In chemistry, the term transition metal (or transition element) has three possible meanings:
English chemist Charles Bury (1890–1968) first used the word transition in this context in 1921, when he referred to a transition series of elements during the change of an inner layer of electrons (for example n = 3 in the 4th row of the periodic table) from a stable group of 8 to one of 18, or from 18 to 32. These elements are now known as the d-block.
In the d-block the atoms of the elements have between 1 and 10 d electrons.
The elements of groups 4–11 are generally recognized as transition metals, justified by their typical chemistry, i.e. a large range of complex ions in various oxidation states, colored complexes, and catalytic properties either as the element or as ions (or both). Sc and Y in group 3 are also generally recognized as transition metals. However, the elements La–Lu and Ac–Lr and group 12 attract different definitions from different authors.
Zinc, cadmium, and mercury are generally excluded from the transition metals, as they have the electronic configuration [ ]d10s2, with no incomplete d shell. In the oxidation state +2 the ions have the electronic configuration [ ]…d10. However, these elements can exist in other oxidation states, including the +1 oxidation state, as in the diatomic ion Hg2+
2. The group 12 elements Zn, Cd and Hg may therefore, under certain criteria, be classed as post-transition metals in this case. However, it is often convenient to include these elements in a discussion of the transition elements. For example, when discussing the crystal field stabilization energy of first-row transition elements, it is convenient to also include the elements calcium and zinc, as both Ca2+
have a value of zero, against which the value for other transition metal ions may be compared. Another example occurs in the Irving–Williams series of stability constants of complexes.
The recent (though disputed and so far not reproduced independently) synthesis of mercury(IV) fluoride (HgF
4) has been taken by some to reinforce the view that the group 12 elements should be considered transition metals, but some authors still consider this compound to be exceptional.
Although meitnerium, darmstadtium, and roentgenium are within the d-block and are expected to behave as transition metals analogous to their lighter congeners iridium, platinum, and gold, this has not yet been experimentally confirmed.
Early transition metals are on the left side of the periodic table from group 3 to group 7. Late transition metals are on the right side of the d-block, from group 8 to 11 (and 12 if it is counted as transition metals).
The general electronic configuration of the d-block elements is [Inert gas] (n − 1)d1–10n s0–2. The period 6 and 7 transition metals also add (n − 2)f0–14 electrons, which are omitted from the tables below.
The Madelung rule predicts that the typical electronic structure of transition metal atoms can be written as [inert gas]ns2(n − 1)dm where the inner d orbital is predicted to be filled after the valence-shell's s orbital is filled. This rule is however only approximate – it only holds for some of the transition elements, and only then in their neutral ground state.
The d-sub-shell is the next-to-last sub-shell and is denoted as -sub-shell. The number of s electrons in the outermost s sub-shell is generally one or two except palladium (Pd), with no electron in that s-sub shell in its ground state. The s-sub-shell in the valence shell is represented as the ns sub-shell, e.g. 4s. In the periodic table, the transition metals are present in eight groups (4 to 11), with some authors including some elements in groups 3 or 12.
The elements in group 3 have an ns2(n − 1)d1 configuration. The first transition series is present in the 4th period, and starts after Ca (Z = 20) of group-2 with the configuration [Ar]4s2, or scandium (Sc), the first element of group 3 with atomic number Z = 21 and configuration [Ar]4s23d1, depending on the definition used. As we move from left to right, electrons are added to the same d-sub-shell till it is complete. The element of group 11 in the first transition series is copper (Cu) with an atypical configuration [Ar]4s13d10. Despite the filled d subshell in metallic copper it nevertheless forms a stable ion with an incomplete d subshell. Since the electrons added fill the orbitals, the properties of the d-block elements are quite different from those of s and p block elements in which the filling occurs either in s or in p-orbitals of the valence shell. The electronic configuration of the individual elements present in all the d-block series are given below:
A careful look at the electronic configuration of the elements reveals that there are certain exceptions, for example Cr and Cu. These are either because of the symmetry or nuclear-electron and electron-electron force.
