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A coordination complex consists of a central
atom Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons. Every solid, liquid, gas, a ...
or ion, which is usually
metal A metal (from ancient Greek, Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electrical resistivity and conductivity, e ...
lic and is called the ''coordination centre'', and a surrounding array of bound
molecules A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bio ...
or ions, that are in turn known as ''
ligand In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elect ...
s'' or complexing agents. Many metal-containing compounds, especially those that include
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
s (elements like
titanium Titanium is a chemical element with the symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion i ...
that belong to the Periodic Table's d-block), are coordination complexes.


Nomenclature and terminology

Coordination complexes are so pervasive that their structures and reactions are described in many ways, sometimes confusingly. The atom within a ligand that is bonded to the central metal atom or ion is called the donor atom. In a typical complex, a metal ion is bonded to several donor atoms, which can be the same or different. A
polydentate In coordination chemistry, denticity () refers to the number of donor groups in a given ligand that bind to the central metal atom in a coordination complex. In many cases, only one atom in the ligand binds to the metal, so the denticity equals ...
(multiple bonded) ligand is a molecule or ion that bonds to the central atom through several of the ligand's atoms; ligands with 2, 3, 4 or even 6 bonds to the central atom are common. These complexes are called chelate complexes; the formation of such complexes is called chelation, complexation, and coordination. The central atom or ion, together with all ligands, comprise the coordination sphere. The central atoms or ion and the donor atoms comprise the first coordination sphere. Coordination refers to the "coordinate covalent bonds" (
dipolar bond In coordination chemistry, a coordinate covalent bond, also known as a dative bond, dipolar bond, or coordinate bond is a kind of two-center, two-electron covalent bond in which the two electrons derive from the same atom. The bonding of metal i ...
s) between the ligands and the central atom. Originally, a complex implied a reversible association of
molecule A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and b ...
s,
atom Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons. Every solid, liquid, gas, a ...
s, or ions through such weak chemical bonds. As applied to coordination chemistry, this meaning has evolved. Some metal complexes are formed virtually irreversibly and many are bound together by bonds that are quite strong. The number of donor atoms attached to the central atom or ion is called the
coordination number In chemistry, crystallography, and materials science, the coordination number, also called ligancy, of a central atom in a molecule or crystal is the number of atoms, molecules or ions bonded to it. The ion/molecule/atom surrounding the central io ...
. The most common coordination numbers are 2, 4, and especially 6. A hydrated ion is one kind of a complex ion (or simply a complex), a species formed between a central metal ion and one or more surrounding ligands, molecules or ions that contain at least one lone pair of electrons. If all the ligands are monodentate, then the number of donor atoms equals the number of ligands. For example, the cobalt(II) hexahydrate ion or the hexaaquacobalt(II) ion  o(H2O)6sup>2+ is a hydrated-complex ion that consists of six water molecules attached to a metal ion Co. The oxidation state and the coordination number reflect the number of bonds formed between the metal ion and the ligands in the complex ion. However, the coordination number of Pt( en) is 4 (rather than 2) since it has two bidentate ligands, which contain four donor atoms in total. Any donor atom will give a pair of electrons. There are some donor atoms or groups which can offer more than one pair of electrons. Such are called bidentate (offers two pairs of electrons) or polydentate (offers more than two pairs of electrons). In some cases an atom or a group offers a pair of electrons to two similar or different central metal atoms or acceptors—by division of the electron pair—into a three-center two-electron bond. These are called bridging ligands.


History

Coordination complexes have been known since the beginning of modern chemistry. Early well-known coordination complexes include dyes such as Prussian blue. Their properties were first well understood in the late 1800s, following the 1869 work of
Christian Wilhelm Blomstrand Christian Wilhelm Blomstrand (20 October 1826 – 5 November 1897) was a Swedish mineralogist and chemist. He was a professor at the University of Lund from 1862-1895, where he isolated the element niobium in 1864. He developed an early version ...
. Blomstrand developed what has come to be known as the ''complex ion chain theory.'' In considering metal amine complexes, he theorized that the ammonia molecules compensated for the charge of the ion by forming chains of the type NH3)Xsup>X+, where X is the coordination number of the metal ion. He compared his theoretical ammonia chains to hydrocarbons of the form (CH2)X. Following this theory, Danish scientist Sophus Mads Jørgensen made improvements to it. In his version of the theory, Jørgensen claimed that when a molecule dissociates in a solution there were two possible outcomes: the ions would bind via the ammonia chains Blomstrand had described or the ions would bind directly to the metal. It was not until 1893 that the most widely accepted version of the theory today was published by
Alfred Werner Alfred Werner (12 December 1866 – 15 November 1919) was a Swiss chemist who was a student at ETH Zurich and a professor at the University of Zurich. He won the Nobel Prize in Chemistry in 1913 for proposing the octahedral configuration ...
. Werner's work included two important changes to the Blomstrand theory. The first was that Werner described the two possibilities in terms of location in the coordination sphere. He claimed that if the ions were to form a chain, this would occur outside of the coordination sphere while the ions that bound directly to the metal would do so within the coordination sphere. In one of his most important discoveries however Werner disproved the majority of the chain theory. Werner discovered the spatial arrangements of the ligands that were involved in the formation of the complex hexacoordinate cobalt. His theory allows one to understand the difference between a coordinated ligand and a charge balancing ion in a compound, for example the chloride ion in the cobaltammine chlorides and to explain many of the previously inexplicable isomers. In 1911, Werner first resolved the coordination complex
hexol In chemistry, hexol is a cation with formula 6+ — a coordination complex consisting of four cobalt cations in oxidation state +3, twelve ammonia molecules , and six hydroxy anions , with a net charge of +6. The hydroxy groups act as bridges ...
into
optical isomers In chemistry, a molecule or ion is called chiral () if it cannot be superposed on its mirror image by any combination of rotations, translations, and some conformational changes. This geometric property is called chirality (). The terms are d ...
, overthrowing the theory that only carbon compounds could possess
chirality Chirality is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek (''kheir''), "hand", a familiar chiral object. An object or a system is ''chiral'' if it is distinguishable from ...
.


