Metal aromaticity or metalloaromaticity is the concept of

aromaticity In chemistry, aromaticity is a chemical property of cyclic ( ring-shaped), ''typically'' planar (flat) molecular structures with pi bonds in resonance (those containing delocalized electrons) that gives increased stability compared to saturate ...

, found in many

organic compound In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. The ...

s, extended to

metals A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...

and metal-containing compounds. The first experimental evidence for the existence of aromaticity in metals was found in aluminium

cluster compound 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 ''microcluster'' ...

s of the type where M stands for

lithium Lithium (from el, λίθος, lithos, lit=stone) is a chemical element with the symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard conditions, it is the least dense metal and the least dense solid el ...

sodium Sodium is a chemical element with the symbol Na (from Latin ''natrium'') and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 of the periodic table. Its only stable iso ...

or copper. These

anion An ion () is an atom or molecule with a net electrical charge. The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...

s can be generated in a

helium Helium (from el, ἥλιος, helios, lit=sun) is a chemical element with the symbol He and atomic number 2. It is a colorless, odorless, tasteless, non-toxic, inert, monatomic gas and the first in the noble gas group in the periodic table. ...

gas by

laser vaporization Laser ablation or photoablation (also called laser blasting) is the process of removing material from a solid (or occasionally liquid) surface by irradiating it with a laser beam. At low laser flux, the material is heated by the absorbed laser ...

of an aluminium /

lithium carbonate Lithium carbonate is an inorganic compound, the lithium salt (chemistry), salt of carbonate with the chemical formula, formula . This white Salt (chemistry), salt is widely used in the processing of metal oxides. It is listed on the World Health O ...

composite or a copper or sodium / aluminium

alloy An alloy is a mixture of chemical elements of which at least one is a metal. Unlike chemical compounds with metallic bases, an alloy will retain all the properties of a metal in the resulting material, such as electrical conductivity, ductility, ...

, separated and selected by

mass spectrometry Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is use ...

and analyzed by

photoelectron spectroscopy Photoemission spectroscopy (PES), also known as photoelectron spectroscopy, refers to energy measurement of electrons emitted from solids, gases or liquids by the photoelectric effect, in order to determine the binding energies of electrons in th ...

. The evidence for aromaticity in these compounds is based on several considerations.

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 m ...

shows that these aluminium clusters consist of a tetranuclear plane and a counterion at the apex of a

square pyramid In geometry, a square pyramid is a pyramid having a square base. If the apex is perpendicularly above the center of the square, it is a right square pyramid, and has symmetry. If all edge lengths are equal, it is an equilateral square pyramid, ...

. The unit is perfectly planar and is not perturbed the presence of the

counterion 160px, Polystyrene sulfonate, a cation-exchange resin, is typically supplied with as the counterion.">cation-exchange_resin.html" ;"title="Polystyrene sulfonate, a cation-exchange resin">Polystyrene sulfonate, a cation-exchange resin, is typical ...

or even the presence of two counterions in the neutral compound . In addition its

HOMO ''Homo'' () is the genus that emerged in the (otherwise extinct) genus ''Australopithecus'' that encompasses the extant species ''Homo sapiens'' ( modern humans), plus several extinct species classified as either ancestral to or closely relate ...

is calculated to be a doubly occupied delocalized pi system making it obey

Hückel's rule In organic chemistry, Hückel's rule predicts that a planar ring molecule will have aromatic properties if it has 4''n'' + 2 π electrons, where ''n'' is a non-negative integer. The quantum mechanical basis for its formulation was fir ...

. Finally a match exists between the calculated values and the experimental photoelectron values for the energy required to remove the first 4 valence electrons. The first fully metal aromatic compound was a cyclogallane with a Ga₃^2- core discovered by Gregory Robinson in 1995. D-orbital aromaticity is found in trinuclear

tungsten Tungsten, or wolfram, is a chemical element with the symbol W and atomic number 74. Tungsten is a rare metal found naturally on Earth almost exclusively as compounds with other elements. It was identified as a new element in 1781 and first isolat ...

and

molybdenum Molybdenum is a chemical element with the symbol Mo and atomic number 42 which is located in period 5 and group 6. The name is from Neo-Latin ''molybdaenum'', which is based on Ancient Greek ', meaning lead, since its ores were confused with lea ...

metal cluster 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 ''microcluster'' ...

s generated by laser vaporization of the pure metals in the presence of

oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...

in a helium stream. In these clusters the three metal centers are bridged by oxygen and each metal has two terminal oxygen atoms. The first signal in the photoelectron spectrum corresponds to the removal of the valence electron with the lowest energy in the anion to the neutral compound. This energy turns out to be comparable to that of bulk

tungsten trioxide Tungsten(VI) oxide, also known as tungsten trioxide is a chemical compound of oxygen and the transition metal tungsten, with formula WO3. The compound is also called tungstic anhydride, reflecting its relation to tungstic acid . It is a light ...

and

molybdenum trioxide Molybdenum trioxide describes a family of inorganic compounds with the formula MoO3(H2O)n where n = 0, 1, 2. These compounds are produced on the largest scale of any molybdenum compound. The anhydrous oxide is a precursor to molybdenum metal, an ...

. The photoelectric signal is also broad which suggests a large difference in conformation between the anion and the neutral species.

shows that the anions and dianions are ideal hexagons with identical metal-to-metal

bond length In molecular geometry, bond length or bond distance is defined as the average distance between nuclei of two bonded atoms in a molecule. It is a transferable property of a bond between atoms of fixed types, relatively independent of the rest of ...

s. Tritantalum oxide clusters (Ta₃O₃⁻) also are observed to exhibit possible D-orbital aromaticity. The molecules discussed thus far only exist diluted in the gas phase. A study exploring the properties of a compound formed in water from

sodium molybdate Sodium molybdate, Na2MoO4, is useful as a source of molybdenum. This white, crystalline salt is often found as the dihydrate, Na2MoO4·2H2O. The molybdate(VI) anion is tetrahedral. Two sodium cations coordinate with every one anion.Braithwaite, E. ...

() and

iminodiacetic acid Iminodiacetic acid is the organic compound with the formula HN(CH2CO2H)2, often abbreviated to IDA. A white solid, the compound is a dicarboxylic acid amine (the nitrogen atom forms a secondary amino group, not an imino group as the name suggests) ...

also revealed evidence of aromaticity, but this compound has actually been isolated.

X-ray crystallography X-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles ...

showed that the sodium atoms are arranged in layers of hexagonal clusters akin to

pentacene Pentacene () is a polycyclic aromatic hydrocarbon consisting of five linearly-fused benzene () rings. This highly conjugated compound is an organic semiconductor. The compound generates excitons upon absorption of ultra-violet ( UV) or visible ...

s. The sodium-to-sodium

s are unusually short (327 pm versus 380 pm in elemental sodium) and, like benzene, the ring is planar. In this compound each sodium atom has a distorted

octahedral molecular geometry In chemistry, octahedral molecular geometry, also called square bipyramidal, describes the shape of compounds with six atoms or groups of atoms or ligands symmetrically arranged around a central atom, defining the vertices of an octahedron. The oc ...

with coordination to molybdenum atoms and water molecules.''Synthesis and structure of 1-D Na6 cluster chain with short Na–Na distance: Organic like aromaticity in inorganic metal cluster'' Snehadrinarayan Khatua, Debesh R. Roy, Pratim K. Chattaraj and Manish Bhattacharjee Chem. Commun., 2007, 135–37, The experimental evidence is supported by computed NICS aromaticity values.

References

{{chemical bonds Cluster chemistry Chemical bonding

See also

References