Edited by
revi~i
ted
Some Aspects of Coordination Chemistry
Charles D. Mickey
Texas ABM University at Galveston, Galveston. TX 77553
Chemists have been intrieued hv coordination comnounds
for almost two centuries. ~ i e i h a c h , Prussian
a pigrnen&aker,
svnthesized the first metal coordination compound a t the
beginning of the 1Ahcentury.This iron hluc &ment,named
I'russ~an hlue, has the composition KFestCNk. The historiral
development of coordination chemistry begins, however, with
B. M. Tassaert's report (1) in 1798 of the discovery of
hexaamminecohalt(II1) chloride. ICo(NHl)clCL.
. -
".", The unusual
characteristics of this A d simil'a; compounds stimulated in-
terest and research in this area of inoreanic chemistrv. Since
the properties of such compounds seemed to defy explanation
by contemporary chemical theory they were characterized as
complex compounds.
Today coordination chemistry, the study of coordination
compounds, has emerged as one of the major focal points for
the inorganic chemist. I t covers a comprehensive range of
intriguing theoretical and practical applications. In industry,
coordination compounds play key roles in homogeneous and
heterogeneous catalysis, water purification, analytical
chemistry, solvent extraction, photography, metallurgy, and
-
electrochemistrv. In hiolow. thev are essential in manv life
processes such as oxygen transport and metal ion control.
Moreover. the studv of coordination comnounds has enabled
the inorganic chemist to mnke aignificant progress in refining
and amvlifvine the concept of chemical bondine and to ex-
plain th'r ir?luence that hhnding has on a comp&d's prop-
erties like its color and magnetic s~tsceptihility.
The Genesis of Modern Coordination Theory
By 1852, Sir Edward Frankland in England had proposed
the concept of valence (21, suggesting that each element f o m s
compounds by uniting with a definite number of other ele-
ments. In 1857. Friedrich A. Kekul6 in Germanv extended
Frankland's concept, advocating the tetravalenc; of carbon
(3).Subsequently, Kekul.6 proposed that carbon atoms com-
hine to form chains ( 4 ) . The theories extolled by Frankland
and Kekul.6 were crucial for developing a structural theory for
organic compounds; however, they did influence and hinder
the development of coordination theory. Thus, Christian W.
Blomstrand (5)proposed that ammonia molecules could form
-NH3- chains, resembling the -CH2- chains in organic
com~ounds.Bv extendine this idea. S o ~ h u Madss Joreensen
a chi& theory & account for the existence ormetal
comnlexes (6).Bv analogv to organic comnounds, he formu-
lated tetraammin~platin&n(II)chloride asshown in structure
Charles D. Mickey
Texas A 8 M at Galveston
Galveston. TX 77553
Although Jorgensen's conjectures seem unsophisticated now,
they were in accord with the available facts of his time. To his
credit, Jorgensen was an extraordinarily proficient experi-
mentalist and eventually participated in disproving his own
chain theory (7).
The Wernerian Sydern
The experimental facts finally were correctly interpreted
by Alfred Werner in Ziirich in 1893. Werner recognized with
amazing insight that metals in coordination com~oundshave
two kinds of valency. He expressed this concept in the fol-
lowing words (8):
Even when, to judge bythe valencenumber,the camhiningpawerof
certain atoms is exhausted, they still pmsess in most eases the power
of participating further in the construction of complex molecules with
the formation of vervdefinite atomic linkaees. The oossibilitv of this
action is to be traced back to the fact that.besides <he sffin& bonds
~ ~ ~~ ~
designated as princ~pnlvnlenries,*till other bundson the awms,rallrd
auxiliary vslenrres, may Ire rsllerl into arlim
I n modern parlance, Werner's principal and auxiliary
valencies correspond to the central atom's oxidation state and
coordination numher, respectively. Werner's concept of dual
atomic valency did much to clarify the idea of chemical
honding more than 20 years before the views of G. N. Lewis
(9) led to our present concept of ionic and covalent
honding.
The existence of geometrical isomers among coordination
compounds was first observed by Jorgensen (10) in dichlo-
robis(ethylenediamine)cohalt(III), chloride,- [CoCl~(en)]Cl,
where en is ethylenediamine, H ~ N C H ~ C H Z NJorgensen
H~.
mistakenly attributed the isomeric variations in the color
Th s featureis almed as a revlev of bawc
chemlca prlncoplss and as a reappraeal of
the state of the an Comments sJqqes-
tions for topics, and contributions &&id
be sent to the feature editor.