Structures

The ions or molecules surrounding the central atom are called
ligand In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elect ...
s. Ligands are classified as L or X (or a combination thereof), depending on how many electrons they provide for the bond between ligand and central atom. L ligands provide two electrons from a
lone electron pair In chemistry, a lone pair refers to a pair of valence electrons that are not shared with another atom in a covalent bondIUPAC '' Gold Book'' definition''lone (electron) pair''/ref> and is sometimes called an unshared pair or non-bonding pair. L ...
, resulting in a
coordinate covalent bond In coordination chemistry, a coordinate covalent bond, also known as a dative bond, dipolar bond, or coordinate bond is a kind of two-center, two-electron covalent bond in which the two electrons derive from the same atom. The bonding of metal i ...
. X ligands provide one electron, with the central atom providing the other electron, thus forming a regular
covalent bond A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between ato ...
. The ligands are said to be coordinated to the atom. For
alkene In organic chemistry, an alkene is a hydrocarbon containing a carbon–carbon double bond. Alkene is often used as synonym of olefin, that is, any hydrocarbon containing one or more double bonds.H. Stephen Stoker (2015): General, Organic ...
s, the pi bonds can coordinate to metal atoms. An example is
ethylene Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon-carbon double bonds). Ethylene ...
in the complex ( Zeise's salt).


Geometry

In coordination chemistry, a structure is first described by its
coordination number In chemistry, crystallography, and materials science, the coordination number, also called ligancy, of a central atom in a molecule or crystal is the number of atoms, molecules or ions bonded to it. The ion/molecule/atom surrounding the central io ...
, the number of ligands attached to the metal (more specifically, the number of donor atoms). Usually one can count the ligands attached , but sometimes even the counting can become ambiguous. Coordination numbers are normally between two and nine, but large numbers of ligands are not uncommon for the lanthanides and actinides. The number of bonds depends on the size, charge, and
electron configuration In atomic physics and quantum chemistry, the electron configuration is the distribution of electrons of an atom or molecule (or other physical structure) in atomic or molecular orbitals. For example, the electron configuration of the neon ato ...
of the metal ion and the ligands. Metal ions may have more than one coordination number. Typically the chemistry of transition metal complexes is dominated by interactions between s and p
molecular orbital In chemistry, a molecular orbital is a mathematical function describing the location and wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of find ...
s of the donor-atoms in the ligands and the d orbitals of the metal ions. The s, p, and d orbitals of the metal can accommodate 18 electrons (see 18-Electron rule). The maximum coordination number for a certain metal is thus related to the electronic configuration of the metal ion (to be more specific, the number of empty orbitals) and to the ratio of the size of the ligands and the metal ion. Large metals and small ligands lead to high coordination numbers, e.g. . Small metals with large ligands lead to low coordination numbers, e.g. . Due to their large size,
lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yt ...
s,
actinide The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The info ...
s, and early transition metals tend to have high coordination numbers. Most structures follow the points-on-a-sphere pattern (or, as if the central atom were in the middle of a
polyhedron In geometry, a polyhedron (plural polyhedra or polyhedrons; ) is a three-dimensional shape with flat polygonal faces, straight edges and sharp corners or vertices. A convex polyhedron is the convex hull of finitely many points, not all o ...
where the corners of that shape are the locations of the ligands), where orbital overlap (between ligand and metal orbitals) and ligand-ligand repulsions tend to lead to certain regular geometries. The most observed geometries are listed below, but there are many cases that deviate from a regular geometry, e.g. due to the use of ligands of diverse types (which results in irregular bond lengths; the coordination atoms do not follow a points-on-a-sphere pattern), due to the size of ligands, or due to electronic effects (see, e.g., Jahn–Teller distortion): *
Linear Linearity is the property of a mathematical relationship ('' function'') that can be graphically represented as a straight line. Linearity is closely related to '' proportionality''. Examples in physics include rectilinear motion, the linear ...
for two-coordination *
Trigonal planar In chemistry, trigonal planar is a molecular geometry model with one atom at the center and three atoms at the corners of an equilateral triangle, called peripheral atoms, all in one plane. In an ideal trigonal planar species, all three ligands ...
for three-coordination * Tetrahedral or
square planar The square planar molecular geometry in chemistry describes the stereochemistry (spatial arrangement of atoms) that is adopted by certain chemical compounds. As the name suggests, molecules of this geometry have their atoms positioned at the corne ...
for four-coordination *
Trigonal bipyramidal In chemistry, a trigonal bipyramid formation is a molecular geometry with one atom at the center and 5 more atoms at the corners of a triangular bipyramid. This is one geometry for which the bond angles surrounding the central atom are not iden ...
for five-coordination * Octahedral for six-coordination * Pentagonal bipyramidal for seven-coordination * Square antiprismatic for eight-coordination * Tricapped trigonal prismatic for nine-coordination The idealized descriptions of 5-, 7-, 8-, and 9- coordination are often indistinct geometrically from alternative structures with slightly differing L-M-L (ligand-metal-ligand) angles, e.g. the difference between square pyramidal and trigonal bipyramidal structures. * Square pyramidal for five-coordination * Capped octahedral or capped trigonal prismatic for seven-coordination * Dodecahedral or bicapped trigonal prismatic for eight-coordination * Capped square antiprismatic for nine-coordination To distinguish between the alternative coordinations for five-coordinated complexes, the τ geometry index was invented by Addison et al. This index depends on angles by the coordination center and changes between 0 for the square pyramidal to 1 for trigonal bipyramidal structures, allowing to classify the cases in between. This system was later extended to four-coordinated complexes by Houser et al. and also Okuniewski et al. In systems with low d electron count, due to special electronic effects such as (second-order) Jahn–Teller stabilization, certain geometries (in which the coordination atoms do not follow a points-on-a-sphere pattern) are stabilized relative to the other possibilities, e.g. for some compounds the trigonal prismatic geometry is stabilized relative to octahedral structures for six-coordination. * Bent for two-coordination *
Trigonal pyramidal In chemistry, a trigonal pyramid is a molecular geometry with one atom at the apex and three atoms at the corners of a trigonal base, resembling a tetrahedron (not to be confused with the tetrahedral geometry). When all three atoms at the corne ...
for three-coordination * Trigonal prismatic for six-coordination