The orbitals that are involved in the transition metals are very significant because they influence such properties as magnetic character, variable oxidation states, formation of colored compounds etc. The valence and orbitals have very little contribution in this regard since they hardly change in the moving from left to the right in a transition series. In transition metals, there is a greater horizontal similarities in the properties of the elements in a period in comparison to the periods in which the d-orbitals are not involved. This is because in a transition series, the valence shell electronic configuration of the elements do not change. However, there are some group similarities as well.
There are a number of properties shared by the transition elements that are not found in other elements, which results from the partially filled d shell. These include
Colour in transition-series metal compounds is generally due to electronic transitions of two principal types.
A metal-to-ligand charge transfer (MLCT) transition will be most likely when the metal is in a low oxidation state and the ligand is easily reduced.
In general charge transfer transitions result in more intense colours than d-d transitions.
In centrosymmetric complexes, such as octahedral complexes, d-d transitions are forbidden by the Laporte rule and only occur because of vibronic coupling in which a molecular vibration occurs together with a d-d transition. Tetrahedral complexes have somewhat more intense colour because mixing d and p orbitals is possible when there is no centre of symmetry, so transitions are not pure d-d transitions. The molar absorptivity (ε) of bands caused by d-d transitions are relatively low, roughly in the range 5-500 M−1cm−1 (where M = mol dm−3). Some d-d transitions are spin forbidden. An example occurs in octahedral, high-spin complexes of manganese(II),
which has a d5 configuration in which all five electron has parallel spins; the colour of such complexes is much weaker than in complexes with spin-allowed transitions. Many compounds of manganese(II) appear almost colourless. The spectrum of [Mn(H
shows a maximum molar absorptivity of about 0.04 M−1cm−1 in the visible spectrum.
A characteristic of transition metals is that they exhibit two or more oxidation states, usually differing by one. For example, compounds of vanadium are known in all oxidation states between −1, such as [V(CO)
, and +5, such as VO3−
Main group elements in groups 13 to 18 also exhibit multiple oxidation states. The "common" oxidation states of these elements typically differ by two. For example, compounds of gallium in oxidation states +1 and +3 exist in which there is a single gallium atom. No compound of Ga(II) is known: any such compound would have an unpaired electron and would behave as a free radical and be destroyed rapidly. The only compounds in which gallium has a formal oxidation state of +2 are dimeric compounds, such as [Ga
, which contain a Ga-Ga bond formed from the unpaired electron on each Ga atom. Thus the main difference in oxidation states, between transition elements and other elements is that oxidation states are known in which there is a single atom of the element and one or more unpaired electrons.
The maximum oxidation state in the first row transition metals is equal to the number of valence electrons from titanium (+4) up to manganese (+7), but decreases in the later elements. In the second row the maximum occurs with ruthenium (+8), and in the third row, the maximum occurs with iridium (+9). In compounds such as [MnO
4 the elements achieve a stable configuration by covalent bonding.
The lowest oxidation states are exhibited in metal carbonyl complexes such as Cr(CO)
6 (oxidation state zero) and [Fe(CO)
(oxidation state −2) in which the 18-electron rule is obeyed. These complexes are also covalent.
Ionic compounds are mostly formed with oxidation states +2 and +3. In aqueous solution the ions are hydrated by (usually) six water molecules arranged octahedrally.
Transition metal compounds are paramagnetic when they have one or more unpaired d electrons. In octahedral complexes with between four and seven d electrons both high spin and low spin states are possible. Tetrahedral transition metal complexes such as [FeCl
are high spin because the crystal field splitting is small so that the energy to be gained by virtue of the electrons being in lower energy orbitals is always less than the energy needed to pair up the spins. Some compounds are diamagnetic. These include octahedral, low-spin, d6 and square-planar d8 complexes. In these cases, crystal field splitting is such that all the electrons are paired up.
