Coordination Compounds
Abstract
Much of the selectivity and efficiency of chemical transformations, which involve metalloproteins is
due to a modulation of the properties of the metal ions by the protein to which they are bound.
Geometric and electronic distortions, enforced by the protein backbone, and specific electrostatic
fields and solvation patterns (e.g. hydrophobic pockets) may lead to a destabilization of the
catalytically active site (metal center(s) and/or enzyme–substrate complex(es)) and, therefore, to a
(selective) activation of certain reaction channels. This is known as the ‘energization theory’ or, for
specific cases, the ‘entatic state’ principle.
Examples, where specifically enforced coordination geometries lead to stresses and enhanced
reactivities range from biological systems (metalloproteins and enzymes) to classical coordination
compounds and processes of industrial importance (catalytic systems which
involve organometallic and transition metal coordination compounds). Hence, entasis is not refined
to metalloproteins; reactions induced by metal-free enzymes or by small coordination compounds
may also involve strained, that is entatic states. Based on few selected examples, which include the
classical cases of the blue copper proteins and of electron transfer in general, as well as simple
coordination compounds and organometallic catalysis, it is shown that a thorough analysis and
interpretation of enhanced reactivities may in general not be assigned exclusively to steric strain.
However, specific coordination geometries, enforced by the ligand sphere (protein or simple organic
compounds) which may or may not be strained are often of importance. One of the main conclusions
is that the understanding, design and synthesis of new compounds with specific and enhanced
reactivities may involve similar thoughts, tools and difficulties as the design and study of highly
preorganized ligands in areas such as metal ion recognition and host–guest interactions in general.
Introduction
The basic ideas of energized states in proteins, metalloproteins and simple transition metal
coordination compounds were developed in the early fifties for a historical overview, for a
comprehensive description of catalysis by metalloproteins in the entatic state, and Refs. for
arguments on the history and on mechanistic differences between metalloproteins in the entatic
state (enforced geometry by a rigid protein,the rack mechanism in metalloproteins (conformational
changes of a protein and allosteric effects that may lead to stretching in a rack action), the induced fit
mechanism (enforced geometry by a locally flexible protein) and enforced conformation of the
protein by the metal ion). In a less than puristic and somewhat simplistic but scientifically useful view
entasis may be defined as the energization due to a misfit between ligands and metal ions
(metalloproteins or simple coordination compounds) or between complex fragments and the
corresponding substrate–catalyst complexes, and this is the definition on which this review is based.
Simple reaction schemes for single step reactions that visualize the conventional interpretation of a
catalyst and that of an enzyme in the entatic state are shown similar diagrams may be drawn for the
generally more relevant multistep mechanisms of catalytic processes. Note, that in a single step
reaction a ligand enforced energization may influence both, the starting materials and the products,
and not necessarily in the same way and by the same amount of energy ); that is, both, the kinetics
and thermodynamics of a single step chemical reaction. Therefore, the thermodynamics of the
catalyst–substrate complexation and the corresponding decomplexation have also been included in,
and thermodynamic as well as kinetic aspects of energized (entatic) states of coordination
compounds in general will be considered here. A prominent and historical example for the entatic
state principle is that involving blue copper proteins, where the oxidized and reduced forms have
similar coordination geometries. Therefore, the basic aspects of the entatic state hypothesis will be
introduced with cupredoxines, and that section will also include recent results and their
interpretations, which started a new controversy with respect to the necessity to involve entatic
states in this and in other cases.
Energized states (strained geometries) may involve stresses due to the ligand backbones or the
electronic preferences of the metal ion, and, apart from steric strain, electronic and entropic strain,
as well as environmental stresses (solvation, crystal lattice effects) may be of importance. These are
the same factors that have to be considered in (selective) host–guest interactions, e.g. in the
optimization of ligands for metal-ion-selective complexation processes. That is, the ligands (proteins
or simple organic molecules) of coordination compounds in the entatic state are highly preorganized
with respect to the transition state structure).