Isomerism

The arrangement of the ligands is fixed for a given complex, but in some cases it is mutable by a reaction that forms another stable
isomer In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. Is ...
. There exist many kinds of
isomerism In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers. Is ...
in coordination complexes, just as in many other compounds.


Stereoisomerism

Stereoisomerism occurs with the same bonds in distinct orientations. Stereoisomerism can be further classified into:


=Cis–trans isomerism and facial–meridional isomerism

=
Cis–trans isomerism ''Cis''–''trans'' isomerism, also known as geometric isomerism or configurational isomerism, is a term used in chemistry that concerns the spatial arrangement of atoms within molecules. The prefixes "''cis''" and "''trans''" are from Latin: " ...
occurs in octahedral and
square planar The square planar molecular geometry in chemistry describes the stereochemistry (spatial arrangement of atoms) that is adopted by certain chemical compounds. As the name suggests, molecules of this geometry have their atoms positioned at the corne ...
complexes (but not tetrahedral). When two ligands are adjacent they are said to be cis, when opposite each other, trans. When three identical ligands occupy one face of an octahedron, the isomer is said to be facial, or fac. In a ''fac'' isomer, any two identical ligands are adjacent or ''cis'' to each other. If these three ligands and the metal ion are in one plane, the isomer is said to be meridional, or mer. A ''mer'' isomer can be considered as a combination of a ''trans'' and a ''cis'', since it contains both trans and cis pairs of identical ligands.
Image:Cis-dichlorotetraamminecobalt(III).png, Image:Trans-dichlorotetraamminecobalt(III).png, Image:Fac-trichlorotriamminecobalt(III).png, Image:Mer-trichlorotriamminecobalt(III).png,


=Optical isomerism

= Optical isomerism occurs when a complex is not superimposable with its mirror image. It is so called because the two isomers are each
optically active Optical rotation, also known as polarization rotation or circular birefringence, is the rotation of the orientation of the plane of polarization about the optical axis of linearly polarized light as it travels through certain materials. Circul ...
, that is, they rotate the plane of
polarized light Polarization ( also polarisation) is a property applying to transverse waves that specifies the geometrical orientation of the oscillations. In a transverse wave, the direction of the oscillation is perpendicular to the direction of motion of t ...
in opposite directions. In the first molecule shown, the symbol Λ (''
lambda Lambda (}, ''lám(b)da'') is the 11th letter of the Greek alphabet, representing the voiced alveolar lateral approximant . In the system of Greek numerals, lambda has a value of 30. Lambda is derived from the Phoenician Lamed . Lambda gave ri ...
'') is used as a prefix to describe the left-handed propeller twist formed by three bidentate ligands. The second molecule is the mirror image of the first, with the symbol Δ ('' delta'') as a prefix for the right-handed propeller twist. The third and fourth molecules are a similar pair of Λ and Δ isomers, in this case with two bidentate ligands and two identical monodentate ligands.
Image:Delta-tris(oxalato)ferrate(III)-3D-balls.png, Image:Lambda-tris(oxalato)ferrate(III)-3D-balls.png, Image:Delta-cis-dichlorobis(ethylenediamine)cobalt(III).png, Image:Lambda-cis-dichlorobis(ethylenediamine)cobalt(III).png,


Structural isomerism

Structural isomerism In chemistry, a structural isomer (or constitutional isomer in the IUPAC nomenclature) of a compound is another compound whose molecule has the same number of atoms of each element, but with logically distinct bonds between them. The term meta ...
occurs when the bonds are themselves different. Four types of structural isomerism are recognized: ionisation isomerism, solvate or hydrate isomerism, linkage isomerism and coordination isomerism. # Ionisation isomerism – the isomers give different ions in solution although they have the same composition. This type of isomerism occurs when the counter ion of the complex is also a potential ligand. For example, pentaamminebromocobalt(III) sulphate is red violet and in solution gives a precipitate with barium chloride, confirming the presence of sulphate ion, while pentaamminesulphatecobalt(III) bromide is red and tests negative for sulphate ion in solution, but instead gives a precipitate of AgBr with silver nitrate.Huheey, James E., ''Inorganic Chemistry'' (3rd ed., Harper & Row 1983), p.524–5 # Solvate or hydrate isomerism – the isomers have the same composition but differ with respect to the number of molecules of solvent that serve as ligand vs simply occupying sites in the crystal. Examples: is violet colored, is blue-green, and is dark green. See
water of crystallization In chemistry, water(s) of crystallization or water(s) of hydration are water molecules that are present inside crystals. Water is often incorporated in the formation of crystals from aqueous solutions. In some contexts, water of crystallization i ...
. #
Linkage isomerism In chemistry, linkage isomerism or ambidentate isomerism is a form of isomerism in which certain coordination compounds have the same composition but differ in their metal atom's connectivity to a ligand. Typical ligands that give rise to linka ...
occurs with ligands with more than one type of donor atom, known as ambidentate ligands. For example,
nitrite The nitrite ion has the chemical formula . Nitrite (mostly sodium nitrite) is widely used throughout chemical and pharmaceutical industries. The nitrite anion is a pervasive intermediate in the nitrogen cycle in nature. The name nitrite also ...
can coordinate through O or N. One pair of nitrite linkage isomers have structures (nitro isomer) and (nitrito isomer). # Coordination isomerism – this occurs when both positive and negative ions of a salt are complex ions and the two isomers differ in the distribution of ligands between the cation and the anion. For example, and .