Charles Mlckey received his BS from
Trinity University in 1957. MA from St.
Mary's University in 1966, and his PhD
from Texas A 8 M University In 1973. He
taught chemistry at Alamo Heights Senior
Hioh School. San Antonio. Texas. for 13
ye&. He also has aver seven years universiiy experience,having taught
at San Antonio Juniw College and Texas A8M University. HB is pmssntiy
an Associate Professor of Chemistry in the Depattment of Marine
Science at the Galveston branch of Texas A&M.
[k. Mickey's excellence and dedication to teaching has been sighted
in his achievement of the ACS James Bryant Conant Award in 1970 and
the 1976-77 "Most Effective Teacher Award: Texas A 8 M University
at Galveston."
Volume 58 Number 3 March 1981 257
(green and violet) to structural isomerism related to the
bonding of the two ethylenediamine molecules as shown in
structures I1 and 111. Werner believed, however, these com-
pounds to he geometrical isomers: thus, he postulated directed
valency bonds and introduced the concept i f stereoisomerism,
i.e., compounds containing the same atoms and bonds that
differ in their spatial orientation. Consequently, Werner
suggested an octahedral disposition of bonds about the central
cobalt atom as shown in structures IV and V.
In the Wernerian system, complex inorganic compounds
contain a central atom functioning as the host for a coordi-
nation sohere. The coordination sohere consists of a discrete
numher bf anions or polar moleculks called ligands (from the
Latin limre.
- . to bind). The liaands are disposed in simple
geometrical patterns around the central atom as shownin
Figure 1.
Experimental Support for Werner's Coordination Theory
Werner, in order to visualize the structure of coordination
compounds, utilized experimental facts such as the following.
A series of cobalt(II1) ammine complexes containing different
numbers of moles of ammonia per mole of the comvlex had
been produced. Their empirical formulas and colors &he basis
of their trivial names) are listed in Table 1.
Werner and Miolati (11) measured the electrical conduc-
tivity of solutions of each complex and calculated the numher
of ionic components in each as shown in Table 1.Additionally,
Werner determined that the reactivities of the chloride ions
were substantially different among the various complexes. For
example, while silver nitrate would precipitate all the chloride
1 A", J CoCls.4NHs
Schematic representation of cwrdination spheres of cobalt(lll) complexes.
258 Journal of ~hernicaiEducation
from a solution of the luteo complex, it only precipitated
two-thirds of the chloride from solutions of the purpureo
complex and one-third from solutions of either the violeo or
praseo complexes. Furthermore, the triammine complex did
not react with silver nitrate. Werner interpreted these results
structurally and reasoned that in each complex, the metal ion
serves as host to different coordination spheres very much
as in Figure 1.
Werner explained that the formation of the purpureo
complex from the luteo complex occurred by evolution of one
ammonia molecule from the coordination sphere and its
suhsequent replacement by a chloride ion
25O'C
[CoCI(NHds]C12+ NH3
[Co(NHdslCls---+
With the conversion of the one chloride ion from a principal
valency to an auxiliary valency there is a concomitant dimi-
nution of the numher of ions available per mole of the com-
plex. This was also reflected by the conductivity measure-
ments (11) which showed that the purpureo complex only
contains three moles of ions per mole of complex. Another very
imvortant observation about this series of comnlexes is the
occurrence of tu,o rompoundi uf identical empiriral furmula,
CoCl.r4NH~,hut havine distinctlv different colurs. Werner
had &eadypredicted the existence of these cis-trans ste-
reoisomers from his octahedral hvvothesis. Furthermore, his
suhsequent discovery of optically active complexes constituted
the experimental proof for this very. important
. deduction that
was hased on his coordination theory.
Like many great theories, Werner's coordination theory was
fundamentally simple, yet ingenious. It has withstood the test
of time, and although it has been amplified by some, it has
reauired verv little revision. Thus. Alfred Werner is eenerallv
recognized as the father of modein coordination ccemistri
Werner's hiehest scientific honor. the Nobel Prize. was
awarded in 1913: for his contributions to inorganic chemistry,
especially the coordination theory.