Ferromagnetism occurs when individual atoms are paramagnetic and the spin vectors are aligned parallel to each other in a crystalline material. Metallic iron and the alloy alnico are examples of ferromagnetic materials involving transition metals. Anti-ferromagnetism is another example of a magnetic property arising from a particular alignment of individual spins in the solid state.
The transition metals and their compounds are known for their homogeneous and heterogeneous catalytic activity. This activity is ascribed to their ability to adopt multiple oxidation states and to form complexes. Vanadium(V) oxide (in the contact process), finely divided iron (in the Haber process), and nickel (in catalytic hydrogenation) are some of the examples. Catalysts at a solid surface (nanomaterial-based catalysts) involve the formation of bonds between reactant molecules and atoms of the surface of the catalyst (first row transition metals utilize 3d and 4s electrons for bonding). This has the effect of increasing the concentration of the reactants at the catalyst surface and also weakening of the bonds in the reacting molecules (the activation energy is lowered). Also because the transition metal ions can change their oxidation states, they become more effective as catalysts.
An interesting type of catalysis occurs when the products of a reaction catalyse the reaction producing more catalyst (autocatalysis). One example is the reaction of oxalic acid with acidified potassium permanganate (or manganate (VII)). Once a little Mn2+ has been produced, it can react with MnO4− forming Mn3+. This then reacts with C2O4− ions forming Mn2+ again.
As implied by the name, all transition metals are metals and thus conductors of electricity.
In general, transition metals possess a high density and high melting points and boiling points. These properties are due to metallic bonding by delocalized d electrons, leading to cohesion which increases with the number of shared electrons. However the group 12 metals have much lower melting and boiling points since their full d subshells prevent d–d bonding, which again tends to differentiate them from the accepted transition metals. Mercury has a melting point of −38.83 °C (−37.89 °F) and is a liquid at room temperature.
A block of the periodic table is a set of chemical elements predominantly characterised by having their highest energy electrons in the same atomic orbital type. The term appears to have been first used by Charles Janet. Each block is named after its characteristic orbital; thus, the blocks are:
f-blockThe block names (s, p, d, f and g) are derived from the spectroscopic notation for the associated atomic orbitals: sharp, principal, diffuse, and fundamental.Carbide
In chemistry, a carbide is a compound composed of carbon and a less electronegative element. Carbides can be generally classified by the chemical bonds type as follows: (i) salt-like, (ii) covalent compounds, (iii) interstitial compounds, and (iv) "intermediate" transition metal carbides. Examples include calcium carbide (CaC2), silicon carbide (SiC), tungsten carbide (WC; often called, simply, carbide when referring to machine tooling), and cementite (Fe3C), each used in key industrial applications. The naming of ionic carbides is not systematic.Chalcogenide
A chalcogenide is a chemical compound consisting of at least one chalcogen anion and at least one more electropositive element. Although all group 16 elements of the periodic table are defined as chalcogens, the term chalcogenide is more commonly reserved for sulfides, selenides, tellurides, and polonides, rather than oxides. Many metal ores exist as chalcogenides. Photoconductive chalcogenide glasses are used in xerography. Some pigments and catalysts are also based on chalcogenides. The metal dichalcogenide MoS2 is a common solid lubricant.Cluster chemistry
In chemistry, a cluster is an ensemble of bound atoms or molecules that is intermediate in size between a molecule and a bulk solid. Clusters exist of diverse stoichiometries and nuclearities. For example, carbon and boron atoms form fullerene and borane clusters, respectively. Transition metals and main group elements form especially robust clusters. Clusters can also consist solely of a certain kind of molecules, such as water clusters.
The phrase cluster was coined by F.A. Cotton in the early 1960s to refer to compounds containing metal–metal bonds. In another definition a cluster compound contains a group of two or more metal atoms where direct and substantial metal bonding is present. The prefixed terms "nuclear" and "metallic" are used and imply different meanings. For example, polynuclear refers to a cluster with more than one metal atom, regardless of the elemental identities. Heteronuclear refers to a cluster with at least two different metal elements.