Based on these aspects of entasis I will review recent results from the classical area of the blue
copper proteins, followed by the discussion of selected examples of low molecular weight transition
metal compounds, relevant to blue copper proteins and other areas of coordination chemistry.
Coordination compounds in nature
Hemoglobin is a protein made up of four polypeptide chains (α1, α2, β1, and β2). Each chain is
attached to a heme group composed of porphyrin (an organic ringlike compound) attached to an iron
atom. These iron-porphyrin complexes coordinate oxygen molecules reversibly, an ability directly
related to the role of hemoglobin in oxygen transport in the blood.
Naturally occurring coordination compounds are vital to living organisms. Metal complexes play a
variety of important roles in biological systems. Many enzymes, the naturally occurring catalysts that
regulate biological processes, are metal complexes (metalloenzymes); for
example, carboxypeptidase, a hydrolytic enzyme important in digestion, contains
a zinc ion coordinated to several amino acid residues of the protein. Another enzyme, catalase,
which is an efficient catalyst for the decomposition of hydrogen peroxide, contains iron-
porphyrin complexes. In both cases, the coordinated metal ions are probably the sites of catalytic
activity. Hemoglobin also contains iron-porphyrin complexes, its role as an oxygen carrier being
related to the ability of the iron atoms to coordinate oxygen molecules reversibly. Other biologically
important coordination compounds include chlorophyll (a magnesium-porphyrin complex)
and vitamin B12, a complex of cobalt with a macrocyclic ligand known as corrin.
Coordination compounds in industry
The applications of coordination compounds in chemistry and technology are many and varied. The
brilliant and intense colours of many coordination compounds, such as Prussian blue, render them of
great value as dyes and pigments. Phthalocyanine complexes (e.g., copper phthalocyanine),
containing large-ring ligands closely related to the porphyrins, constitute an important class of dyes
for fabrics.
Several important hydrometallurgical processes utilize metal complexes. Nickel, cobalt,
and copper can be extracted from their ores as ammine complexes using aqueous ammonia.
Differences in the stabilities and solubilities of the ammine complexes can be utilized in selective
precipitation procedures that bring about separation of the metals. The purification of nickel can be
effected by reaction with carbon monoxide to form the volatile tetracarbonylnickel complex, which
can be distilled and thermally decomposed to deposit the pure metal. Aqueous cyanide solutions
usually are employed to separate gold from its ores in the form of the extremely stable
dicyanoaurate(−1) complex. Cyanide complexes also find application in electroplating.
Chemical Bonding in Coordination Compounds
The essence of coordination compounds lies in the coordination bond, formed by the interaction
between the metal center and ligands. This bonding is primarily electrostatic but can possess
covalent characteristics depending on the nature of the metal-ligand interaction. Ligands are
classified based on their donor atoms and coordination number, offering diverse stereochemical
arrangements within these complexes. The coordination theory developed by Werner laid the
groundwork for comprehending the structural diversity of coordination compounds.
Structures of Coordination Compounds
Coordination compounds come in diverse structures, primarily determined by the central metal ion,
ligands, and coordination number. Common geometries include octahedral (with six ligands),
tetrahedral (with four ligands), square planar (with four ligands in a flat plane), trigonal bipyramidal
(with five ligands), and less common structures like square pyramidal and pentagonal bipyramidal for
other coordination numbers. These structures exhibit various isomerisms, showcasing different
spatial arrangements of ligands around the metal ion. The actual structure of a coordination
compound is influenced by factors such as the metal ion's size, ligand properties (size, charge, and
electron properties), and the preferences of both the metal ion and ligands involved in bonding.
Coordination Numbers and Valence Bond Theory
Coordination number represents the number of bonds formed between the central metal ion and
the surrounding ligands in a coordination compound. This count defines the spatial arrangement
around the metal ion and determines the compound's geometry. For instance, a coordination
number of 6 results in an octahedral geometry, where six ligands are arranged around the central
metal ion in a symmetrical manner. Different coordination numbers lead to distinct geometries like
tetrahedral, octahedral, or trigonal bipyramidal structures.
