Lecture 15
Lecture 15
Lecture 15
Gerken Page89
Sc Ti V Cr Mn Fe Co Ni Cu Zn
Y Zr Nb Mo Tc Ru Rh Pd Ag Cd
Hf Ta W Re Os Ir Pt Au Hg
Rf Db Sg Bh Hs Mt
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Ac Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
The transition elements comprise those metals in Groups 3 to 12, i.e. the d-block elements, as well as the so-called “inner
transition elements” which are the lanthanides and actinides, also know as the f-block elements. These are all metallic
elements, so they are often called the transition metals, which we take to be synonymous with the transition elements. The
transition metals include many of the most important structural metals for an industrial society, including iron (Fe), chromium
(Cr), nickel (Ni) and copper (Cu). The text-book describes how some of these metals are won from their ores. Our focus in
lecture is going to be on coordination complexes of these elements.
We could study the properties of the transition elements in crystalline solids. However, there are complexities. First of all,
many additional crystal structure types would have to be studied. Many of these structures involve a large amount of covalent
bonding, so that our simple ionic model is not completely adequate. But in reality, we could do so, and the decision to move to
soluble coordination compounds is a deliberate one. The study of the transition metals in solids have been dominated by solid-
state physicists, and is closely tied to important technical advances, such as the development of the first Ruby lasers. Chemists
have been more involved in studying soluble metal complexes, and today these have become extremely important compounds
for industrial chemical processes (e.g. in the petrochemical and pharmaceutical industries), as well as in medicine an as model
systems for many plant and animal proteins and enzymes.
There is a strong conceptual relationship between the metals in a solid and in solution. In a coordination compound, we
surround the metal ion by the same kind of donor atoms as are in the anions found in their crystalline compounds. Thus, to
mimic an oxide environment, we can simply use water, or another oxygen-containing species. Of course, the metal ions will
act as Lewis acids (both hard and soft acids are found among the transition elements, as well as everything in between), and the
donor atoms act as Lewis bases. Thus coordination compounds are nothing more or less than Lewis acid-base complexes.
You should review your tables of hard and soft acids and bases at this time.
If we want to mimic a crystalline metal halide (from the hard fluoride to the soft iodide), we can employ the halogen
anions as the donor atoms. Alternatively, we can employ donor atoms such as nitrogen or carbon that are rare in solids,
although nitrides and carbides of these metals do exist. In summary, a coordination compound is a Lewis acid/base complex
that solubilizes the metal ion while preserving the local environment found in crystalline solids of these metals. The
coordination number of the central ion, the geometry and the nature of the donor atom found in solids can often be mimicked
quite accurately in soluble complexes.
¨: - :O:
:Cl :C O:
¨ H H
When a metal such as Fe2+ is dissolved in water, the resulting Fe2+(aq) ion is in reality a coordination complex between iron(II)
and water:
Fe2+ + 6 H2O → [Fe(OH2)6]2+ (here water is written OH2 to emphasize that the electron pair on oxygen of
water is acting as the Lewis base donor site to the metal; the charge on the resulting complex ion is simply the sum of the
charges of the metal ion and those on the ligands; square brackets are used to isolated the complex ion, and we refer to the six
water molecules as comprising the primary coordination sphere of the Fe(II) ion.
Copper(II) ions in the presence of a high concentration of chloride ion forms a chloro complex:
Cu2+ + 4 Cl- → [CuCl4]2- (here the overall charge is -2 since that is the sum of the ligands and the metal ion)
Nickel when finely divided reacts readily with an atmosphere of gaseous carbon monoxide to form the liquid nickel
tetracarbonyl:
Ni + 4 CO → [Ni(CO)4] (here the overall charge is 0, since the metal and the CO are all uncharged)
In summary, coordination compounds can be overall neutral, cationic or anionic, and the charge is the sum of all the
constituents. Charged complex compounds are called complex ions, and these can form salts with appropriate counter ions.
For example, the complexes mentioned above might be isolated as the salts [Fe(OH2)6]Br2 and K2[CuCl4]
You have already met several transition metal coordination complexes back during the Chemistry 2000 laboratory. For
example, in the first lab you prepared, and then analyzed, the complex salt K3[Fe(C2O4)3].3H2O. Later on, you determine the
relative number of thiocyanate and water ligands in complex ions of the type [Fe(SCN)n(H2O)6 - n](3-n)-. Several of the
compounds you may prepare in lab 6, the Thirteen Mystery Test Tubes, are in fact coordination compounds, while you may
also have met copper complexes [Cu(OH2)4]2+ and [Cu(NH3)4]2+. In the 2810 lab you will study the electronic spectra of a
number of simple aqua, chloro and ammine complexes of the d and f elements.