The main cluster types are "naked" clusters (without stabilizing ligands) and those with ligands. For transition metal clusters, typical stabilizing ligands include carbon monoxide, halides, isocyanides, alkenes, and hydrides. For main group elements, typical clusters are stabilized by hydride ligands.
Transition metal clusters are frequently composed of refractory metal atoms. In general metal centers with extended d-orbitals form stable clusters because of favorable overlap of valence orbitals. Thus, metals with a low oxidation state for the later metals and mid-oxidation states for the early metals tend to form stable clusters. Polynuclear metal carbonyls are generally found in late transition metals with low formal oxidation states. The polyhedral skeletal electron pair theory or Wade's electron counting rules predict trends in the stability and structures of many metal clusters. Jemmis mno rules have provided additional insight into the relative stability of metal clusters.Coordination complex
In chemistry, a coordination complex consists of a central atom or ion, which is usually metallic and is called the coordination centre, and a surrounding array of bound molecules or ions, that are in turn known as ligands or complexing agents. Many metal-containing compounds, especially those of transition metals, are coordination complexes. A coordination complex whose centre is a metal atom is called a metal complex.Group 7 element
Group 7, numbered by IUPAC nomenclature, is a group of elements in the periodic table. They are manganese (Mn), technetium (Tc), rhenium (Re), and bohrium (Bh). All known elements of group 7 are transition metals.
Like other groups, the members of this family show patterns in their electron configurations, especially the outermost shells resulting in trends in chemical behavior.Group 8 element
Group 8 is a group (column) of chemical elements in the periodic table. It consists of iron (Fe), ruthenium (Ru), osmium (Os) and hassium (Hs). They are all transition metals.
Like other groups, the members of this family show patterns in electron configuration, especially in the outermost shells, resulting in trends in chemical behavior.
"Group 8" is the modern standard designation for this group, adopted by the IUPAC in 1990.In the older group naming systems, this group was combined with group 9 (cobalt, rhodium, iridium, and meitnerium) and group 10 (nickel, palladium, platinum, and darmstadtium) and called group "VIIIB" in the Chemical Abstracts Service (CAS) "U.S. system", or "VIII" in the old IUPAC (pre-1990) "European system" (and in Mendeleev's original table).
Group 8 (current IUPAC) should not be confused with "group VIIIA" in the CAS system, which is group 18 (current IUPAC), the noble gases.
While groups (columns) of the periodic table are sometimes named after their lighter member (as in "the oxygen group" for group 16), the term iron group does not mean "group 8". Most often, it means a set of adjacent elements on period (row) 4 of the table that includes iron, such as chromium, manganese, iron, cobalt, and nickel; or only the last three; or some other set — depending on the context.Group 9 element
Group 9 is a group (column) of chemical elements in the periodic table. Members are cobalt (Co), rhodium (Rh), iridium (Ir) and meitnerium (Mt). These are all transition metals in the d-block.
Like other groups, the members of this family show patterns in electron configuration, especially in the outermost shells, resulting in trends in chemical behavior; however, rhodium deviates from the pattern.