Valence bond theory explains how these bonds are formed in coordination compounds. It focuses on
the overlap of atomic orbitals between the central metal atom and the ligands. When the metal's
vacant d-orbitals interact with the orbitals of the ligands (often s, p, or d orbitals), they form
coordinate covalent bonds. This overlapping process determines the directionality of the bonds and
contributes to the overall shape of the complex.
Hybridization is a key concept in valence bond theory. It occurs when the metal's atomic orbitals
hybridize to create new hybrid orbitals that match the symmetry of the ligand orbitals. These hybrid
orbitals are then involved in bonding with the ligands, influencing the geometry of the coordination
compound. For instance, in an octahedral complex with a coordination number of 6, the metal's
available d-orbitals hybridize to form six new orbitals, each of which interacts with a ligand orbital to
create bonds.
The coordination number directly corresponds to the available orbitals for bonding on the central
metal ion. For example, a coordination number of 6 in an octahedral complex means the metal ion
utilizes six available d-orbitals to form bonds with six ligands. In a tetrahedral complex with a
coordination number of 4, the metal ion employs four available d-orbitals for bonding with four
ligands.
Valence bond theory's predictions align well with experimentally observed geometries for various
coordination numbers. This theory provides a comprehensive understanding of how coordination
compounds form bonds and adopt specific structures, contributing significantly to our
comprehension of their properties, reactivity, and applications in different fields.
Physical Properties of Coordination Compounds
Coordination compounds are molecules or ions that contain a central metal atom or ion bonded to
one or more ligands by coordinate covalent bonds. The physical properties of coordination
compounds are influenced by several factors:
1. Color: Many coordination compounds exhibit vivid colors due to the absorption of specific
wavelengths of light. This color arises from the interaction between the metal ion and the
ligands, causing electronic transitions within the compound. For example, the different colors
of transition metal complexes in solution or solid state are due to this phenomenon.
2. Magnetic Properties: Some coordination compounds exhibit magnetic properties based on
the presence of unpaired electrons in the metal's d-orbitals. Paramagnetic compounds have
unpaired electrons and are weakly attracted to a magnetic field, while diamagnetic
compounds lack unpaired electrons and are weakly repelled by a magnetic field.
3. Solubility: The solubility of coordination compounds varies widely depending on the nature
of both the metal ion and the ligands. Some are highly soluble in water or organic solvents,
while others may be sparingly soluble or insoluble.
4. Complex Formation: Coordination compounds often form complex structures with unique
properties. These complexes may have different physical states (solid, liquid, gas) and can
sometimes form crystals with distinct geometries and symmetries.
5. Stability: Stability refers to the tendency of a coordination compound to retain its structure
under certain conditions, such as changes in temperature, pH, or presence of other
chemicals. Stability can affect the compound's physical properties and its applications in
various fields.
6. Conductivity: In some cases, coordination compounds can conduct electricity, especially
when dissolved in a solvent or in the molten state. This property is dependent on the ability
of the compound to dissociate into ions that can carry an electric charge.
Chemical Properties and Reactions of Coordination Compounds
Coordination compounds exhibit various chemical properties and engage in diverse reactions due to
the presence of a central metal ion or atom bonded to ligands. Some important chemical properties
and reactions include:
1. Ligand Substitution: Ligand substitution reactions occur when one or more ligands in a
coordination compound are replaced by other ligands. This process often depends on the
relative strengths of the incoming and existing ligands as well as the coordination number
and geometry of the complex. For instance, in a square planar complex, ligand substitution
reactions often occur via a dissociative or associative mechanism.
2. Isomerism: Coordination compounds can exhibit different types of isomerism, such as
structural isomerism (different spatial arrangements of atoms), geometrical isomerism
(different spatial arrangements due to restricted rotation around a bond, common in
octahedral complexes), and optical isomerism (chirality when the molecule lacks a plane of
symmetry).
3. Redox Reactions: Many coordination compounds are involved in redox reactions, where the
central metal ion changes its oxidation state. These reactions can occur within the
coordination sphere or involve the ligands. For example, metal ions in different oxidation
states can be interconverted by gaining or losing electrons.