Amplification of Werner's Theory
In 1916, G. N. Lewis ( 9 ) a t the Universitv of California-
Berkeley expressed Werner's ideas of coordination in terms
of the coordinate covalent bond. The bond joining the central
metal and each of its ligands was pictured as a pair of electrons
donated by the ligand. Therefore, metal-ligand reactions could
-
he classified as acid-base reactions accordine to the Lewis
definition. Subsequently, considerations of the Lewis concept
of coordinate covalence counled with a knowledge of the
electronic configuration of metal ions enabled N. v."Sidgwick
to postulate that a central metal would accommodate enough
ligands by coordination so that, in the resulting complex, the
metal's effectiue atomic number would be the same as the
atomic numher of the next noble gas (12,13). The effectiue
atomic number (EAN) was defined as the sum of the electrons
on the metal plus the electrons donated by the ligands. This
concept is illustrated with the formation of the hexaam-
minecohalt(II1) cation, [Co(NH&]3+.
A cobalt atom has 27 electrons d~stributedin four energy
levels:
2)e- 8)e- 15)C 2)e-
When the simple cohalt(II1) cation is formed, three electrons
are lost, resulting in a structure containing 24 electrons
Co3+2)e- 8)ec 14)e-
Table 1. Cobalt(1ll) Ammlne Complexes
Trivial Name # Ions per
Em~iricalFormula Color Prefix miecule
CoCI36NH3 Yellow Lute0 4
CoCI3.5NH3 Purple Purpureo 3
CoCIs.4NH3 Violet Violeo 2
Green Prase0 2
CoCId3NH3 Violet - 0
In the complex cation [Co(NH&]3+, the six ammonia mole-
cules donate six airs of electrons to the central cobalt(II1)
cation, making a total of 36 electrons owned or shared by co-
halt
[Co(NH&I3+ 2)e- 8)ec 18)e- 8)e-
Therefore, the EAN of Co(II1) in the complex is 36, the same
as krypton's atomic number. Presumably the stability of the
complex is attendant on the resulting noble gas electron
confieuration. Althoueh the EAN rule has little ouantitative
significance and muny exceptions, its use cuntinues a s a rule
<,Ithumb for oredict ina- the structures otmetrll carhonvk and
nitrosyls.
From 1910 to the present, two independent developments
have facilitated thk great strides made in coor&nation
chemistrv. The first of these was the development of sophis-
ticated instrumental methods for charac&rizing chemical
compounds. This began with the development of X-ray
crvstalloeraohv as a tool for structure elucidation and was
foilowed bybtier physical techniques which include electron
diffraction. and the interoretation of ultraviolet. infrared.
micn,waw, Ri~man,and nuclear magnetic resonance spectra.
All ofthise methods are usef~~l in thrrc-dimensimal structural
analysis and have served to escalate the interest in, and rapid
growth of, coordination chemistry. Coincidental with the
development of methods for structural analysis, Heitler and
London (14) were providina a theoretical extension of the
Lewis and ~idgwickmodelsof coordinate covalence.
By the mid 1930's several research groups, including one
headed hv Linus Pauline at the California Institute of Tech-
nolqy, acre regul~rlydetermining the strurtures of caordt-
nation comnounds. 'l'h~swork r)n>videdthe itimulus for and
was culminated in Pauling's tre'atise, "Nature of the Chemical
Bond." which a ~ o e a r e din several editions beainnina in 1940.
~ a u l i n ~effort
's marked the first successfu~appl~ation of
hondina theorv to coordination compounds. Moreover, it
provided the best available expostion of the oalence bond
theory. Although the valence bond model had several critical
defects (e.g., it did not permit the interpretation or prediction
of visible spectra), it was used extensively to explain the theory
of metal-ligand bonding until the 195$s.
The theories that eventually would supplant the valence
hond theory were promulgated by Pauling's contemporaries.
For example, the foundations of crystal field theory, a model
based on the electrostatic interactions between a metal and
its ligands, is found in the work of Hans Bethe (15). The
leadina ...Drooonent
. of the l i ~ a n dfield theorv, a modification
of crystal field theory that jncludes the concept of covalency,
was .I. H. Van Vleck (16).\'an Vleck was also the first to apply
the molecular orbital approach to bonding in coordina%on
compounds (17). Subsequently, J. E. Lennard-Jones (18) and
Robert S. Mulliken (19, 20) refined and amplified the mo-,
lecular orbital theory as it applies to metal-ligand bonding.
