A coordination complex is a chemical compound consisting 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 that include transition metals, are coordination complexes.
In coordination chemistry, a ligand is an ion or molecule with a functional group that binds to a central metal atom to form a coordination complex. The bonding with the metal generally involves formal donation of one or more of the ligand's electron pairs, often through Lewis bases. The nature of metal–ligand bonding can range from covalent to ionic. Furthermore, the metal–ligand bond order can range from one to three. Ligands are viewed as Lewis bases, although rare cases are known to involve Lewis acidic "ligands".
In chemistry, a molecular orbital is a mathematical function describing the location and wave-like behavior of an electron in a molecule. This function can be used to calculate chemical and physical properties such as the probability of finding an electron in any specific region. The terms atomic orbital and molecular orbital were introduced by Robert S. Mulliken in 1932 to mean one-electron orbital wave functions. At an elementary level, they are used to describe the region of space in which a function has a significant amplitude.
In chemistry, molecular orbital theory is a method for describing the electronic structure of molecules using quantum mechanics. It was proposed early in the 20th century.
Valence shell electron pair repulsion (VSEPR) theory, is a model used in chemistry to predict the geometry of individual molecules from the number of electron pairs surrounding their central atoms. It is also named the Gillespie-Nyholm theory after its two main developers, Ronald Gillespie and Ronald Nyholm.
In molecular physics, crystal field theory (CFT) describes the breaking of degeneracies of electron orbital states, usually d or f orbitals, due to a static electric field produced by a surrounding charge distribution. This theory has been used to describe various spectroscopies of transition metal coordination complexes, in particular optical spectra (colors). CFT successfully accounts for some magnetic properties, colors, hydration enthalpies, and spinel structures of transition metal complexes, but it does not attempt to describe bonding. CFT was developed by physicists Hans Bethe and John Hasbrouck van Vleck in the 1930s. CFT was subsequently combined with molecular orbital theory to form the more realistic and complex ligand field theory (LFT), which delivers insight into the process of chemical bonding in transition metal complexes. CFT can be complicated further by breaking assumptions made of relative metal and ligand orbital energies, requiring the use of inverted ligand field theory (ILFT) to better describe bonding.
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 octahedron has eight faces, hence the prefix octa. The octahedron is one of the Platonic solids, although octahedral molecules typically have an atom in their centre and no bonds between the ligand atoms. A perfect octahedron belongs to the point group Oh. Examples of octahedral compounds are sulfur hexafluoride SF6 and molybdenum hexacarbonyl Mo(CO)6. The term "octahedral" is used somewhat loosely by chemists, focusing on the geometry of the bonds to the central atom and not considering differences among the ligands themselves. For example, [Co(NH3)6]3+, which is not octahedral in the mathematical sense due to the orientation of the N−H bonds, is referred to as octahedral.
The term coordination geometry is used in a number of related fields of chemistry and solid state chemistry/physics.
The square planar molecular geometry in chemistry describes the stereochemistry that is adopted by certain chemical compounds. As the name suggests, molecules of this geometry have their atoms positioned at the corners.
Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry. In the Mond process, nickel tetracarbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometallic complexes.
In chemistry the polyhedral skeletal electron pair theory (PSEPT) provides electron counting rules useful for predicting the structures of clusters such as borane and carborane clusters. The electron counting rules were originally formulated by Kenneth Wade, and were further developed by others including Michael Mingos; they are sometimes known as Wade's rules or the Wade–Mingos rules. The rules are based on a molecular orbital treatment of the bonding. These rules have been extended and unified in the form of the Jemmis mno rules.
In a tetrahedral molecular geometry, a central atom is located at the center with four substituents that are located at the corners of a tetrahedron. The bond angles are cos−1(−1⁄3) = 109.4712206...° ≈ 109.5° when all four substituents are the same, as in methane as well as its heavier analogues. Methane and other perfectly symmetrical tetrahedral molecules belong to point group Td, but most tetrahedral molecules have lower symmetry. Tetrahedral molecules can be chiral.
