Metal carbonylMetal 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.
Intersystem crossingIntersystem crossing (ISC) is an isoenergetic radiationless process involving a transition between the two electronic states with different spin multiplicity. When an electron in a molecule with a singlet ground state is excited (via absorption of radiation) to a higher energy level, either an excited singlet state or an excited triplet state will form. Singlet state is a molecular electronic state such that all electron spins are paired.
Electron configurationIn atomic physics and quantum chemistry, the electron configuration is the distribution of electrons of an atom or molecule (or other physical structure) in atomic or molecular orbitals. For example, the electron configuration of the neon atom is 1s2 2s2 2p6, meaning that the 1s, 2s and 2p subshells are occupied by 2, 2 and 6 electrons respectively. Electronic configurations describe each electron as moving independently in an orbital, in an average field created by all other orbitals.
Emission spectrumThe emission spectrum of a chemical element or chemical compound is the spectrum of frequencies of electromagnetic radiation emitted due to an electron making a transition from a high energy state to a lower energy state. The photon energy of the emitted photon is equal to the energy difference between the two states. There are many possible electron transitions for each atom, and each transition has a specific energy difference. This collection of different transitions, leading to different radiated wavelengths, make up an emission spectrum.
Transition metal alkene complexIn organometallic chemistry, a transition metal alkene complex is a coordination compound containing one or more alkene ligands. The inventory is large. Such compounds are intermediates in many catalytic reactions that convert alkenes to other organic products. The simplest monoalkene is ethene. Many complexes of ethene are known, including Zeise's salt (see figure), Rh2Cl2(C2H4)4, Cp*2Ti(C2H4), and the homoleptic Ni(C2H4)3. Substituted monoalkene include the cyclic cyclooctene, as found in chlorobis(cyclooctene)rhodium dimer.
Absorption spectroscopyAbsorption spectroscopy refers to spectroscopic techniques that measure the absorption of electromagnetic radiation, as a function of frequency or wavelength, due to its interaction with a sample. The sample absorbs energy, i.e., photons, from the radiating field. The intensity of the absorption varies as a function of frequency, and this variation is the absorption spectrum. Absorption spectroscopy is performed across the electromagnetic spectrum.
Crystal field theoryIn 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 (anion neighbors). 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.
Free electron modelIn solid-state physics, the free electron model is a quantum mechanical model for the behaviour of charge carriers in a metallic solid. It was developed in 1927, principally by Arnold Sommerfeld, who combined the classical Drude model with quantum mechanical Fermi–Dirac statistics and hence it is also known as the Drude–Sommerfeld model.
Transition metalIn 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. Since they are metals, they are lustrous and have good electrical and thermal conductivity.
Organometallic chemistryOrganometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide (metal carbonyls), cyanide, or carbide, are generally considered to be organometallic as well.
Orbital hybridisationIn chemistry, orbital hybridisation (or hybridization) is the concept of mixing atomic orbitals to form new hybrid orbitals (with different energies, shapes, etc., than the component atomic orbitals) suitable for the pairing of electrons to form chemical bonds in valence bond theory. For example, in a carbon atom which forms four single bonds the valence-shell s orbital combines with three valence-shell p orbitals to form four equivalent sp3 mixtures in a tetrahedral arrangement around the carbon to bond to four different atoms.
Atomic absorption spectroscopyAtomic absorption spectroscopy (AAS) and atomic emission spectroscopy (AES) is a spectroanalytical procedure for the quantitative determination of chemical elements by free atoms in the gaseous state. Atomic absorption spectroscopy is based on absorption of light by free metallic ions. In analytical chemistry the technique is used for determining the concentration of a particular element (the analyte) in a sample to be analyzed.
X-ray crystallographyX-ray crystallography is the experimental science determining the atomic and molecular structure of a crystal, in which the crystalline structure causes a beam of incident X-rays to diffract into many specific directions. By measuring the angles and intensities of these diffracted beams, a crystallographer can produce a three-dimensional picture of the density of electrons within the crystal. From this electron density, the mean positions of the atoms in the crystal can be determined, as well as their chemical bonds, their crystallographic disorder, and various other information.
Ligand field theoryLigand field theory (LFT) describes the bonding, orbital arrangement, and other characteristics of coordination complexes. It represents an application of molecular orbital theory to transition metal complexes. A transition metal ion has nine valence atomic orbitals - consisting of five nd, one (n+1)s, and three (n+1)p orbitals. These orbitals are of appropriate energy to form bonding interaction with ligands. The LFT analysis is highly dependent on the geometry of the complex, but most explanations begin by describing octahedral complexes, where six ligands coordinate to the metal.
LigandIn 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".
Post-transition metalThe metallic elements in the periodic table located between the transition metals to their left and the chemically weak nonmetallic metalloids to their right have received many names in the literature, such as post-transition metals, poor metals, other metals, p-block metals and chemically weak metals. The most common name, post-transition metals, is generally used in this article. Physically, these metals are soft (or brittle), have poor mechanical strength, and usually have melting points lower than those of the transition metals.
Spin–lattice relaxationDuring nuclear magnetic resonance observations, spin–lattice relaxation is the mechanism by which the longitudinal component of the total nuclear magnetic moment vector (parallel to the constant magnetic field) exponentially relaxes from a higher energy, non-equilibrium state to thermodynamic equilibrium with its surroundings (the "lattice"). It is characterized by the spin–lattice relaxation time, a time constant known as T1.
Electromagnetic absorption by waterThe absorption of electromagnetic radiation by water depends on the state of the water. The absorption in the gas phase occurs in three regions of the spectrum. Rotational transitions are responsible for absorption in the microwave and far-infrared, vibrational transitions in the mid-infrared and near-infrared. Vibrational bands have rotational fine structure. Electronic transitions occur in the vacuum ultraviolet regions. Liquid water has no rotational spectrum but does absorb in the microwave region.
Pi backbondingIn chemistry, π backbonding, also called π backdonation, is when electrons move from an atomic orbital on one atom to an appropriate symmetry antibonding orbital on a π-acceptor ligand. It is especially common in the organometallic chemistry of transition metals with multi-atomic ligands such as carbon monoxide, ethylene or the nitrosonium cation. Electrons from the metal are used to bond to the ligand, in the process relieving the metal of excess negative charge. Compounds where π backbonding occurs include Ni(CO)4 and Zeise's salt.
Cyclopentadienyl complexA cyclopentadienyl complex is a coordination complex of a metal and cyclopentadienyl groups (C5H5−, abbreviated as Cp−). Cyclopentadienyl ligands almost invariably bind to metals as a pentahapto (η5-) bonding mode. The metal–cyclopentadienyl interaction is typically drawn as a single line from the metal center to the center of the Cp ring. Biscyclopentadienyl complexes are called metallocenes. A famous example of this type of complex is ferrocene (FeCp2), which has many analogues for other metals, such as chromocene (CrCp2), cobaltocene (CoCp2), and nickelocene (NiCp2).