Electronic properties

Many of the properties of transition metal complexes are dictated by their electronic structures. The electronic structure can be described by a relatively ionic model that ascribes formal charges to the metals and ligands. This approach is the essence of
crystal field theory Crystal field theory (CFT) describes the breaking of degeneracies of electron orbital states, usually ''d'' or ''f'' orbitals, due to a static electric field produced by a surrounding charge distribution (anion neighbors). This theory has been used ...
(CFT). Crystal field theory, introduced by
Hans Bethe Hans Albrecht Bethe (; July 2, 1906 – March 6, 2005) was a German-American theoretical physicist who made major contributions to nuclear physics, astrophysics, quantum electrodynamics, and solid-state physics, and who won the 1967 Nobel ...
in 1929, gives a quantum mechanically based attempt at understanding complexes. But crystal field theory treats all interactions in a complex as ionic and assumes that the ligands can be approximated by negative point charges. More sophisticated models embrace covalency, and this approach is described by ligand field theory (LFT) and
Molecular orbital theory In chemistry, molecular orbital theory (MO theory or MOT) is a method for describing the electronic structure of molecules using quantum mechanics. It was proposed early in the 20th century. In molecular orbital theory, electrons in a molec ...
(MO). Ligand field theory, introduced in 1935 and built from molecular orbital theory, can handle a broader range of complexes and can explain complexes in which the interactions are
covalent A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atom ...
. The chemical applications of
group theory In abstract algebra, group theory studies the algebraic structures known as groups. The concept of a group is central to abstract algebra: other well-known algebraic structures, such as rings, fields, and vector spaces, can all be seen ...
can aid in the understanding of crystal or ligand field theory, by allowing simple, symmetry based solutions to the formal equations. Chemists tend to employ the simplest model required to predict the properties of interest; for this reason, CFT has been a favorite for the discussions when possible. MO and LF theories are more complicated, but provide a more realistic perspective. The electronic configuration of the complexes gives them some important properties:


Color of transition metal complexes

Transition metal complexes often have spectacular colors caused by electronic transitions by the absorption of light. For this reason they are often applied as pigments. Most transitions that are related to colored metal complexes are either d–d transitions or
charge transfer band 193px, The intense color of tris(bipyridine)ruthenium(II) arises from a metal-to-ligand charge-transfer band. Charge-transfer bands are a characteristic feature of the optical spectra of many compounds. These bands are typically more intense tha ...
s. In a d–d transition, an electron in a d orbital on the metal is excited by a photon to another d orbital of higher energy, therefore d–d transitions occur only for partially-filled d-orbital complexes (d1–9). For complexes having d0 or d10 configuration, charge transfer is still possible even though d–d transitions are not. A charge transfer band entails promotion of an electron from a metal-based orbital into an empty ligand-based orbital ( metal-to-ligand charge transfer or MLCT). The converse also occurs: excitation of an electron in a ligand-based orbital into an empty metal-based orbital ( ligand-to-metal charge transfer or LMCT). These phenomena can be observed with the aid of electronic spectroscopy; also known as UV-Vis. For simple compounds with high symmetry, the d–d transitions can be assigned using
Tanabe–Sugano diagram In coordination chemistry, Tanabe–Sugano diagrams are used to predict absorptions in the ultraviolet (UV), visible and infrared (IR) electromagnetic spectrum of coordination compounds. The results from a Tanabe–Sugano diagram analysis of a ...
s. These assignments are gaining increased support with
computational chemistry Computational chemistry is a branch of chemistry that uses computer simulation to assist in solving chemical problems. It uses methods of theoretical chemistry, incorporated into computer programs, to calculate the structures and properties of mo ...
.


Colors of lanthanide complexes

Superficially
lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yt ...
complexes are similar to those of the transition metals in that some are colored. However, for the common Ln3+ ions (Ln = lanthanide) the colors are all pale, and hardly influenced by the nature of the ligand. The colors are due to 4f electron transitions. As the 4f orbitals in lanthanides are "buried" in the xenon core and shielded from the ligand by the 5s and 5p orbitals they are therefore not influenced by the ligands to any great extent leading to a much smaller
crystal field Crystal field theory (CFT) describes the breaking of degeneracies of electron orbital states, usually ''d'' or ''f'' orbitals, due to a static electric field produced by a surrounding charge distribution (anion neighbors). This theory has been used ...
splitting than in the transition metals. The absorption spectra of an Ln3+ ion approximates to that of the free ion where the electronic states are described by spin-orbit coupling. This contrasts to the transition metals where the ground state is split by the crystal field. Absorptions for Ln3+ are weak as electric dipole transitions are parity forbidden ( Laporte forbidden) but can gain intensity due to the effect of a low-symmetry ligand field or mixing with higher electronic states (''e.g.'' d orbitals). f-f absorption bands are extremely sharp which contrasts with those observed for transition metals which generally have broad bands. This can lead to extremely unusual effects, such as significant color changes under different forms of lighting.