In chemistry, a diradical is a molecular species with two electrons occupying molecular orbitals (MOs) which are degenerate. The term "diradical" is mainly used to describe organic compounds, where most diradicals are extremely reactive and in fact rarely isolated. Diradicals are even-electron molecules but have one fewer bond than the number permitted by the octet rule.
The 18-electron rule is a chemical rule of thumb used primarily for predicting and rationalizing formulas for stable transition metal complexes, especially organometallic compounds. The rule is based on the fact that the valence orbitals in the electron configuration of transition metals consist of five (n−1)d orbitals, one ns orbital, and three np orbitals, where n is the principal quantum number. These orbitals can collectively accommodate 18 electrons as either bonding or non-bonding electron pairs. This means that the combination of these nine atomic orbitals with ligand orbitals creates nine molecular orbitals that are either metal-ligand bonding or non-bonding. When a metal complex has 18 valence electrons, it is said to have achieved the same electron configuration as the noble gas in the period, lending stability to the complex. Transition metal complexes that deviate from the rule are often interesting or useful because they tend to be more reactive. The rule is not helpful for complexes of metals that are not transition metals. The rule was first proposed by American chemist Irving Langmuir in 1921.
A molecular orbital diagram, or MO diagram, is a qualitative descriptive tool explaining chemical bonding in molecules in terms of molecular orbital theory in general and the linear combination of atomic orbitals (LCAO) method in particular. A fundamental principle of these theories is that as atoms bond to form molecules, a certain number of atomic orbitals combine to form the same number of molecular orbitals, although the electrons involved may be redistributed among the orbitals. This tool is very well suited for simple diatomic molecules such as dihydrogen, dioxygen, and carbon monoxide but becomes more complex when discussing even comparatively simple polyatomic molecules, such as methane. MO diagrams can explain why some molecules exist and others do not. They can also predict bond strength, as well as the electronic transitions that can take place.
An electronic effect influences the structure, reactivity, or properties of molecule but is neither a traditional bond nor a steric effect. In organic chemistry, the term stereoelectronic effect is also used to emphasize the relation between the electronic structure and the geometry (stereochemistry) of a molecule.
The d electron count or number of d electrons is a chemistry formalism used to describe the electron configuration of the valence electrons of a transition metal center in a coordination complex. The d electron count is an effective way to understand the geometry and reactivity of transition metal complexes. The formalism has been incorporated into the two major models used to describe coordination complexes; crystal field theory and ligand field theory, which is a more advanced version based on molecular orbital theory. However the d electron count of an atom in a complex is often different from the d electron count of a free atom or a free ion of the same element.
Spin states when describing transition metal coordination complexes refers to the potential spin configurations of the central metal's d electrons. For several oxidation states, metals can adopt high-spin and low-spin configurations. The ambiguity only applies to first row metals, because second- and third-row metals are invariably low-spin. These configurations can be understood through the two major models used to describe coordination complexes; crystal field theory and ligand field theory.
In chemistry, the capped octahedral molecular geometry describes the shape of compounds where seven atoms or groups of atoms or ligands are arranged around a central atom defining the vertices of a gyroelongated triangular pyramid. This shape has C3v symmetry and is one of the three common shapes for heptacoordinate transition metal complexes, along with the pentagonal bipyramid and the capped trigonal prism.
Water is a simple triatomic bent molecule with C2v molecular symmetry and bond angle of 104.5° between the central oxygen atom and the hydrogen atoms. Despite being one of the simplest triatomic molecules, its chemical bonding scheme is nonetheless complex as many of its bonding properties such as bond angle, ionization energy, and electronic state energy cannot be explained by one unified bonding model. Instead, several traditional and advanced bonding models such as simple Lewis and VSEPR structure, valence bond theory, molecular orbital theory, isovalent hybridization, and Bent's rule are discussed below to provide a comprehensive bonding model for H
2O, explaining and rationalizing the various electronic and physical properties and features manifested by its peculiar bonding arrangements.