The Nature of Cornolex Ions
Complex ions are charged aggregates formed when a metal
atom or ion is bonded directlv to a arouo of liaands. The
chemical basis for this union is the cmrbinate hond, therefore,
comolex formation is usuallv visualized as a Lewis acid-base
reaction
M"++ x:L+ M(:L),"'
In other words, metal ions generally make use of their empty
orbitals hv means of coordinate bondina. The extent of this
outer-orhkal participation depends o n t h e energy of these
orbitals and, for the representative metals is roughly parallel
to their electronegativity. Thus, the tendency for coordinate
bond formation is very slight for the alkali metals, and in-
rreases across a period in the periodir tahle. The transition
metal ions with their empty inner orbitals are particularly
strong complex formers.
Any metal ion in aqueous solution is usually perceived as
having its coordination requirements saturated by water
molecules very much as the hexaaquonickel(I1) cation in
structure VI. The number of water molecules attached to the
IY~I
central atom or ion, i.e., its coordination number, depends on
the central atom or ion's charge, its size, and the relative
charge and size of its ligands. Coordination numbers ranging
from two through twelve are known; however, two, four, and
six are the most common. Inasmuch as the interactions be-
tween the central atom and its lieands are verv com~lex.it is
difficult tv reliably predict the n x d i n a t i o n number's size.
Some cations such as CU-.. A-C .. and Hr " have ~(mrdination
requirements of two in many of their c&plexes. Metals such
as Pt2+, Pd2+, Zn2+, C U ~ +Co2+,, and Cd2+have coordination
numbers of four. The cations such as Cr", Few+,Mn2+,and
Ni2+ have coordination numbers of six in many of their com-
plexes.
The central atom-donor atom bond may he highly polar but
is essentially a covalent interaction in typical systems. In the
extreme, however, such as with the alkali metals (Li, Na, K,
Rb, Cs), the metal ions have little electron pair acceptor ten-
dency, and in aqueous solution they are hydrated by pre-
dominantly ion-dipole interactions. The electron pair acceptor
tendency increases among the smaller ions, such as Be2+,
which also have the lowest energy orbitals and greatest co-
valency in their interactions.
Hydrated metal ions, particularly those with a charge of +3
or more, tend to lose protons in aqueous sdution. The proton
Iors from neutral liaandr IS facilitated through changes in the
electron density of the bonds joining the protons to the donor
atom. For strong Bronsted bases (i.e., ligands which form weak
- ~ there
acids). ~ ~will~be ~a comoetition
~ ~ ~ ~ . . between the nrotons and
the metal for the ligand, hence complexing will be influenced
bv DH.The result mav he the formation of hvdroxo (OH-) or
&d (02-) complexes:ln other words, an a i u o complex may
he partially or even completely deprotonated. Such behavior
is characteristic of iron, e.g.,
.IFe(H?O)nl3+ - . + Hs0+
- -. + HPO+ IFeOH(HsO)sIZ+
The hexaaquo cation and the monodeprotonated complexes
are shown in structures VII and VIII, respectively. The hy-
droxide ion. OH-. coordinated to iron(II1)
. -
. mav function as
a bridge joining twoor more cations ions together, forming a
polymer much as shown in structure 1X.Other common metal
ions that form polymeric species with hydroxide bridging
groups include A P , Cu2+,Be2+,Co3+, Pb2+, Sn2+,Sn4+,and
Ce4+. This sort of metal ion behavior may have a profound
effect upon the aquatic environment. A good example is the
acid mine drainage, formed by the exposure of pyrite, FeS2,
to air and moisture. The iron(I1) in pyrite is oxidized to iron-
(111) and is subsequently hydrated to form [Fe(H20)6]". The
Volume 58 Number 3 March 1981 259
shift of electron densitv to the central iron(II1) ion and awav Table 2. Some Typical Coordinating Ligands
from the O-H bonds of the coordinated ligands makes the; Donor
protons acidic and results in dissociation equilibria Camoound Name Formula Liaand Name Atom
+ H30+
[Fe(H20)6I3++ H20 = [FeOH(H20)s12+ Neutral Molecules
K , = 8.9 X Water H20: Aquo 0
[FeOH(H20)slt2+ Hz0 [Fe(OH)dH20)# + HsO+ Carbon Monoxide :wO: Carbonyl C
Ammonia :NH3 Ammine N
K, = 5.5 X 10P Nitric Oxide :N E O : Nitrosy1 N
If this material is transported in sufficient quantity by surface Phosphine :PH, Phosphine P
waters into the natural drainage system, the resulting flow 1.2-Diarninoethane HZN-CH-CH,-NH~ Ethylene- N
may in many cases he of such an acidic level that it is unsat- diamine
Anions
isfactory for supporting plant and animal life.