Magnetism

Metal complexes that have unpaired electrons are
magnetic Magnetism is the class of physical attributes that are mediated by a magnetic field, which refers to the capacity to induce attractive and repulsive phenomena in other entities. Electric currents and the magnetic moments of elementary particl ...
. Considering only monometallic complexes, unpaired electrons arise because the complex has an odd number of electrons or because electron pairing is destabilized. Thus, monomeric Ti(III) species have one "d-electron" and must be (para)magnetic, regardless of the geometry or the nature of the ligands. Ti(II), with two d-electrons, forms some complexes that have two unpaired electrons and others with none. This effect is illustrated by the compounds TiX2 CH3)2PCH2CH2P(CH3)2sub>2: when X =  Cl, the complex is paramagnetic ( high-spin configuration), whereas when X =  CH3, it is diamagnetic ( low-spin configuration). It is important to realize that ligands provide an important means of adjusting the
ground state The ground state of a quantum-mechanical system is its stationary state of lowest energy; the energy of the ground state is known as the zero-point energy of the system. An excited state is any state with energy greater than the ground state. ...
properties. In bi- and polymetallic complexes, in which the individual centres have an odd number of electrons or that are high-spin, the situation is more complicated. If there is interaction (either direct or through ligand) between the two (or more) metal centres, the electrons may couple ( antiferromagnetic coupling, resulting in a diamagnetic compound), or they may enhance each other ( ferromagnetic coupling). When there is no interaction, the two (or more) individual metal centers behave as if in two separate molecules.


Reactivity

Complexes show a variety of possible reactivities: * Electron transfers *:
Electron transfer Electron transfer (ET) occurs when an electron relocates from an atom or molecule to another such chemical entity. ET is a mechanistic description of certain kinds of redox reactions involving transfer of electrons. Electrochemical processes ar ...
(ET) between metal ions can occur via two distinct mechanisms,
inner Interior may refer to: Arts and media * ''Interior'' (Degas) (also known as ''The Rape''), painting by Edgar Degas * ''Interior'' (play), 1895 play by Belgian playwright Maurice Maeterlinck * ''The Interior'' (novel), by Lisa See * Interior de ...
and
outer sphere electron transfer Outer sphere refers to an electron transfer (ET) event that occurs between chemical species that remain separate and intact before, during, and after the ET event. In contrast, for inner sphere electron transfer the participating redox sites under ...
s. In an inner sphere reaction, a
bridging ligand In coordination chemistry, a bridging ligand is a ligand that connects two or more atoms, usually metal ions. The ligand may be atomic or polyatomic. Virtually all complex organic compounds can serve as bridging ligands, so the term is usually ...
serves as a conduit for ET. * (Degenerate)
ligand exchange In coordination chemistry, a ligand is an ion or molecule (functional group) that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's elect ...
*: One important indicator of reactivity is the rate of degenerate exchange of ligands. For example, the rate of interchange of coordinate water in (H2O)6sup>''n''+ complexes varies over 20 orders of magnitude. Complexes where the ligands are released and rebound rapidly are classified as labile. Such labile complexes can be quite stable thermodynamically. Typical labile metal complexes either have low-charge (Na+), electrons in d-orbitals that are
antibonding In chemical bonding theory, an antibonding orbital is a type of molecular orbital that weakens the chemical bond between two atoms and helps to raise the energy of the molecule relative to the separated atoms. Such an orbital has one or more no ...
with respect to the ligands (Zn2+), or lack covalency (Ln3+, where Ln is any lanthanide). The lability of a metal complex also depends on the high-spin vs. low-spin configurations when such is possible. Thus, high-spin Fe(II) and Co(III) form labile complexes, whereas low-spin analogues are inert. Cr(III) can exist only in the low-spin state (quartet), which is inert because of its high formal oxidation state, absence of electrons in orbitals that are M–L antibonding, plus some "ligand field stabilization" associated with the d3 configuration. * Associative processes *: Complexes that have unfilled or half-filled orbitals are often capable of reacting with substrates. Most substrates have a singlet ground-state; that is, they have lone electron pairs (e.g., water, amines, ethers), so these substrates need an empty orbital to be able to react with a metal centre. Some substrates (e.g., molecular oxygen) have a triplet ground state, which results that metals with half-filled orbitals have a tendency to react with such substrates (it must be said that the dioxygen molecule also has lone pairs, so it is also capable to react as a 'normal' Lewis base). If the ligands around the metal are carefully chosen, the metal can aid in (
stoichiometric Stoichiometry refers to the relationship between the quantities of reactants and products before, during, and following chemical reactions. Stoichiometry is founded on the law of conservation of mass where the total mass of the reactants equ ...
or catalytic) transformations of molecules or be used as a sensor.


