Metal aromaticity or metalloaromaticity is the concept of

aromaticity In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugation alone. The e ...

, found in many

organic compound Some chemical authorities define an organic compound as a chemical compound that contains a carbon–hydrogen or carbon–carbon bond; others consider an organic compound to be any chemical compound that contains carbon. For example, carbon-co ...

s, extended to

metals A metal () is a material that, when polished or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. These properties are all associated with having electrons available at the Fermi level, as against no ...

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

cluster compound Nanoclusters are atomically precise, crystalline materials most often existing on the 0-2 nanometer scale. They are often considered kinetically stable intermediates that form during the synthesis of comparatively larger materials such as semic ...

s of the type where M stands for

lithium Lithium (from , , ) is a chemical element; it has chemical symbol, symbol Li and atomic number 3. It is a soft, silvery-white alkali metal. Under standard temperature and pressure, standard conditions, it is the least dense metal and the ...

sodium Sodium is a chemical element; it has Symbol (chemistry), symbol Na (from Neo-Latin ) and atomic number 11. It is a soft, silvery-white, highly reactive metal. Sodium is an alkali metal, being in group 1 element, group 1 of the peri ...

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 conven ...

s can be generated in a

helium Helium (from ) is a chemical element; it has chemical symbol, symbol He and atomic number 2. It is a colorless, odorless, non-toxic, inert gas, inert, monatomic gas and the first in the noble gas group in the periodic table. Its boiling point is ...

gas by laser vaporization of an aluminium /

lithium carbonate Lithium carbonate is an inorganic compound, the lithium salt of carbonic acid with the chemical formula, formula . This white Salt (chemistry), salt is widely used in processing metal oxides. It is on the WHO Model List of Essential Medicines, Wor ...

composite or a copper or sodium / aluminium

alloy An alloy is a mixture of chemical elements of which in most cases at least one is a metal, metallic element, although it is also sometimes used for mixtures of elements; herein only metallic alloys are described. Metallic alloys often have prop ...

, 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 used ...

and analyzed by photoelectron spectroscopy. The evidence for aromaticity in these compounds is based on several considerations.

Computational chemistry Computational chemistry is a branch of chemistry that uses computer simulations to assist in solving chemical problems. It uses methods of theoretical chemistry incorporated into computer programs to calculate the structures and properties of mol ...

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 (geometry), pyramid with a square base and four triangles, having a total of five faces. If the Apex (geometry), apex of the pyramid is directly above the center of the square, it is a ''right square p ...

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

counterion 160px, cation-exchange_resin.html" ;"title="Polystyrene sulfonate, a cation-exchange resin">Polystyrene sulfonate, a cation-exchange resin, is typically supplied with as the counterion. In chemistry, a counterion (sometimes written as "counter ...

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

HOMO ''Homo'' () is a genus of great ape (family Hominidae) that emerged from the genus ''Australopithecus'' and encompasses only a single extant species, ''Homo sapiens'' (modern humans), along with a number of extinct species (collectively called ...

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 f ...

. 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 (also called wolfram) is a chemical element; it has symbol W and atomic number 74. It is a metal found naturally on Earth almost exclusively in compounds with other elements. It was identified as a distinct element in 1781 and first ...

and

molybdenum Molybdenum is a chemical element; it has Symbol (chemistry), symbol Mo (from Neo-Latin ''molybdaenum'') and atomic number 42. The name derived from Ancient Greek ', meaning lead, since its ores were confused with lead ores. Molybdenum minerals hav ...

metal clusters generated by laser vaporization of the pure metals in the presence of

oxygen Oxygen is a chemical element; it has chemical symbol, symbol O and atomic number 8. It is a member of the chalcogen group (periodic table), group in the periodic table, a highly reactivity (chemistry), reactive nonmetal (chemistry), non ...

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. The anhydrous compound is produced on the largest scale of any molybdenum compound since it is the main intermediate produced when molybd ...

. 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 Atomic nucleus, nuclei of two chemical bond, bonded atoms in a molecule. It is a Transferability (chemistry), transferable property of a bond between at ...

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 encountered as the dihydrate, Na2MoO4·2H2O. Preparation Dissolution of MoO3 in sodium hydroxide at 50–70 °C followed by crystallizing t ...

() and iminodiacetic acid also revealed evidence of aromaticity, but this compound has actually been isolated.

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

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

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