The common donor atoms are the halide ions, the atoms 0 , Hydride H- Hydrido H
N, S, Se, As, and P in their compounds and carbon in ligands Cyanide CN- Cynno C
Sulfide S2- Thio S
such as CO and CN-. Some typical coordinating ligands are Disultide SgZ- Disulfido S
shown in Table 2. Fluoride F- Fluoro F
Ligands which occupy a single coordination site are classi- Chloride CI- Chloro CI
fied as unidentate (single-toothed) and include such species Bromide Bri Bromo Br
as CO, NHs, H20, and F-. Complexity increases, however, Iodide 1- lodo I
when a particular ligand can simultaneously occupy more than Oxide D2- 0x0 0
one coordination site. The ligands that possess two or more Hydroxide OH- Hydroxo 0
electron-donor centers and thus simultaneouslv occuuv Pemxide OZ2- Perox0 0
. . two,
Sulfate Sulfato 0
three, four, five, or six nxrdinntion siteson the central atom
Thiosulfate S20a2- Thiowlfato 0
are called mul/id~n/ute(manv-toothed)limnds ur rhelntiny
(from the Greek chele, clawjagents. such chelating agents following its name. Anionic lipands are named first followed
are called bidentate, tridentate, quadridentate, quinquiden- hy neutral and cationic ligandsin the dame urder that they are
tate, and sexidentate, respectively. ~thylenediamine cited in the tormuln. Neutral and cationic liaand.; are named
(H2N-CH2CH2-NH2) behaves as if it were two ammonia without change, except that water and ammonia ligands are
molecules and is a good example of a bidentate ligand and called aquo and ammine, respectively. The names for anionic
chelating agent. Other common bidentate ligands are the ligands end with -0. Generally, if the anion name ends with
carbonate (C012-) and oxalate ( C 1 0 P ) ions. Bis(2-ami- -ide, -ite, or -ate, the final -e is replaced by -0,giving -ido, -ito,
noethyl)a&ne, HN ( c H ~ c H ~ N H' ~and ~ ~ ,tris(2-ami. and d o . resoectivelv. Some anions do not follow exactlv this
noethyl)amine, N(CH2CHzNH2)3,are examples of tridentate rule heckse'their mbdified forms have become firmly estab-
and quadridentate ligands, respectively. Quinquidentate li- lished. For example: F-, fluoro; C1-, chloro; Br-, hromo; I-,
gands are uncommon, however, sexidentate ligands such as iodo; 02-, 0x0; OH-, hydroxo; 0z2-, peroxo; HS-, thiolo; S2-,
ethylenediaminetetraeketate ion (EDTA4+)are widely used. thin; and CN-, cyano are exceptions. Groups such as NO, NS,
Provided that metal-ligand interactions are similar and that CO, and CS, when coordinated to the central atom, are called
steric requirements can he met by the donor atoms, chelate nitrosvl, thionitrosvl,. . carhnnvl,. . and thiocarhonvl.. . resoec-
.
complexes are generally more stable than those of analogous tively.
unidentate ligands; the greater the degree of chelation, the Thus, Li[AlHa] is lithium tetrahydridoaluminate;
greater is the stability. The size of the chelate ring is also of [CoCI(NH3)5]C12is chloropentaamminecobalt(III) chloride;
nrime imnortance. Five-membered rines (including the metal [AI(OH)(H20)#+ is hydroxopentaaquoaluminum ion; and
ion) are'most stable, followed clos&' by six-membered K4[Fe(CN)6]is potassium hexacyanoferrate(I1). More com-
rings. .plete discussions of coordination nomenclature are available
Formulas and Nomenclature for Complexes in the literature (21,22).
