+(aq)+6OH(aq)+nH2O(l)2Fe2O3·(n+3)H2O(s)4Fe3+(aq)+6OH(aq)+nH2O(l)2Fe2O3·(n+3)H2O(s)

These substances do not contain hydroxide ions. However, both the hydroxides and the hydrated oxides react with acids to form salts and water. When precipitating a metal from solution, it is necessary to avoid an excess of hydroxide ion, as this may lead to complex ion formation as discussed later in this chapter. The precipitated metal hydroxides can be separated for further processing or for waste disposal.

32.1.10.4 Carbonates

Many of the elements of the first transition series form insoluble carbonates. It is possible to prepare these carbonates by the addition of a soluble carbonate salt to a solution of a transition metal salt. For example, nickel carbonate can be prepared from solutions of nickel nitrate and sodium carbonate according to the following net ionic equation:

Ni2+(aq)+CO32−NiCO3(s)Ni2+(aq)+CO32−NiCO3(s)

The reactions of the transition metal carbonates are similar to those of the active metal carbonates. They react with acids to form metals salts, carbon dioxide, and water. Upon heating, they decompose, forming the transition metal oxides.

32.1.10.5 Other Salts

In many respects, the chemical behavior of the elements of the first transition series is very similar to that of the main group metals. In particular, the same types of reactions that are used to prepare salts of the main group metals can be used to prepare simple ionic salts of these elements.

A variety of salts can be prepared from metals that are more active than hydrogen by reaction with the corresponding acids: Scandium metal reacts with hydrobromic acid to form a solution of scandium bromide:

2Sc(s)+6HBr(aq)2ScBr3(aq)+3H2(g)2Sc(s)+6HBr(aq)2ScBr3(aq)+3H2(g)

The common compounds that we have just discussed can also be used to prepare salts. The reactions involved include the reactions of oxides, hydroxides, or carbonates with acids. For example:

Ni(OH)2(s)+2H3O+(aq)+2ClO4(aq)Ni2+(aq)+2ClO4(aq)+4H2O(l)Ni(OH)2(s)+2H3O+(aq)+2ClO4(aq)Ni2+(aq)+2ClO4(aq)+4H2O(l)

Substitution reactions involving soluble salts may be used to prepare insoluble salts. For example:

Ba2+(aq)+2Cl(aq)+2K+(aq)+CrO42−(aq)BaCrO4(s)+2K+(aq)+2Cl(aq)Ba2+(aq)+2Cl(aq)+2K+(aq)+CrO42−(aq)BaCrO4(s)+2K+(aq)+2Cl(aq)

In our discussion of oxides in this section, we have seen that reactions of the covalent oxides of the transition elements with hydroxides form salts that contain oxyanions of the transition elements.

32.1.11 HOW SCIENCES INTERCONNECT

High Temperature Superconductors

A superconductor is a substance that conducts electricity with no resistance. This lack of resistance means that there is no energy loss during the transmission of electricity. This would lead to a significant reduction in the cost of electricity.

Most currently used, commercial superconducting materials, such as NbTi and Nb3Sn, do not become superconducting until they are cooled below 23 K (−250 °C). This requires the use of liquid helium, which has a boiling temperature of 4 K and is expensive and difficult to handle. The cost of liquid helium has deterred the widespread application of superconductors.

One of the most exciting scientific discoveries of the 1980s was the characterization of compounds that exhibit superconductivity at temperatures above 90 K. (Compared to liquid helium, 90 K is a high temperature.) Typical among the high-temperature superconducting materials are oxides containing yttrium (or one of several rare earth elements), barium, and copper in a 1:2:3 ratio. The formula of the ionic yttrium compound is YBa2Cu3O7.

The new materials become superconducting at temperatures close to 90 K (Figure 32.9), temperatures that can be reached by cooling with liquid nitrogen (boiling temperature of 77 K). Not only are liquid nitrogen-cooled materials easier to handle, but the cooling costs are also about 1000 times lower than for liquid helium.

