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. The lanthanide and actinide elements (the f-block) are called inner transition metals and are sometimes considered to be transition metals as well.
They are lustrous metals with good electrical and thermal conductivity. Most (with the exception of group 11 and group 12) are hard and strong, and have high melting and boiling temperatures. They form compounds in any of two or more different oxidation states and bind to a variety of ligands to form coordination complexes that are often coloured. They form many useful alloys and are often employed as catalysts in elemental form or in compounds such as coordination complexes and oxides. Most are strongly paramagnetic because of their unpaired d electrons, as are many of their compounds. All of the elements that are ferromagnetic near room temperature are transition metals (iron, cobalt and nickel) or inner transition metals (gadolinium).
English chemist Charles Rugeley 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.Bury, Charles Rugeley. Encyclopedia.com Complete dictionary of scientific biography (2008). These elements are now known as the d-block.
Definition and classification The 2011 IUPAC Principles of Chemical Nomenclature describe a "transition metal" as any element in groups 3 to 12 on the periodic table. This corresponds exactly to the d-block elements, and many scientists use this definition.Housecroft, C. E. and Sharpe, A. G. (2005) Inorganic Chemistry, 2nd ed, Pearson Prentice-Hall, pp. 20–21. In actual practice, the f-block lanthanide and actinide series are called "inner transition metals". The 2005 Red Book allows for the group 12 elements to be excluded, but not the 2011 Principles.
The IUPAC Gold Book defines a transition metal as "an element whose atom has a partially filled d sub-shell, or which can give rise to cations with an incomplete d sub-shell", but this definition is taken from an old edition of the Red Book and is no longer present in the current edition.
In the d-block, the atoms of the elements have between zero and ten d electrons. Transition metals in the d-block Group 3 4 5 6 7 8 9 10 11 12 Period 4 21Sc 22Ti 23V 24Cr 25Mn 26Fe 27Co 28Ni 29Cu 30Zn 5 39Y 40Zr 41Nb 42Mo 43Tc 44Ru 45Rh 46Pd 47Ag 48Cd 6 71Lu 72Hf 73Ta 74W 75Re 76Os 77Ir 78Pt 79Au 80Hg 7 103Lr 104Rf 105Db 106Sg 107Bh 108Hs 109Mt 110Ds 111Rg 112Cn
Published texts and periodic tables show variation regarding the heavier members of group 3. The common placement of lanthanum and actinium in these positions is not supported by physical, chemical, and electronic evidence, which overwhelmingly favour putting lutetium and lawrencium in those places. Some authors prefer to leave the spaces below yttrium blank as a third option, but there is confusion on whether this format implies that group 3 contains only scandium and yttrium, or if it also contains all the lanthanides and actinides; additionally, it creates a 15-element-wide f-block, when quantum mechanics dictates that the f-block should only be 14 elements wide. The form with lutetium and lawrencium in group 3 is supported by a 1988 IUPAC report on physical, chemical, and electronic grounds, and again by a 2021 IUPAC preliminary report as it is the only form that allows simultaneous (1) preservation of the sequence of increasing atomic numbers, (2) a 14-element-wide f-block, and (3) avoidance of the split in the d-block. Argumentation can still be found in the contemporary literature purporting to defend the form with lanthanum and actinium in group 3, but many authors consider it to be logically inconsistent (a particular point of contention being the differing treatment of actinium and thorium, which both can use 5f as a valence orbital but have no 5f occupancy as single atoms); the majority of investigators considering the problem agree with the updated form with lutetium and lawrencium.
The group 12 elements zinc, cadmium, and mercury are sometimes excluded from the transition metals. This is because they have the electronic configuration [ ]d10s2, where the d shell is complete,Cotton, F. Albert; Wilkinson, G.; Murillo, C. A. (1999). Advanced Inorganic Chemistry (6th ed.). New York: Wiley, . and they still have a complete d shell in all their known oxidation states. 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 and 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. Moreover, Zn, Cd, and Hg can use their d orbitals for bonding even though they are not known in oxidation states that would formally require breaking open the d-subshell, which sets them apart from the p-block elements.
The 2007 (though disputed and so far not reproduced independently) synthesis of mercury(IV) fluoride () 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. Copernicium is expected to be able to use its d electrons for chemistry as its 6d subshell is destabilised by strong relativistic effects due to its very high atomic number, and as such is expected to have transition-metal-like behaviour and show higher oxidation states than +2 (which are not definitely known for the lighter group 12 elements). Even in bare dications, Cn2+ is predicted to be 6d87s2, unlike Hg2+ which is 5d106s0.