4. Catalytic Activity: Some coordination compounds exhibit catalytic activity due to the
presence of transition metals. They can act as catalysts in various chemical reactions by
providing an active site for the reaction to occur, without being consumed in the process.
5. Acid-Base Reactions: Coordination compounds can behave as Lewis acids or bases. The
central metal ion can act as a Lewis acid by accepting an electron pair from a Lewis base (the
ligand), leading to the formation of the coordinate covalent bond.
6. Photochemical Reactions: Certain coordination compounds can undergo photochemical
reactions upon absorption of light energy. This can lead to structural changes or initiate
chemical reactions, and it's often utilized in fields such as photovoltaics or photodynamic
therapy in medicine.
7. Chelation: Chelation involves the formation of a ring structure called a chelate, where a
ligand binds to a metal ion at multiple points. This complexation is often more stable and
influences the compound's properties, including its chemical reactivity.
Understanding and manipulating these chemical properties and reactions are crucial for applications
in various fields, including medicine, industry, catalysis, and materials science. Scientists and
researchers explore these properties to design compounds with specific functions and tailored
characteristics for practical use.
Applications of Coordination Compounds
Coordination compounds find a multitude of applications across various fields due to their diverse
properties and reactivity. Some prominent applications include:
1. Catalysis: Transition metal complexes serve as catalysts in numerous industrial processes,
such as the Haber process for ammonia synthesis and the catalytic converters in automobiles
for pollutant reduction. They accelerate chemical reactions without being consumed, making
processes more efficient.
2. Medicine: Coordination compounds are crucial in medicine, especially in chemotherapy.
Metal-based drugs like cisplatin are used to treat various cancers by binding to DNA and
interfering with cell division. Additionally, some coordination compounds are investigated for
targeted drug delivery systems and imaging agents in medical diagnostics.
3. Dyes and Pigments: Many coordination compounds exhibit vibrant colors due to their
electronic transitions. These properties are harnessed in dyes and pigments for textiles,
paints, and inks, offering a wide range of colors and stability.
4. Electronics and Materials Science: Coordination compounds play a role in developing
advanced materials, such as conducting polymers and metal-organic frameworks (MOFs).
MOFs, for example, have applications in gas storage, catalysis, and even in electronics for
sensors and devices.
5. Environmental Remediation: Certain coordination compounds are used for environmental
purposes, such as in wastewater treatment to remove heavy metals or pollutants. They can
form complexes with contaminants, aiding in their removal or neutralization.
6. Photovoltaics and Solar Energy: Some coordination compounds exhibit photochemical
properties, making them useful in solar cells and photovoltaic devices. They can absorb light
and convert it into electrical energy efficiently.
7. Coordination Polymers: These compounds have applications in gas storage, separation, and
catalysis due to their porous structures, enabling the selective adsorption of gases.
8. Biological Studies and Sensors: Coordination compounds are employed as probes and
sensors to detect various ions and molecules in biological systems. They play a vital role in
understanding biological processes and signaling mechanisms.
9. Industrial Processes: Coordination compounds are utilized in industrial settings for various
purposes, including metal extraction, refining processes, and as additives to enhance the
performance of materials.
The versatility of coordination compounds and their ability to be tailored for specific functions make
them invaluable in a wide array of scientific, industrial, and technological applications. Researchers
continue to explore and develop new coordination compounds with enhanced properties for
emerging applications in different fields.
Future Prospects and Conclusion
The field of coordination chemistry continues to evolve, with burgeoning avenues for exploration. As
nanotechnology, renewable energy, and materials science advance, coordination compounds are
poised to play pivotal roles in these domains. Their versatility and tailored properties make them
promising candidates for innovations in various scientific and industrial applications.
In conclusion, coordination compounds represent a captivating branch of chemistry, characterized by
their structural diversity, unique properties, and multifaceted applications across diverse fields.
Understanding and harnessing the potential of these compounds are crucial for scientific
advancements and technological innovations.