Classification

Metal complexes, also known as coordination compounds, include virtually all metal compounds. The study of "coordination chemistry" is the study of "inorganic chemistry" of all
alkali In chemistry, an alkali (; from ar, القلوي, al-qaly, lit=ashes of the saltwort) is a basic, ionic salt of an alkali metal or an alkaline earth metal. An alkali can also be defined as a base that dissolves in water. A solution of a ...
and
alkaline earth metal The alkaline earth metals are six chemical elements in group 2 of the periodic table. They are beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).. The elements have very similar properties: they are all ...
s,
transition metal In chemistry, a transition metal (or transition element) is a chemical element in the d-block of the periodic table (groups 3 to 12), though the elements of group 12 (and less often group 3) are sometimes excluded. They are the elements that can ...
s,
lanthanide The lanthanide () or lanthanoid () series of chemical elements comprises the 15 metallic chemical elements with atomic numbers 57–71, from lanthanum through lutetium. These elements, along with the chemically similar elements scandium and yt ...
s,
actinides The actinide () or actinoid () series encompasses the 15 metallic chemical elements with atomic numbers from 89 to 103, actinium through lawrencium. The actinide series derives its name from the first element in the series, actinium. The inform ...
, and
metalloid A metalloid is a type of chemical element which has a preponderance of properties in between, or that are a mixture of, those of metals and nonmetals. There is no standard definition of a metalloid and no complete agreement on which elements are ...
s. Thus, coordination chemistry is the chemistry of the majority of the periodic table. Metals and metal ions exist, in the condensed phases at least, only surrounded by ligands. The areas of coordination chemistry can be classified according to the nature of the ligands, in broad terms: * Classical (or " Werner Complexes"): Ligands in classical coordination chemistry bind to metals, almost exclusively, via their
lone pair In chemistry, a lone pair refers to a pair of valence electrons that are not shared with another atom in a covalent bondIUPAC '' Gold Book'' definition''lone (electron) pair''/ref> and is sometimes called an unshared pair or non-bonding pair. L ...
s of electrons residing on the main-group atoms of the ligand. Typical ligands are H2O, NH3, Cl, CN, en. Some of the simplest members of such complexes are described in
metal aquo complex In chemistry, metal aquo complexes are coordination compounds containing metal ions with only water as a ligand. These complexes are the predominant species in aqueous solutions of many metal salts, such as metal nitrates, sulfates, and perchlorat ...
es, metal ammine complexes, : Examples: o(EDTA).html"_;"title="EDTA.html"_;"title="o(EDTA">o(EDTA)">EDTA.html"_;"title="o(EDTA">o(EDTA)sup>−,_Cobalt(III)_hexammine_chloride.html" ;"title="EDTA">o(EDTA).html" ;"title="EDTA.html" ;"title="o(EDTA">o(EDTA)">EDTA.html" ;"title="o(EDTA">o(EDTA)sup>−, Cobalt(III) hexammine chloride">[Co(NH3)6sup>3+, Potassium ferrioxalate, [Fe(C2O4)3]3- *
Organometallic chemistry Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and s ...
: Ligands are organic (alkenes, alkynes, alkyls) as well as "organic-like" ligands such as phosphines, hydride, and CO. : Example: (C5H5)Fe(CO)2CH3 *
Bioinorganic chemistry Bioinorganic chemistry is a field that examines the role of metals in biology. Bioinorganic chemistry includes the study of both natural phenomena such as the behavior of metalloproteins as well as artificially introduced metals, including those t ...
: Ligands are those provided by nature, especially including the side chains of amino acids, and many cofactors such as porphyrins. : Example:
hemoglobin Hemoglobin (haemoglobin BrE) (from the Greek word αἷμα, ''haîma'' 'blood' + Latin ''globus'' 'ball, sphere' + ''-in'') (), abbreviated Hb or Hgb, is the iron-containing oxygen-transport metalloprotein present in red blood cells (erythroc ...
contains
heme Heme, or haem (pronounced / hi:m/ ), is a precursor to hemoglobin, which is necessary to bind oxygen in the bloodstream. Heme is biosynthesized in both the bone marrow and the liver. In biochemical terms, heme is a coordination complex "consis ...
, a porphyrin complex of iron : Example:
chlorophyll Chlorophyll (also chlorophyl) is any of several related green pigments found in cyanobacteria and in the chloroplasts of algae and plants. Its name is derived from the Greek words , ("pale green") and , ("leaf"). Chlorophyll allow plants to ...
contains a porphyrin complex of magnesium : Many natural ligands are "classical" especially including water. *
Cluster chemistry In chemistry, an atom cluster (or simply cluster) is an ensemble of bound atoms or molecules that is intermediate in size between a simple molecule and a nanoparticle; that is, up to a few nanometers (nm) in diameter. The term ''microclus ...
: Ligands include all of the above as well as other metal ions or atoms as well. : Example Ru3(CO)12 * In some cases there are combinations of different fields: :Example: e4S4(Scysteinyl)4sup>2−, in which a cluster is embedded in a biologically active species.
Mineralogy Mineralogy is a subject of geology specializing in the scientific study of the chemistry, crystal structure, and physical (including optical) properties of minerals and mineralized artifacts. Specific studies within mineralogy include the proce ...
, materials science, and
solid state chemistry Solid-state chemistry, also sometimes referred as materials chemistry, is the study of the synthesis, structure, and properties of solid phase materials, particularly, but not necessarily exclusively of, non-molecular solids. It therefore has a str ...
 – as they apply to metal ions – are subsets of coordination chemistry in the sense that the metals are surrounded by ligands. In many cases these ligands are oxides or sulfides, but the metals are coordinated nonetheless, and the principles and guidelines discussed below apply. In
hydrate In chemistry, a hydrate is a substance that contains water or its constituent elements. The chemical state of the water varies widely between different classes of hydrates, some of which were so labeled before their chemical structure was understo ...
s, at least some of the ligands are water molecules. It is true that the focus of mineralogy, materials science, and solid state chemistry differs from the usual focus of coordination or inorganic chemistry. The former are concerned primarily with polymeric structures, properties arising from a collective effects of many highly interconnected metals. In contrast, coordination chemistry focuses on reactivity and properties of complexes containing individual metal atoms or small ensembles of metal atoms.


