What are ligands in chemistry11.03.2021
Ligands are ions or neutral molecules that bond to a central metal atom or ion. Ligands act as Lewis bases (electron pair donors), and the central atom acts as a Lewis acid (electron pair acceptor). Ligands have at least one donor atom with an electron pair used to form covalent bonds with the central atom. Ligand, in chemistry, any atom or molecule attached to a central atom, usually a metallic element, in a coordination or complex compound. The atoms and molecules used as ligands are almost always those that are capable of functioning as the electron-pair donor in the electron-pair bond (a coordinate covalent bond) formed with the metal atom.
Ligandin chemistryany atom or molecule attached to a central atom, usually a metallic element, in a coordination or complex compound. The atoms and molecules used as ligands are almost always those that are capable of functioning as the electron-pair donor in the electron-pair bond a coordinate covalent bond formed with the metal atom.
Occasionally, ligands can be cations e. Attachment of the ligand to the metal may be through a single atom, in which case it is called a monodentate ligand, or through two or more atoms, in which case it is called a how to make sweet butter or polydentate ligand.
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Ligand s are ions or neutral molecules with what are ligands in chemistry pairs that they can donate to the metal atom to form a coordinate-covalent bond. Coordination compounds include such substances as vitamin B 12hemoglobin, and chlorophyll, dyes and pigments, and catalysts used in preparing organic substances. History at your fingertips. Sign up here to see what happened On This Dayevery day in your inbox!
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11 rows · A ligand is an ion or molecule, which binds to the central metal atom to form a .
In coordination chemistry , a ligand [a] 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 electron pairs often through Lewis Bases. Furthermore, the metal—ligand bond order can range from one to three.
Ligands are viewed as Lewis bases , although rare cases are known to involve Lewis acidic "ligands". Metals and metalloids are bound to ligands in almost all circumstances, although gaseous "naked" metal ions can be generated in a high vacuum. Ligands in a complex dictate the reactivity of the central atom, including ligand substitution rates, the reactivity of the ligands themselves, and redox. Ligand selection is a critical consideration in many practical areas, including bioinorganic and medicinal chemistry , homogeneous catalysis , and environmental chemistry.
Ligands are classified in many ways, including: charge, size bulk , the identity of the coordinating atom s , and the number of electrons donated to the metal denticity or hapticity. The size of a ligand is indicated by its cone angle. The composition of coordination complexes have been known since the early s, such as Prussian blue and copper vitriol. The key breakthrough occurred when Alfred Werner reconciled formulas and isomers. He showed, among other things, that the formulas of many cobalt III and chromium III compounds can be understood if the metal has six ligands in an octahedral geometry.
The first to use the term "ligand" were Alfred Werner and Carl Somiesky, in relation to silicon chemistry. The theory allows one to understand the difference between coordinated and ionic chloride in the cobalt ammine chlorides and to explain many of the previously inexplicable isomers.
He resolved the first coordination complex called hexol into optical isomers, overthrowing the theory that chirality was necessarily associated with carbon compounds. In general, ligands are viewed as electron donors and the metals as electron acceptors, i.
This description has been semi-quantified in many ways, e. ECW model. Bonding is often described using the formalisms of molecular orbital theory. Metal ions preferentially bind certain ligands. In general, 'hard' metal ions prefer weak field ligands, whereas 'soft' metal ions prefer strong field ligands. Metal ions bound to strong-field ligands follow the Aufbau principle , whereas complexes bound to weak-field ligands follow Hund's rule.
Binding of the metal with the ligands results in a set of molecular orbitals, where the metal can be identified with a new HOMO and LUMO the orbitals defining the properties and reactivity of the resulting complex and a certain ordering of the 5 d-orbitals which may be filled, or partially filled with electrons.
In an octahedral environment, the 5 otherwise degenerate d-orbitals split in sets of 2 and 3 orbitals for a more in depth explanation, see crystal field theory. This ordering of ligands is almost invariable for all metal ions and is called spectrochemical series. For complexes with a tetrahedral surrounding, the d-orbitals again split into two sets, but this time in reverse order.
When the coordination number is neither octahedral nor tetrahedral, the splitting becomes correspondingly more complex. The arrangement of the d-orbitals on the central atom as determined by the 'strength' of the ligand , has a strong effect on virtually all the properties of the resulting complexes. It turns out that valence electrons occupying orbitals with significant 3 d-orbital character absorb in the — nm region of the spectrum UV—visible range.
The absorption of light what we perceive as the color by these electrons that is, excitation of electrons from one orbital to another orbital under influence of light can be correlated to the ground state of the metal complex, which reflects the bonding properties of the ligands. The relative change in relative energy of the d-orbitals as a function of the field-strength of the ligands is described in Tanabe—Sugano diagrams. In cases where the ligand has low energy LUMO, such orbitals also participate in the bonding.
The metal—ligand bond can be further stabilised by a formal donation of electron density back to the ligand in a process known as back-bonding. In this case a filled, central-atom-based orbital donates density into the LUMO of the coordinated ligand. Carbon monoxide is the preeminent example a ligand that engages metals via back-donation. Complementarily, ligands with low-energy filled orbitals of pi-symmetry can serve as pi-donor. Especially in the area of organometallic chemistry , ligands are classified as L and X or combinations of the two.