primary coordination sphere for six water molecules in the complex ion [Fe(OH2)6]3+, it only has room for three chelating
bidentate oxalate ions in the complex ion [Fe(C2O4)3]3-. Can you see why? The pictures show some computer-drawn "ball and
stick" diagrams of coordination complexes with chelating ligands. The structure of [Co(en)3]3+ is that of a complex cation,
which can be isolated from solution as a salt with any suitably charged anions. On the other hand, [CoEDTA] where the cobalt
is in the +3 oxidation state can be a neutral molecule (an hence is not particularly soluble in water.) Alternatively, you should
get used to interpreting simple line diagrams of typical coordination complexes, such as the following examples:
3-
O
C O
3+ C
2+ 2+ OH2 O
OH2 NH3 O
H2O OH2 C O O
Cu Cu Fe Fe
H2O OH2 H3N NH3 C
H2O OH2 O O O
OH2 NH3
OH2 O
C
C O
O
Perspective line drawings of some typical coordination complexes
We identify the total number of Lewis base attachments to a given metal center as the coordination number. Thus in the
example discussed above, both [Fe(OH2)6]3+ and [Fe(C2O4)3]3- have a coordination number of six. In fact the iron(III) ion does
not particularly care whether the six oxygen donor atoms come from six monodentate water molecules or three bidentate
oxalate ions. One of the most amazing ligands is EDTA, which supplies up to six donor atoms to a single metal ion, the ligand
wrapping around the metal and encasing it. EDTA4- is a hexadentate ligand. In general, chelating ligands have additional
stability over non-chelating or monodentate ligands. One of the reasons that the oxalate ion displaces H2O during the
preparation of [Fe(C2O4)3]3- in the Chem2000 lab experiment is that oxalate is a chelating ligand.
-O O -
H2NCH2CH2NH2 ethyelenediamine en ¨ H2 H2 ¨ bidentate 0
C C
H2N NH2
¨ ¨
C12H8N2 phenanthroline phen bidentate 0
N N
¨H H2 ¨
C10H12O8 ethylenediamine- EDTA C
2
C
hexadentate 4–
tetraacetato N N
-O C ¨ ¨ -
CO2
2
-O C CO
-
2 2
The table above lists a group of common ligands that you need to learn to be able to answer the assignment and test
questions for this course. You need to remember the name and abbreviation of each complex, the number of donor atoms, as
Chemistry 2810 Lecture Notes Dr. M. Gerken Page92
well as the overall charge on the ligand (typically either zero or some negative number; there do exist a very small number of
positively charged ligands, but these are extremely rare.) All questions will be restricted to complexes using only this small set
of ligands.
As you read through the rules, notice how they apply to the examples above:
1. In naming a coordination compound that is a salt, name the cation first and then the anion. (This is how all salts are
commonly named).
2. When giving the name of the complex ion or molecule, name the ligands first, in alphabetical order, followed by the name
of the metal.
a. If a ligand is an anion whose name ends in -ite or -ate, the final e is changed to o (as in sulfate → sulfato or nitrite →
nitrito).
b. If the ligand is an anion whose name ends in -ide, the ending is changed to o (as in chloride → chloro or cyanide →
cyano).
c. If the ligand is a neutral molecule, its common name is usually used. The important exceptions to this rule are water,
which is called aqua, ammonia, which is called ammine, and CO, called carbonyl.
d. When there is more than one of a particular monodentate ligand with a simple name, the number of ligands is
designated by the appropriate pre-fix: di, tri, tetra, penta, or hexa. If the ligand name is complicated (whether
monodentate or bidentate), the prefix changes to bis, tris, tetrakis, pentakis, or hexakis, followed by the ligand name in
parentheses.
3. If the complex ion is an anion, the suffix -ate is added to the metal name.
4. Following the name of the metal, the oxidation number of the metal is given in Roman numerals. Complexes can be
considerably more complicated than those described in this chapter; then, even more rules of nomenclature must be
applied. The brief rules just outlined, however, are sufficient for the vast majority of complexes.
complete salt which you will prepare next week in the laboratory: potassium trioxalatoferrate(III) trihydrate. That’s
quite a mouthful! You can see why, on the whole, chemists prefer a picture of a molecule to its name.
If CN = 4, the geometry may be one of two structures: square planar or tetrahedral. For example, the complexes
[Cu(OH2)4]2+ and [Cu(NH3)4]2+ are both tetrahedral, as indicated in the picture above. On the other hand, the complex
[Ni(CN)4]2- has the square-planar shape. Note that these shapes in general are not predictable by VSEPR theory. They must be
established by experiment. Isomerism is not possible in tetrahedral complexes unless all four attached groups are different.