Nomenclature of coordination complexes

The basic procedure for naming a complex is: # When naming a complex ion, the ligands are named before the metal ion. # The ligands' names are given in alphabetical order. Numerical prefixes do not affect the order. #* Multiple occurring monodentate ligands receive a prefix according to the number of occurrences: ''di-'', ''tri-'', ''tetra-'', ''penta-'', or ''hexa-''. #* Multiple occurring polydentate ligands (e.g., ethylenediamine, oxalate) receive ''bis-'', ''tris-'', ''tetrakis-'', etc. #* Anions end in ''o''. This replaces the final 'e' when the anion ends with '-ide', '-ate' or '-ite', e.g. ''chloride'' becomes ''chlorido'' and ''sulfate'' becomes ''sulfato''. Formerly, '-ide' was changed to '-o' (e.g. ''chloro'' and ''cyano''), but this rule has been modified in the 2005 IUPAC recommendations and the correct forms for these ligands are now ''chlorido'' and ''cyanido''. #* Neutral ligands are given their usual name, with some exceptions: NH3 becomes '' ammine''; H2O becomes ''aqua'' or ''aquo''; CO becomes ''carbonyl''; NO becomes ''nitrosyl''. # Write the name of the central atom/ion. If the complex is an anion, the central atom's name will end in ''-ate'', and its Latin name will be used if available (except for mercury). # The oxidation state of the central atom is to be specified (when it is one of several possible, or zero), and should be written as a Roman numeral (or 0) enclosed in parentheses. # Name of the cation should be preceded by the name of anion. (if applicable, as in last example) Examples: : d(CN)2(en)2→ dicyanidobis(ethylenediamine)cadmium(II) : oCl(NH3)5O4 → pentaamminechloridocobalt(III) sulfate : u(H2O)62+ → hexaaquacopper(II) ion : uCl5NH3sup>3− → amminepentachloridocuprate(II) ion : K4 e(CN)6→ potassium hexacyanidoferrate(II) : iCl4sup>2− → tetrachloridonickelate(II) ion (The use of chloro- was removed from IUPAC naming convention) The coordination number of ligands attached to more than one metal (bridging ligands) is indicated by a subscript to the Greek symbol μ placed before the ligand name. Thus the
dimer Dimer may refer to: * Dimer (chemistry), a chemical structure formed from two similar sub-units ** Protein dimer, a protein quaternary structure ** d-dimer * Dimer model, an item in statistical mechanics, based on ''domino tiling'' * Julius Dimer ( ...
of
aluminium trichloride Aluminium chloride, also known as aluminium trichloride, is an inorganic compound with the formula . It forms hexahydrate with the formula , containing six water molecules of hydration. Both are colourless crystals, but samples are often contam ...
is described by Al2Cl42-Cl)2. Any anionic group can be electronically stabilized by any cation. An anionic complex can be stabilised by a hydrogen cation, becoming an acidic complex which can dissociate to release the cationic hydrogen. This kind of complex compound has a name with "ic" added after the central metal. For example, H2 t(CN)4has the name tetracyanoplatinic (II) acid.


Stability constant

The affinity of metal ions for ligands is described by a stability constant, also called the formation constant, and is represented by the symbol Kf. It is the
equilibrium constant The equilibrium constant of a chemical reaction is the value of its reaction quotient at chemical equilibrium, a state approached by a dynamic chemical system after sufficient time has elapsed at which its composition has no measurable tendency ...
for its assembly from the constituent metal and ligands, and can be calculated accordingly, as in the following example for a simple case: :xM (aq) + yL (aq) zZ (aq) :K_f = \frac where : x, y, and z are the
stoichiometric Stoichiometry refers to the relationship between the quantities of reactants and products before, during, and following chemical reactions. Stoichiometry is founded on the law of conservation of mass where the total mass of the reactants equ ...
coefficients of each species. M stands for metal / metal ion , the L for Lewis bases , and finally Z for complex ions. Formation constants vary widely. Large values indicate that the metal has high affinity for the ligand, provided the system is at equilibrium. Sometimes the stability constant will be in a different form known as the constant of destability. This constant is expressed as the inverse of the constant of formation and is denoted as Kd = 1/Kf . This constant represents the reverse reaction for the decomposition of a complex ion into its individual metal and ligand components. When comparing the values for Kd, the larger the value, the more unstable the complex ion is. As a result of these complex ions forming in solutions they also can play a key role in solubility of other compounds. When a complex ion is formed it can alter the concentrations of its components in the solution. For example: :Ag + 2NH3 Ag(NH3) :AgCl(s) + H2O(l) Ag + Cl If these reactions both occurred in the same reaction vessel, the solubility of the silver chloride would be increased by the presence of NH4OH because formation of the Diammine argentum(I) complex consumes a significant portion of the free silver ions from the solution. By
Le Chatelier's principle Le Chatelier's principle (pronounced or ), also called Chatelier's principle (or the Equilibrium Law), is a principle of chemistry used to predict the effect of a change in conditions on chemical equilibria. The principle is named after French ...
, this causes the equilibrium reaction for the dissolving of the silver chloride, which has silver ion as a product, to shift to the right. This new solubility can be calculated given the values of Kf and Ksp for the original reactions. The solubility is found essentially by combining the two separate equilibria into one combined equilibrium reaction and this combined reaction is the one that determines the new solubility. So Kc, the new solubility constant, is denoted by: :K_c = K_ K_f


Application of coordination compounds

As metals only exist in solution as coordination complexes, it follows then that this class of compounds is useful in a wide variety of ways.