Further advances during the same period included materials that became superconducting at even higher temperatures and with a wider array of materials. The DuPont team led by Uma Chowdry and Arthur Sleight identified Bismouth-Strontium-Copper-Oxides that became superconducting at temperatures as high as 110 K and, importantly, did not contain rare earth elements. Advances continued through the subsequent decades until, in 2020, a team led by Ranga Dias at University of Rochester announced the development of a room-temperature superconductor, opening doors to widespread applications. More research and development is needed to realize the potential of these materials, but the possibilities are very promising.

Figure 32.9

The resistance of the high-temperature superconductor YBa2Cu3O7 varies with temperature. Note how the resistance falls to zero below 92 K, when the substance becomes superconducting.

A graph is shown. “Temperature (K)” appears on the horizontal axis, with axis labels present at 0, 100, 200, and 300. The vertical axis is labeled, “Resistance.” This axis begins at 0 and no additional markings are given. The upper end of this axis is terminated with an arrow head pointing upward unlike the horizontal axis. From the origin, a red line segment extends right to a point just left of 100 K. From this point, the plot continues with a vertical red line segment about five sixths of the way to the top of the graph. From the top of this line segment, another red line segment extends up and nearly to the top of the graph to the right.

Although the brittle, fragile nature of these materials presently hampers their commercial applications, they have tremendous potential that researchers are hard at work improving their processes to help realize. Superconducting transmission lines would carry current for hundreds of miles with no loss of power due to resistance in the wires. This could allow generating stations to be located in areas remote from population centers and near the natural resources necessary for power production. The first project demonstrating the viability of high-temperature superconductor power transmission was established in New York in 2008.

Researchers are also working on using this technology to develop other applications, such as smaller and more powerful microchips. In addition, high-temperature superconductors can be used to generate magnetic fields for applications such as medical devices, magnetic levitation trains, and containment fields for nuclear fusion reactors (Figure 32.10).

Figure 32.10

(a) This magnetic levitation train (or maglev) uses superconductor technology to move along its tracks. (b) A magnet can be levitated using a dish like this as a superconductor. (credit a: modification of work by Alex Needham; credit b: modification of work by Kevin Jarrett)

A photo is shown of a white levitation train on its tracks. A building appears to the right in the background.

32.2 Coordination Chemistry of Transition Metals

Learning Objectives

By the end of this section, you will be able to:

  • List the defining traits of coordination compounds
  • Describe the structures of complexes containing monodentate and polydentate ligands
  • Use standard nomenclature rules to name coordination compounds

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 32.11). In the remainder of this chapter, we will consider the structure and bonding of these remarkable compounds.

Figure 32.11

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)

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.

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 32.12). 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.

Figure 32.12

(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.)

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.

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 32.13). 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.

Figure 32.13

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.

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.

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 32.14). 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.

Figure 32.14

(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+[Co(en)3]3+ contains three of these ligands, each forming two bonds to the cobalt ion.

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.

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 32.14 showed one example of a chelate. The heme complex in hemoglobin is another important example (Figure 32.15). It contains a polydentate ligand with four donor atoms that coordinate to iron.

Figure 32.15

The single ligand heme contains four nitrogen atoms that coordinate to iron in hemoglobin to form a chelate.

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.

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, NH2CH2CO2NH2CH2CO2 (Figure 32.16) 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 32.15) is a tetradentate ligand.

Figure 32.16

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.

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.

32.2.1 The Naming of Complexes

The nomenclature of the complexes is patterned after a system suggested by Alfred Werner, a Swiss chemist and Nobel laureate, whose outstanding work more than 100 years ago laid the foundation for a clearer understanding of these compounds. The following five rules are used for naming complexes:

  1. If a coordination compound is ionic, name the cation first and the anion second, in accordance with the usual nomenclature.
  2. Name the ligands first, followed by the central metal. Name the ligands alphabetically. Negative ligands (anions) have names formed by adding -o to the stem name of the group. For examples, see Table 32.1. For most neutral ligands, the name of the molecule is used. The four common exceptions are aqua (H2O), ammine (NH3), carbonyl (CO), and nitrosyl (NO). For example, name [Pt(NH3)2Cl4] as diamminetetrachloroplatinum(IV).