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. Whether copernicium behaves more like mercury or has properties more similar to those of the noble gas radon is not clear. Relative inertness of Cn would come from the relativistically expanded 7s–7p1/2 energy gap, which is already adumbrated in the 6s–6p1/2 gap for Hg, weakening metallic bonding and causing its well-known low melting and boiling points.
Transition metals with lower or higher group numbers are described as 'earlier' or 'later', respectively. When described in a two-way classification scheme, early transition metals are on the left side of the d-block from group 3 to group 7. Late transition metals are on the right side of the d-block, from group 8 to 11 (or 12, if they are counted as transition metals). In an alternative three-way scheme, groups 3, 4, and 5 are classified as early transition metals, 6, 7, and 8 are classified as middle transition metals, and 9, 10, and 11 (and sometimes group 12) are classified as late transition metals.
The heavy group 2 elements calcium, strontium, and barium do not have filled d-orbitals as single atoms, but are known to have d-orbital bonding participation in some compounds, and for that reason have been called "honorary" transition metals. The same is likely true of radium.
The f-block elements La–Yb and Ac–No have chemical activity of the (n−1)d shell, but importantly also have chemical activity of the (n−2)f shell that is absent in d-block elements. Hence they are often treated separately as inner transition elements.
Electronic configuration
The general electronic configuration of the d-block atoms is [noble gas](n − 1)d0–10ns0–2np0–1. Here "[noble gas]" is the electronic configuration of the last noble gas preceding the atom in question, and n is the highest principal quantum number of an occupied orbital in that atom. For example, Ti (Z = 22) is in period 4 so that n = 4, the first 18 electrons have the same configuration of Ar at the end of period 3, and the overall configuration is [Ar]3d24s2. The period 6 and 7 transition metals also add core (n − 2)f14 electrons, which are omitted from the tables below. The p orbitals are almost never filled in free atoms (the one exception being lawrencium due to relativistic effects that become important at such high Z), but they can contribute to the chemical bonding in transition metal compounds.
The Madelung rule predicts that the inner d orbital is filled after the valence-shell s orbital. The typical electronic structure of transition metal atoms is then written as [noble gas]ns2(n − 1)dm. This rule is approximate, but holds for most of the transition metals. Even when it fails for the neutral ground state, it accurately describes a low-lying excited state.
The d subshell is the next-to-last subshell and is denoted as (n − 1)d subshell. The number of s electrons in the outermost s subshell is generally one or two except palladium (Pd), with no electron in that s sub shell in its ground state. The s subshell in the valence shell is represented as the ns subshell, e.g. 4s. In the periodic table, the transition metals are present in ten groups (3 to 12).
The elements in group 3 have an ns2(n − 1)d1 configuration, except for lawrencium (Lr): its 7s27p1 configuration exceptionally does not fill the 6d orbitals at all. 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 subshell till it is complete. Since the electrons added fill the (n − 1)d 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:Miessler, G. L. and Tarr, D. A. (1999) Inorganic Chemistry, 2nd edn, Prentice-Hall, p. 38-39
+ First (3d) d-block Series (Sc–Zn) Group 3 4 5 6 7 8 9 10 11 12 Atomic number 21 22 23 24 25 26 27 28 29 30 Element Sc Ti V Cr Mn Fe Co Ni Cu Zn Electronconfiguration 3d14s2 3d24s2 3d34s2 3d54s1 3d54s2 3d64s2 3d74s2 3d84s2 3d104s1 3d104s2
+ Second (4d) d-block Series (Y–Cd) Atomic number 39 40 41 42 43 44 45 46 47 48 Element Y Zr Nb Mo Tc Ru Rh Pd Ag Cd Electronconfiguration 4d15s2 4d25s2 4d45s1 4d55s1 4d55s2 4d75s1 4d85s1 4d105s0 4d105s1 4d105s2
+ Third (5d) d-block Series (Lu–Hg) Atomic number 71 72 73 74 75 76 77 78 79 80 Element Lu Hf Ta W Re Os Ir Pt Au Hg Electronconfiguration 5d16s2 5d26s2 5d36s2 5d46s2 5d56s2 5d66s2 5d76s2 5d96s1 5d106s1 5d106s2
+ Fourth (6d) d-block Series (Lr–Cn)(Configurations predicted for Mt–Cn) Atomic number 103 104 105 106 107 108 109 110 111 112 Element Lr Rf Db Sg Bh Hs Mt Ds Rg Cn Electronconfiguration 7s27p1 6d27s2 6d37s2 6d47s2 6d57s2 6d67s2 6d77s2 6d87s2 6d97s2 6d107s2