This is an extremely rare situation for coordination compounds (but happens fairly frequently for sp3-hybridized carbon atoms).
One of the consequences of square planar geometry is that cis and trans isomers are possible. Such geometrical isomers
only show up if there are two different types of ligands present on the molecules. A very famous example of this kind of
isomerism occurs for the formula [PtCl2(NH3)2]. The cis form of this neutral coordination complex is a potent anticancer drug
know in medicine as cisplatin. The trans form has no antitumor activity at all, and is useless as a drug.
If CN = 6, the structure is almost always octahedral. This is also the most common geometry for transition metal
coordination complexes. Octahedral complexes have a wide range of possible isomers, depending on the type of ligands
attached. If the general formula is MX4Y2, cis and trans geometrical isomers are possible. On the other hand, if the general
formula is MX3Y3, mer and fac geometrical isomers are possible. Multidentate ligands can change the general picture. For
example M(X∩X)3 complexes, in which X∩X represents a chelating bidentate ligand, have only one feasible geometry;
however such complexes do form optical isomers. This means that they are chemically indistinguishable, but rotate plane
polarized light in opposite directions. You will learn more about optical isomers in introductory organic chemistry classes.
You should be aware, however, that optical isomerism is rooted purely in the geometry of the molecule, not in the types of
elements involved. Chelating complexes of the general formula M(X∩X)2Y2 can exist as cis and trans geometrical isomers.
The cis form of M(X∩X)2Y2 exists as two optical isomers as well.
2+ +
NH3 NH3 2+ NH3 +
Cl Cl Cl
H3N NH3
H3N NH3 H3N NH3 H3N NH3
Cl Pt Cl Cl Pt NH3 Pt
Pt Pt Pt
H3N Cl
NH3 Cl H3N NH3 H3N Cl Cl Cl
Cl
Cl Cl NH3
trans-[PtCl2(NH3)2] cis-[PtCl2(NH3)2]
trans-[PtCl2(NH3)4]2+ cis-[PtCl2(NH3)4]2+ mer-[PtCl3(NH3)3]+ fac-[PtCl3(NH3)3]+
All of these isomers are due to only to geometry.
You are encouraged to make some models and
prove to yourself that these differences are
possible, and that they are the only possible
variations. In addition, you should obtain the
point groups for each structure. The computer-
generated ball-and-stick diagrams at right
illustrate cis and trans isomerism for six-
coordinate octahedral shapes. Note that the cis
isomer in this case involves a chelating ligand, so
it will exist in two optical isomers, i.e. it is an
example of M(X∩X)2Y2. cis isomer of [Co(en)2Cl2]+ trans isomer of [Co(en)2Cl2]+
eg
t2g
t2
Finally, for square planar complexes, a third possibility occurs. The pattern here is more complicated, with dxz, and dyz
lowest, followed by dz2, dxy, and then dx2-y2. The spacing between the last two is called ∆SP, the square-planar crystal field
splitting energy. We will not consider the square planar case, except to say that typically ∆SP is very large.
{small orbital splitting, ∆} Halides < C2O42- < H2O < NH3 = en < phen < CN- {large orbital splitting, ∆}
Ligands at the left of the series are often called weak field ligands, while those at the right are strong field ligands.
d1 d2 d3 d8 d9 d10
d4 d5 d6 d7 d4 d5 d6 d7
"high spin" forms "low spin" forms
The high spin forms predominate for small orbital splitting, and with both water and oxalate ligands, most complexes will be
high spin. So the iron(II) and iron(III) complexes will have 5 and 4 unpaired electrons. On the other hand, if cyanide ligands
were present there would be large orbital splitting and the low spin forms would predominate, so that [Fe(CN)6]4- and
[Fe(CN)6]3- will have 1 and 0 unpaired electrons. Notice also that this last example is diamagnetic (for a definition, see Kotz
& Treichel, p. 358), while a free Fe3+ ion is definitely paramagnetic.
Exercise - Work out the possibilities that exist for tetrahedral crystal fields as a function of the d counts. For which can high
and low spin conditions exist (i.e. those cases where there is a net difference between the two distributions)? In fact, we need
only consider the high spin case, since tetrahedral crystal fields are too small to cause spin pairing.
Chemistry 2810 Lecture Notes Dr. M. Gerken Page96
d1 d2 d3 d1 d2 d3
d4 d5 d6 d7 d4 d5 d6 d7
d8 d9 d10 d8 d9 d10