    Table 32.17

    Examples of Anionic Ligands

    Anionic Ligand Name
    F fluoro
    Cl chloro
    Br bromo
    I iodo
    CN cyano
    NO3NO3 nitrato
    OH hydroxo
    O2– oxo
    C2O42−C2O42− oxalato
    CO32−CO32− carbonato
  3. If more than one ligand of a given type is present, the number is indicated by the prefixes di- (for two), tri- (for three), tetra- (for four), penta- (for five), and hexa- (for six). Sometimes, the prefixes bis- (for two), tris- (for three), and tetrakis- (for four) are used when the name of the ligand already includes di-, tri-, or tetra-, or when the ligand name begins with a vowel. For example, the ion bis(bipyridyl)osmium(II) uses bis- to signify that there are two ligands attached to Os, and each bipyridyl ligand contains two pyridine groups (C5H4N).

When the complex is either a cation or a neutral molecule, the name of the central metal atom is spelled exactly like the name of the element and is followed by a Roman numeral in parentheses to indicate its oxidation state (Table 32.2 and Table 32.3). When the complex is an anion, the suffix -ate is added to the stem of the name of the metal, followed by the Roman numeral designation of its oxidation state (Table 32.4). Sometimes, the Latin name of the metal is used when the English name is clumsy. For example, ferrate is used instead of ironate, plumbate instead leadate, and stannate instead of tinate. The oxidation state of the metal is determined based on the charges of each ligand and the overall charge of the coordination compound. For example, in [Cr(H2O)4Cl2]Br, the coordination sphere (in brackets) has a charge of 1+ to balance the bromide ion. The water ligands are neutral, and the chloride ligands are anionic with a charge of 1− each. To determine the oxidation state of the metal, we set the overall charge equal to the sum of the ligands and the metal: +1 = −2 + x, so the oxidation state (x) is equal to 3+.

Table 32.18

Examples in Which the Complex Is a Cation

[Co(NH3)6]Cl3 hexaamminecobalt(III) chloride
[Pt(NH3)4Cl2]2+ tetraamminedichloroplatinum(IV) ion
[Ag(NH3)2]+ diamminesilver(I) ion
[Cr(H2O)4Cl2]Cl tetraaquadichlorochromium(III) chloride
[Co(H2NCH2CH2NH2)3]2(SO4)3 tris(ethylenediamine)cobalt(III) sulfate

Table 32.19

Examples in Which the Complex Is Neutral

[Pt(NH3)2Cl4] diamminetetrachloroplatinum(IV)
[Ni(H2NCH2CH2NH2)2Cl2] dichlorobis(ethylenediamine)nickel(II)

Table 32.20

Examples in Which the Complex Is an Anion

[PtCl6]2− hexachloroplatinate(IV) ion
Na2[SnCl6] sodium hexachlorostannate(IV)

EXAMPLE 32.2.2

Coordination Numbers and Oxidation States

Determine the name of the following complexes and give the coordination number of the central metal atom.

(a) Na2[PtCl6]

(b) K3[Fe(C2O4)3]

(c) [Co(NH3)5Cl]Cl2

Solution

(a) There are two Na+ ions, so the coordination sphere has a negative two charge: [PtCl6]2−. There are six anionic chloride ligands, so −2 = −6 + x, and the oxidation state of the platinum is 4+. The name of the complex is sodium hexachloroplatinate(IV), and the coordination number is six. (b) The coordination sphere has a charge of 3− (based on the potassium) and the oxalate ligands each have a charge of 2−, so the metal oxidation state is given by −3 = −6 + x, and this is an iron(III) complex. The name is potassium trisoxalatoferrate(III) (note that tris is used instead of tri because the ligand name starts with a vowel). Because oxalate is a bidentate ligand, this complex has a coordination number of six. (c) In this example, the coordination sphere has a cationic charge of 2+. The NH3 ligand is neutral, but the chloro ligand has a charge of 1−. The oxidation state is found by +2 = −1 + x and is 3+, so the complex is pentaamminechlorocobalt(III) chloride and the coordination number is six.

Check Your Learning

The complex potassium dicyanoargenate(I) is used to make antiseptic compounds. Give the formula and coordination number.

K[Ag(CN)2]; coordination number two

Suggested Citation

General College Chemistry. https://edtechbooks.org/general_college_chemistry_2

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Flowers, P., et al. (2019). Chemistry: Atoms First 2e. https://openstax.org/details/books/chemistry-atoms-first-2e (19.1-19.2)
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