General standards of nomenclature have been established Complexes In the Environment
by the International Union of Pure and Applied Chemistry The sea is an enormous and extremely complicated system
(IUPAC). The rules were established to minimize the inven- containing all of the natural elements. Fresh water in lakes and
tion of non-systematic names fur new compounds. The rurrent streams is a dilute solution and most of the ionic solutes are
disrussion is limited to a general descriotion of the onttern of oresent as their s i m.~ l hvdrates.
e Seawater. on the other hand.
coordination nomencla&re and complex formuiation. In is much more concentrated and offers many opportunities for
writing formulas for comulex comuounds the svmbol for the ionic interactions. Thus. manv comoonents of seawater are
centraiatom should be piaced firsifexcept in f'rmulas which complex ions, usually of ligan& suck as chloride, hydroxide,
are primarily structural), followed by the anionic and neutral carbonate, bicarbonate, sulfate, or phosphates. These natural
ligands. The anionic ligands should be listed in the following complexes, e.g., [CaHC03]+ and [ F e ( H P ~ 0 ~ ) ~ 1play
3 - , im-
order: H-, 02-, OH-, monoatomic anions, polyatomic anions, portant roles in the ecosystem of the sea. Contamination of
and organic anions in alphabetical order. Neutral ligands the sea by other complexing agents, or by metal ions com-
should appear in the order: water, ammonia, other inorganic peting for natural ligands, may have significant effects on
ligands (the ligand's coordinating element is used to specify aquatic life. For example, mercury pollution is generally a
their sequence and follows the order: B, Si, C, Sb, As, P, N, H, localized problem in fresh water, since most mercury com-
Te. Se. S. At. I. Br. CI. 0. F). and oreanic molecules listed in pounds are quite insoluble. In salt waters, however, stable
alihadetical &der.'~hef b r i u ~ for
a ihe whole complex ion or water-soluble chloro complexes help maintain mercury pol-
molecule should he placed in hrackets [ 1. lutants in solution for widespread distribution:
In writing names the central atom should be placed after
the ligands. The names of complex anions are terminated with
the suffix -ate, while complex cations and neutral molecules Most naturally occurring organic ligands are deccmposition
are given no distinguishing termination. The oxidation products or by-products of living organisms. These include
number of the central atom-is designated by means of the "humus," polyhydroxy compounds like carbonates and sug-
Stock System. In other words the centrals atom's oxidation ars, and compoundssuch as amino acids, formed hv the de-
number is indicated by using Roman numerals immediately composition of proteins. For example, consider that the or-

280 Journal of Chemical Education

-
eanic matter of marine sediments and terrestrial soils consists
mainly of a series of complex high molecular weight, brown
nitrogenous ~olvmers,collectivel~referred to as "humus."
One Fraction-of the humus is a family of compounds known
as "fulvic acid," which can help transport trace metals into
plants via a series of soluble complexes. Although "fulvic acid"
is a family of compounds, rather than a single species, its
complexing action occurs because of the presence of typical
units such as:
do
These units from the "fulvic acid" act as chelating agents and
have a high capacity for binding metal ions:
Chelates In Medlclne
Chelation is a chemical process wherein ions of a metal are
seized in a claw-like structure by a chemical complexing agent.
The medical importance of chelating agents hinges on the fact
that metals play many critical roles in the living organism.
Metabolic processes depend on the presence of magnesium,
iron, sodium. ~otassium,calcium, and traces of such metals
as zinc, manganese, copper and cobalt. However, certain other
metals, even in rnicnxluantities, are extremely toxic. Conse-
quently, rhelating drug.; with appropriate properties can play
several therapeutic roles. For example, rhelating agents have
been desiened that will hind toxic metals. formine a stable
complex &at can be excreted. ~th~lenediaminete&aacetate
ion (EDTA4+)is usually the treatment choice for lead poi-
soning. It increases the urinary excretion of lead dramatically,
according to the following reaction:
Pb2++ EDTA4- = [Pb(EDTA)IZ-
On the other hand, some cbelates are designed to bind es-
sential trace elements and deliver them to appropriate tissue
sites. For example, one of the functions of the antipyretic and
analgesic drug aspirin is toscavenge Cu2+ions from the blood
and return them to the cell sites from which they were lost.
The salicylate ion from the original aspirin acts as the che-
lating agent
Complexlng In Natural Systems
The importance of complexes becomes even more clear by
recalling that the cytochromes, hemoglobin, vitamin B12, and
chlorophyll, which are all compounds that play key roles in
life processes, are chelates of iron, cobalt, and magnesium.
These complexes, the porphyrins, are based on the tetrapyrole
nucleus shown in structure X. Substituents on the porphyrin
skeleton, and minor changes in the ring structure, are found
in the various naturallv occurrineu comoounds
. of this class.