"Group 9" is the modern standard designation for this group, adopted by the IUPAC in 1990.In the older group naming systems, this group was combined with group 8 (iron, ruthenium, osmium, and hassium) and group 10 (nickel, palladium, platinum, and darmstadtium) and called group "VIIIB" in the Chemical Abstracts Service (CAS) "U.S. system", or "VIII" in the old IUPAC (pre-1990) "European system" (and in Mendeleev's original table).Inorganic chemistry
Inorganic chemistry deals with the synthesis and behavior of inorganic and organometallic compounds. This field covers all chemical compounds except the myriad organic compounds (carbon-based compounds, usually containing C-H bonds), which are the subjects of organic chemistry. The distinction between the two disciplines is far from absolute, as there is much overlap in the subdiscipline of organometallic chemistry. It has applications in every aspect of the chemical industry, including catalysis, materials science, pigments, surfactants, coatings, medications, fuels, and agriculture.Osmium dioxide
Osmium dioxide is an inorganic compound with the formula OsO2. It exists as brown to black crystalline powder, but single crystals are golden and exhibit metallic conductivity. The compound crystallizes in the rutile structural motif, i.e. the connectivity is very similar to that in the mineral rutile.Oxide
An oxide is a chemical compound that contains at least one oxygen atom and one other element in its chemical formula. "Oxide" itself is the dianion of oxygen, an O2– atom. Metal oxides thus typically contain an anion of oxygen in the oxidation state of −2. Most of the Earth's crust consists of solid oxides, the result of elements being oxidized by the oxygen in air or in water. Hydrocarbon combustion affords the two principal carbon oxides: carbon monoxide and carbon dioxide. Even materials considered pure elements often develop an oxide coating. For example, aluminium foil develops a thin skin of Al2O3 (called a passivation layer) that protects the foil from further corrosion. Individual elements can often form multiple oxides, each containing different amounts of the element and oxygen. In some cases these are distinguished by specifying the number of atoms as in carbon monoxide and carbon dioxide, and in other cases by specifying the element's oxidation number, as in iron(II) oxide and iron(III) oxide. Certain elements can form many different oxides, such as those of nitrogen.Period (periodic table)
A period in the periodic table is a row of chemical elements. All elements in a row have the same number of electron shells. Each next element in a period has one more proton and is less metallic than its predecessor. Arranged this way, groups of elements in the same column have similar chemical and physical properties, reflecting the periodic law. For example, the alkali metals lie in the first column (group 1) and share similar properties, such as high reactivity and the tendency to lose one electron to arrive at a noble-gas electronic configuration. As of 2016, a total of 118 elements have been discovered and confirmed.
Modern quantum mechanics explains these periodic trends in properties in terms of electron shells. As atomic number increases, shells fill with electrons in approximately the order shown at right. The filling of each shell corresponds to a row in the table.
In the s-block and p-block of the periodic table, elements within the same period generally do not exhibit trends and similarities in properties (vertical trends down groups are more significant). However, in the d-block, trends across periods become significant, and in the f-block elements show a high degree of similarity across periods.Period 4 element
A period 4 element is one of the chemical elements in the fourth row (or period) of the periodic table of the elements. The periodic table is laid out in rows to illustrate recurring (periodic) trends in the chemical behaviour of the elements as their atomic number increases: a new row is begun when chemical behaviour begins to repeat, meaning that elements with similar behaviour fall into the same vertical columns. The fourth period contains 18 elements, beginning with potassium and ending with krypton. As a rule, period 4 elements fill their 4s shells first, then their 3d and 4p shells, in that order; however, there are exceptions, such as chromium.Period 5 element
A period 5 element is one of the chemical elements in the fifth row (or period) of the periodic table of the elements. The periodic table is laid out in rows to illustrate recurring (periodic) trends in the chemical behaviour of the elements as their atomic number increases: a new row is begun when chemical behaviour begins to repeat, meaning that elements with similar behaviour fall into the same vertical columns. The fifth period contains 18 elements, beginning with rubidium and ending with xenon. As a rule, period 5 elements fill their 5s shells first, then their 4d, and 5p shells, in that order; however, there are exceptions, such as rhodium.Period 7 element
A period 7 element is one of the chemical elements in the seventh row (or period) of the periodic table of the chemical elements. The periodic table is laid out in rows to illustrate recurring (periodic) trends in the chemical behaviour of the elements as their atomic number increases: a new row is begun when chemical behaviour begins to repeat, meaning that elements with similar behaviour fall into the same vertical columns. The seventh period contains 32 elements, tied for the most with period 6, beginning with francium and ending with oganesson, the heaviest element currently discovered. As a rule, period 7 elements fill their 7s shells first, then their 5f, 6d, and 7p shells, in that order; however, there are exceptions, such as plutonium.Post-transition metal
Post-transition metals are a set of metallic elements in the periodic table located between the transition metals to their left, and the metalloids to their right. Depending on where these adjacent groups are judged to begin and end, there are at least five competing proposals for which elements to include: the three most common contain six, ten and thirteen elements, respectively (see image). All proposals include gallium, indium, tin, thallium, lead, and bismuth.
