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5: Transition Metals and Coordination Chemistry

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  • Transition metals are defined as those elements that have (or readily form) partially filled d orbitals. These include the d-block (groups 3–11) and f-block element elements. The variety of properties exhibited by transition metals is due to their complex valence shells. Unlike most main group metals where one oxidation state is normally observed, the valence shell structure of transition metals means that they usually occur in several different stable oxidation states. In addition, electron transitions in these elements can correspond with absorption of photons in the visible electromagnetic spectrum, leading to colored compounds. Because of these behaviors, transition metals exhibit a rich and fascinating chemistry.

    • 5.0: Properties of Transition Metals and Their Compounds
      The transition metals are elements with partially filled d orbitals, located in the d-block of the periodic table. The reactivity of the transition elements varies widely from very active metals such as scandium and iron to almost inert elements, such as the platinum metals. The type of chemistry used in the isolation of the elements from their ores depends upon the concentration of the element in its ore and the difficulty of reducing ions of the elements to the metals.
    • 5.1: Metal Complexes
      A complex ion has a metal ion at its center with a number of other molecules or ions surrounding it. These can be considered to be attached to the central ion by coordinate (dative covalent) bonds (in some cases, the bonding is actually more complicated than that. The molecules or ions surrounding the central metal ion are called ligands. Simple ligands include water, ammonia and chloride ions.
    • 5.2: Ligands with more than one Donor Atom
      Ligands can be further characterized as monodentate, bidentate, tridentate etc. where the concept of teeth (dent) is introduced. Monodentate ligands bind through only one donor atom. Monodentate means "one-toothed." The halides, phosphines, ammonia and amines seen previously are monodentate ligands. Bidentate ligands bind through two donor sites. Bidentate means "two-toothed." It can bind to a metal via two donor atoms at once.
    • 5.3: Nomenclature of Coordination Chemistry
      Coordination complexes have their own classes of isomers, different magnetic properties and colors, and various applications (photography, cancer treatment, etc), so it makes sense that they would have a naming system as well.
    • 5.4: Isomerization
      Two compounds that have the same formula and the same connectivity do not always have the same shape. There are two reasons why this may happen. In one case, the molecule may be flexible, so that it can twist into different shapes via rotation around individual sigma bonds. This phenomenon is called conformation, and it is covered in a different chapter. The second case occurs when two molecules appear to be connected the same way on paper, but are connected in two different ways in three dimens
    • 5.5: Color and Magnetism
      Crystal field theory, which assumes that metal–ligand interactions are only electrostatic in nature, explains many important properties of transition-metal complexes, including their colors, magnetism, structures, stability, and reactivity.
    • 5.6: Crystal Field Theory
      Crystal field theory treats interactions between the electrons on the metal and the ligands as a simple electrostatic effect. The presence of the ligands near the metal ion changes the energies of the metal d orbitals relative to their energies in the free ion. Both the color and the magnetic properties of a complex can be attributed to this crystal field splitting. The magnitude of the splitting depends on the nature of the ligands bonded to the metal.
    • 5.E: Chemistry of Coordination Chemistry (Exercises)
      These are homework exercises to accompany the Textmap created for "Chemistry: The Central Science" by Brown et al.

    Thumbnail: Structure of the \(trans-[CoCl_2(NH_3)_4]^+\) complex ion. Image used with permission (Public domain; Benjah-bmm27).