Green and "is based on the notion that there are three basic types [of ligands] Example is alkoxy ligands which is regularly known as X ligand too. L ligands are derived from charge-neutral precursors and are represented by amines , phosphines , CO , N 2 , and alkenes.
X ligands typically are derived from anionic precursors such as chloride but includes ligands where salts of anion do not really exist such as hydride and alkyl. Cp is classified as an L 2 X ligand. Many ligands are capable of binding metal ions through multiple sites, usually because the ligands have lone pairs on more than one atom. Ligands that bind via more than one atom are often termed chelating. A ligand that binds through two sites is classified as bidentate , and three sites as tridentate.
The " bite angle " refers to the angle between the two bonds of a bidentate chelate. Chelating ligands are commonly formed by linking donor groups via organic linkers.
A classic example of a polydentate ligand is the hexadentate chelating agent EDTA , which is able to bond through six sites, completely surrounding some metals. In practice, the n value of a ligand is not indicated explicitly but rather assumed.
The binding affinity of a chelating system depends on the chelating angle or bite angle. Complexes of polydentate ligands are called chelate complexes. They tend to be more stable than complexes derived from monodentate ligands.
This enhanced stability, the chelate effect , is usually attributed to effects of entropy , which favors the displacement of many ligands by one polydentate ligand. When the chelating ligand forms a large ring that at least partially surrounds the central atom and bonds to it, leaving the central atom at the centre of a large ring. The more rigid and the higher its denticity, the more inert will be the macrocyclic complex.
Heme is a good example: the iron atom is at the centre of a porphyrin macrocycle, being bound to four nitrogen atoms of the tetrapyrrole macrocycle. The very stable dimethylglyoximate complex of nickel is a synthetic macrocycle derived from the anion of dimethylglyoxime.
Trans-spanning ligands are bidentate ligands that can span coordination positions on opposite sides of a coordination complex. Unlike polydentate ligands, ambidentate ligands can attach to the central atom in two places. Such compounds give rise to linkage isomerism.
Polyfunctional ligands, see especially proteins, can bond to a metal center through different ligand atoms to form various isomers. A bridging ligand links two or more metal centers.
Virtually all inorganic solids with simple formulas are coordination polymers , consisting of metal ion centres linked by bridging ligands. This group of materials includes all anhydrous binary metal ion halides and pseudohalides. Bridging ligands also persist in solution. Polyatomic ligands such as carbonate are ambidentate and thus are found to often bind to two or three metals simultaneously.
Most inorganic solids are polymers by virtue of the presence of multiple bridging ligands. Bridging ligands, capable of coordinating multiple metal ions, have been attracting considerable interest because of their potential use as building blocks for the fabrication of functional multimetallic assemblies.
Binucleating ligands bind two metal ions. Some ligands can bond to a metal center through the same atom but with a different number of lone pairs. This bond angle is often referred to as being linear or bent with further discussion concerning the degree to which the angle is bent. For example, an imido ligand in the ionic form has three lone pairs. One lone pair is used as a sigma X donor, the other two lone pairs are available as L-type pi donors. A spectator ligand is a tightly coordinating polydentate ligand that does not participate in chemical reactions but removes active sites on a metal.
Spectator ligands influence the reactivity of the metal center to which they are bound. Bulky ligands are used to control the steric properties of a metal center.
They are used for many reasons, both practical and academic. On the practical side, they influence the selectivity of metal catalysts, e. Of academic interest, bulky ligands stabilize unusual coordination sites, e. Often bulky ligands are employed to simulate the steric protection afforded by proteins to metal-containing active sites. Of course excessive steric bulk can prevent the coordination of certain ligands. Chiral ligands are useful for inducing asymmetry within the coordination sphere.
Often the ligand is employed as an optically pure group. In some cases, such as secondary amines, the asymmetry arises upon coordination. Chiral ligands are used in homogeneous catalysis , such as asymmetric hydrogenation. Hemilabile ligands contain at least two electronically different coordinating groups and form complexes where one of these is easily displaced from the metal center while the other remains firmly bound, a behaviour which has been found to increase the reactivity of catalysts when compared to the use of more traditional ligands.
Non-innocent ligands bond with metals in such a manner that the distribution of electron density between the metal center and ligand is unclear. Describing the bonding of non-innocent ligands often involves writing multiple resonance forms that have partial contributions to the overall state. Virtually every molecule and every ion can serve as a ligand for or "coordinate to" metals. Monodentate ligands include virtually all anions and all simple Lewis bases. Thus, the halides and pseudohalides are important anionic ligands whereas ammonia , carbon monoxide , and water are particularly common charge-neutral ligands.
The steric properties of some ligands are evaluated in terms of their cone angles. Beyond the classical Lewis bases and anions, all unsaturated molecules are also ligands, utilizing their pi electrons in forming the coordinate bond. In complexes of non-innocent ligands , the ligand is bonded to metals via conventional bonds, but the ligand is also redox-active.
The entries in the table are sorted by field strength, binding through the stated atom i. The 'strength' of the ligand changes when the ligand binds in an alternative binding mode e. A ligand exchange also ligand substitution is a type of chemical reaction in which a ligand in a compound is replaced by another. One type of pathway for substitution is the ligand dependent pathway. In organometallic chemistry this can take place via associative substitution or by dissociative substitution.