Bioinorganic chemistry

In
bioinorganic chemistry Bioinorganic chemistry is a field that examines the role of metals in biology. Bioinorganic chemistry includes the study of both natural phenomena such as the behavior of metalloproteins as well as artificially introduced metals, including those t ...
and bioorganometallic chemistry, coordination complexes serve either structural or catalytic functions. An estimated 30% of proteins contain metal ions. Examples include the intensely colored vitamin B12, the heme group in
hemoglobin Hemoglobin (haemoglobin BrE) (from the Greek word αἷμα, ''haîma'' 'blood' + Latin ''globus'' 'ball, sphere' + ''-in'') (), abbreviated Hb or Hgb, is the iron-containing oxygen-transport metalloprotein present in red blood cells (erythroc ...
, the
cytochrome Cytochromes are redox-active proteins containing a heme, with a central Fe atom at its core, as a cofactor. They are involved in electron transport chain and redox catalysis. They are classified according to the type of heme and its mode of ...
s, the chlorin group in
chlorophyll Chlorophyll (also chlorophyl) is any of several related green pigments found in cyanobacteria and in the chloroplasts of algae and plants. Its name is derived from the Greek words , ("pale green") and , ("leaf"). Chlorophyll allow plants to ...
, and
carboxypeptidase A carboxypeptidase ( EC number 3.4.16 - 3.4.18) is a protease enzyme that hydrolyzes (cleaves) a peptide bond at the carboxy-terminal (C-terminal) end of a protein or peptide. This is in contrast to an aminopeptidases, which cleave peptide b ...
, a hydrolytic enzyme important in digestion. Another complex ion enzyme is
catalase Catalase is a common enzyme found in nearly all living organisms exposed to oxygen (such as bacteria, plants, and animals) which catalyzes the decomposition of hydrogen peroxide to water and oxygen. It is a very important enzyme in protecting t ...
, which decomposes the cell's waste
hydrogen peroxide Hydrogen peroxide is a chemical compound with the formula . In its pure form, it is a very pale blue liquid that is slightly more viscous than water. It is used as an oxidizer, bleaching agent, and antiseptic, usually as a dilute solution (3 ...
. Synthetic coordination compounds are also used to bind to proteins and especially nucleic acids (e.g. anticancer drug
cisplatin Cisplatin is a chemotherapy medication used to treat a number of cancers. These include testicular cancer, ovarian cancer, cervical cancer, breast cancer, bladder cancer, head and neck cancer, esophageal cancer, lung cancer, mesothelioma, ...
).


Industry

Homogeneous catalysis In chemistry, homogeneous catalysis is catalysis by a soluble catalyst in a solution. Homogeneous catalysis refers to reactions where the catalyst is in the same phase as the reactants, principally in solution. In contrast, heterogeneous catalysi ...
is a major application of coordination compounds for the production of organic substances. Processes include
hydrogenation Hydrogenation is a chemical reaction between molecular hydrogen (H2) and another compound or element, usually in the presence of a catalyst such as nickel, palladium or platinum. The process is commonly employed to reduce or saturate organic ...
,
hydroformylation Hydroformylation, also known as oxo synthesis or oxo process, is an industrial process for the production of aldehydes from alkenes. This chemical reaction entails the net addition of a formyl group (CHO) and a hydrogen atom to a carbon-carbon ...
,
oxidation Redox (reduction–oxidation, , ) is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or ...
. In one example, a combination of titanium trichloride and triethylaluminium gives rise to Ziegler–Natta catalysts, used for the
polymerization In polymer chemistry, polymerization (American English), or polymerisation (British English), is a process of reacting monomer molecules together in a chemical reaction to form polymer chains or three-dimensional networks. There are many f ...
of ethylene and propylene to give polymers of great commercial importance as fibers, films, and plastics. Nickel, cobalt, and copper can be extracted using hydrometallurgical processes involving complex ions. They are extracted from their ores as ammine complexes. Metals can also be separated using the selective precipitation and solubility of complex ions. Cyanide is used chiefly for extraction of gold and silver from their ores. Phthalocyanine complexes are an important class of pigments.


Analysis

At one time, coordination compounds were used to identify the presence of metals in a sample.
Qualitative inorganic analysis Classical qualitative inorganic analysis is a method of analytical chemistry which seeks to find the elemental composition of inorganic compounds. It is mainly focused on detecting ions in an aqueous solution, therefore materials in other forms m ...
has largely been superseded by instrumental methods of analysis such as
atomic absorption spectroscopy Atomic absorption spectroscopy (AAS) and atomic emission spectroscopy (AES) is a spectroanalytical procedure for the quantitative determination of chemical elemlight) by free atoms in the gaseous state. Atomic absorption spectroscopy is based ...
(AAS), inductively coupled plasma atomic emission spectroscopy (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS).


See also

*
Activated complex In chemistry an activated complex is defined by the International Union of Pure and Applied Chemistry (IUPAC) as "that assembly of atoms which corresponds to an arbitrary infinitesimally small region at or near the col (saddle point) of a potential ...
* IUPAC nomenclature of inorganic chemistry *
Coordination cage Coordination cages are three-dimensional ordered structures in solution that act as hosts in host–guest chemistry. They are self-assembled in solution from organometallic precursors, and often rely solely on noncovalent interactions rather than co ...
*
Coordination geometry The term coordination geometry is used in a number of related fields of chemistry and solid state chemistry/physics. Molecules The coordination geometry of an atom is the geometrical pattern formed by atoms around the central atom. Inorganic coo ...
*
Coordination isomerism Coordination isomerism is a form of structural isomerism in which the composition of the coordination complex A coordination complex consists of a central atom or ion, which is usually metallic and is called the ''coordination centre'', and a sur ...
* Coordination polymers, in which coordination complexes are the repeating units. *
Inclusion compound In host–guest chemistry In supramolecular chemistry, host–guest chemistry describes complexes that are composed of two or more molecules or ions that are held together in unique structural relationships by forces other than those of full cova ...
s *
Organometallic chemistry Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and s ...
deals with a special class of coordination compounds where organic fragments are bonded to a metal at least through one C atom.


References


Further reading

* De Vito, D.; Weber, J. ; Merbach, A. E. “Calculated Volume and Energy Profiles for Water Exchange on t2g 6 Rhodium(III) and Iridium(III) Hexaaquaions: Conclusive Evidence for an Ia Mechanism” Inorganic Chemistry, 2004, Volume 43, pages 858–863. * Zumdahl, Steven S. Chemical Principles, Fifth Edition. New York: Houghton Mifflin, 2005. 943–946, 957. * Harris, D., Bertolucci, M., ''Symmetry and Spectroscopy''. 1989 New York, Dover Publications


External links


Naming Coordination Compounds
{{DEFAULTSORT:Coordination Complex Inorganic chemistry Transition metals Coordination chemistry