The porphyrin ring is planar, with sufficient room in the
center of the rine svstem for coordinatine a metal ion as shown
by the following structure
Metal ions that have six coordination sites may coordinate
ligands above and below this plane. This provides the chemical
basis of oxygen transport by heme, the iron-containing por-
phyrin complex in hemoglobin. Oxygen is ligated to the iron
in heme when its partial pressure is high and released when
it is low. Other ligands may bond to iron's coordination site,
and if they are not readily replaced (as is the case with carbon
monoxide, which forms a strong bond with the iron(I1) in
heme), the oxygen transport function is blocked.
The cvtochromes are a verv i m ~ o r t a ngrow
t of substances
that mediate the oxidation-reduction reactions in living cells.
The best known is Cytochrome c; a molecule that contains a
heme group similar to but not identical with that of hemo-
globin. Unlike hemoglobin, Cytochrome c does not combine
with oxygen or carbon monoxide, and its central atom, iron,
undergoes a cycle of oxidations and reductions from iron(I1)
to ~~~~~,
iron(II1) as it nerforms its biochemical role.
~~
chlorodhy1l,t'he pigment found in the chloroplasts of all
green plants, is the key material in nature's biological solar
cells. I t is the principal agent that enables plants to convert
solar energy into chemical energy by photosynthesis. Chlo-
rophyll is a porphyrin chelate, differing from hemglobin in
that the chelated metal is magnesium rather than iron.
Cobalamin, vitamin B12, i s i water soluble complex mole-
cule containing-a Dor~hvrin
. . . ring chelated to a central cobalt-
(11) ion. Pernicious anemia may result from inadequate ah-
somtion of vitamin BIZ.It apparently functions as a coenzyme
during amino acid m&boli& as well as during the conve&on
of ribonucleotides to deoxyribonucleotides.
Industrial ApDlIcatlon of Complexes
..
Hydrometallurgy is concerned with methods of producing
metals, or some of their com~ounds,by reactions which take
place in water. The first h ~ d r o m e t a ~ l u r ~ imethods
cal were
used for the recovery of gold, silver, and copper. Recently, the
methods of hydrometallurgy have been extended to include
other elements, especially uranium. The principal operations
--
used in hvdrometallurev include leachine. " solution ourifica-
tion, and precipitation. Leaching is aprocess of dissolving the
desired mineral by the chosen solvent. For example, silver is
obtained from its sulfide ore, AgzS, by a process which starts
-
bv leachine with dilute cvanide solution. according to the
equation:
Following solution purification, silver is then obtained by
treatment of the solution with zinc or aluminum
2[Ag(CN)21-(,1+ Znw = 2 A m + [Zn(CN)rl-2i.q~
Many other practical applications for complexes appear in the
literature (23-25).
Literature Clted
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(2) Frankland, E.,Phil. T r o w Roy. Soe. London. 142,417 (18521.
(31 Keku1O.F. A..Ann. Chem.. 104.129l18571.
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I51 Biornstrsnd,C. W.,Bel..4,40l18711.
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(8) Werner. A,, "Neucre Anachauungen aufden Gebieteder Anorgmischen Chernie."Ith
Ed., Friedrich Viawag & Sohn, Braunachwcig. 1920.
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I231 ~ c O n n &R.. Mickey, C. D..and Hassell. A.,"Soiuing Problems inchemistry: 2nd
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1121 Sidgwiek,N.V.. J Chem. Soe., 123,725 (19281. 1241 Marfe1l.A. E.,J.CHXM. EDUC., 29,270 11952).
113) Sidpwiek, N. V.. "The Electronic T h w r y of Vslenee? Clarmdon Press. Oxford. 125) Kirsehner.S.. J.CHEM. EDUC.35. 139 (19581.
1927.
I141 Heitler, W. and London,F..Z. Phyr.,dd.455 (19271. Suggested Supplementary Reading
IlSI Bethe. H..Ann. Physib.3.135 11929).
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1171 VsnVleck,J.H., J. Chern. Phys.3.803 119351. New York. 1956.
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119) Mulliken,R.S.,Phyr.Rev.,43,279119331. 1964.
(20) Mulliken. R.S.. J. Chem. Phys.23.1833 (1955). C m o n . F. A. and Wilkinron, G.."Advanced Inorganic Chemistry." 4th Ed., Interscience
121) ACS Commentary on lUPAC Rules. J. Arne,. Cham. Sor Publishers, New York. 1980.
Kauffman, G.H.,Ed.. 'Werner C e n t a n i d ? Advance inChemirtrySerie8,Vol. 62.Americsn
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262 Journal of Chemical Education