Physically, post-transition metals are soft (or brittle), have poor mechanical strength, and have melting points lower than those of the transition metals. Being close to the metal-nonmetal border, their crystalline structures tend to show covalent or directional bonding effects, having generally greater complexity or fewer nearest neighbours than other metallic elements.
Chemically, they are characterised—to varying degrees—by covalent bonding tendencies, acid-base amphoterism and the formation of anionic species such as aluminates, stannates, and bismuthates (in the case of aluminium, tin, and bismuth, respectively). They can also form Zintl phases (half-metallic compounds formed between highly electropositive metals and moderately electronegative metals or metalloids).
The name is universally used, but not officially sanctioned by any organization such as the IUPAC. The origin of the term is unclear: one early use was in 1940 in a chemistry text. Alternate names for this group are B-subgroup metals, other metals, and p-block metals; and at least eleven other labels.Rhenium disulfide
Rhenium disulfide is an inorganic compound of rhenium and sulfur with the formula ReS2. It has a layered structure where atoms are strongly bonded within each layer. The layers are held together by weak Van der Waals bonds, and can be easily peeled off from the bulk material. It is a two-dimensional (2D) group VII transition metal dichalcogenide (TMD). Different to other TMDs, ReS2 has shown layer-independent electrical, optical, and vibrational properties.Nanostructured ReS2 can usually be achieved through mechanical exfoliation, chemical vapor deposition (CVD), and chemical and liquid exfoliations. It is widely used in electronic and optoelectronic device, energy storage, photocatalytic and electrocatalytic reactions.Transition metal carbene complex
A transition metal carbene complex is an organometallic compound featuring a divalent organic ligand. The divalent organic ligand coordinated to the metal center is called a carbene. Carbene complexes for almost all transition metals have been reported. Many methods for synthesizing them and reactions utilizing them have been reported. The term carbene ligand is a formalism since many are not derived from carbenes and almost none exhibit the reactivity characteristic of carbenes. Described often as M=CR2, they represent a class of organic ligands intermediate between alkyls (−CR3) and carbynes (≡CR). They feature in some catalytic reactions, especially alkene metathesis, and are of value in the preparation of some fine chemicals.Tungsten trioxide
Tungsten(VI) oxide, also known as tungsten trioxide or tungstic anhydride, WO3, is a chemical compound containing oxygen and the transition metal tungsten. It is obtained as an intermediate in the recovery of tungsten from its minerals. Tungsten ores are treated with alkalis to produce WO3. Further reaction with carbon or hydrogen gas reduces tungsten trioxide to the pure metal. Tungsten trioxide is a strong oxidative agent, it reacts rare-earth elements, iron, copper, aluminium, manganese, zinc, chromium, molybdenum, carbon, hydrogen and silver to make the pure tungsten metal, and gold and platinum to make the tungsten dioxide.
2 WO3 + 3 C → 2 W + 3 CO2 (high temperature)
WO3 + 3 H2 → W + 3 H2O (550 - 850 °C)
WO3 + 2Fe → W + Fe2O3
2WO3 + Pt → 2WO2 + PtO2Tungsten(VI) oxide occurs naturally in the form of hydrates, which include minerals: tungstite WO3·H2O, meymacite WO3·2H2O and hydrotungstite (of the same composition as meymacite, however sometimes written as H2WO4). These minerals are rare to very rare secondary tungsten minerals.
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