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In chemistry, reactions that involve a change in spin state are known as spin-forbidden reactions Such reactions show increased activation energy when compared to a similar reaction in which the spin states of the reactant and product are isomorphic. As a result of this increased activation energy, a decreased rate of reaction is observed. A famous example of spin-forbidden reaction is the very slow reaction of O
2 with hydrocarbons.
The dissociation of nitrous oxide is a well-studied process: [1]
O atoms have a triplet ground state.
Methoxy cation has a triplet ground state. In a mass spectrometer, it dissociates into singlet products (formyl cation and H2):
Numerous spin-forbidden reactions are encountered in transition metal chemistry since many metal ions can adopt multiple spin states. For example, ferrous porphyrin complexes containing one axial donor are high spin ferrous. These complexes, which are represented by myoglobin and hemoglobin, bind CO to give singlet products:
Cobalt(I) dicarbonyl complexes of a trispyrazolylborate are diamagnetic. The corresponding monocarbonyls have triplet ground states.
The addition of CO to Fe(CO)4 is an example showing the slowing effect of spin-forbidden reaction takes place when Fe(CO)x is placed under CO pressure. [3]
When a reaction converts a metal from a singlet to triplet state (or vice versa):
Strong spin-orbital coupling can satisfy the 2nd condition. Parameter 1, however, can lead to very slow reactions due to large disparities between the metal complex's potential energy surfaces, which only cross at high energy leading to a substantial activation barrier. [4]
Spin-forbidden reactions formally fall into the category of electronically non-adiabatic reactions. [5] In general, potential energy surfaces fall into either the adiabatic and diabatic classification. Potential Energy Surfaces that are adiabatic rely on the use of the full electronic Hamiltonian, which includes the spin-orbit term. Those that are diabatic are likewise derived by solving the eigenvalues of the Schrödinger equation, but in this case one or more terms are omitted. [1]
Once a minimum energy crossing point is reached and parameter 1 above is satisfied, the system needs to hop from one diabatic surface to the other, as stated above by parameter 2. At a given energy (E), the rate coefficient [k(E)] of a spin-forbidden reaction can be calculated using the density of rovibrational states of the reactant [ρ(E)] and the effective integrated density of states in the crossing seam between the two surfaces [Ner(E)].
where
The probability of hopping (psh) is calculated from Landau-Zener theory giving
where
in which the spin-orbit coupling derived off the diagonal Hamiltonian matrix element between two electronic states (H12), the relative slope of the two surfaces at the crossing seam [F(Δ)], the reduced mass of the system through its movement along the hopping coordinate (μ), and the kinetic energy of the system passing through the crossing point (E) are used.
It is useful to note that when Eh < Ec (when below the minimum energy crossing point) the probability of hopping between spin states is null. [6]
Insertion into C-H bonds, known as C-H activation, is an integral first step in C-H functionalization. [7] For some metal complexes with identical ligands, C-H activation is rapid when one metal is used and slow when other metals are used, often first row transition metals, due to the spin allowed nature of the former case and the spin-forbidden nature of the latter case. The difference in rates of C-H activation of methane for CoCp(CO), RhCp(CO), and IrCp(CO) readily demonstrate this property. CoCp(CO), the starting material in a C-H activation, exists in a triplet spin state while RhCp(CO) exists in a singlet state, with the triplet state only 5.9 kcal/mol away. IrCp(CO) is unique among these complexes in that its starting state is essentially degenerate between the triplet and singlet states. The given product of C-H insertion, CpMH(CO)(CH3), where M = Co, Rh, Ir, is in a singlet state meaning that the C-H activation with CoCp(CO) must reach the minimum energy crossing point for the reactant and product's potential energy surfaces, thus requiring relatively high energies to proceed. [8]
Metal-oxo species, due to their small spatial extent of metal-centered d orbitals leading to weak bonding, often have similar energies for both the low spin () and high spin configuration (). [9] This similarity in energy between the low- and high spin configurations of oxo-species lends itself to the study of spin-forbidden reactions, such as Mn(salen)-catalyzed epoxidation. The Mn(salen)-oxo species can exist in either a triplet or quintet state. While the product of the quintet lies at a lower energy, both the triplet and quintet products can be observed. [10]
Photochemistry is the branch of chemistry concerned with the chemical effects of light. Generally, this term is used to describe a chemical reaction caused by absorption of ultraviolet, visible (400–750 nm), or infrared radiation (750–2500 nm).
Intersystem crossing (ISC) is an isoenergetic radiationless process involving a transition between the two electronic states with different spin multiplicity.
In organic chemistry, a carbene is a molecule containing a neutral carbon atom with a valence of two and two unshared valence electrons. The general formula is R−:C−R' or R=C: where the R represents substituents or hydrogen atoms.
Singlet oxygen, systematically named dioxygen(singlet) and dioxidene, is a gaseous inorganic chemical with the formula O=O (also written as 1
[O
2] or 1
O
2), which is in a quantum state where all electrons are spin paired. It is kinetically unstable at ambient temperature, but the rate of decay is slow.
A transition metal carbene complex is an organometallic compound featuring a divalent carbon ligand, itself also called a carbene. Carbene complexes have been synthesized from most transition metals and f-block metals, using many different synthetic routes such as nucleophilic addition and alpha-hydrogen abstraction. The term carbene ligand is a formalism since many are not directly derived from carbenes and most are much less reactive than lone carbenes. Described often as =CR2, carbene ligands are intermediate between alkyls (−CR3) and carbynes (≡CR). Many different carbene-based reagents such as Tebbe's reagent are used in synthesis. They also feature in catalytic reactions, especially alkene metathesis, and are of value in both industrial heterogeneous and in homogeneous catalysis for laboratory- and industrial-scale preparation of fine chemicals.
Photosensitizers are light absorbers that alter the course of a photochemical reaction. They usually are catalysts. They can function by many mechanisms, sometimes they donate an electron to the substrate, sometimes they abstract a hydrogen atom from the substrate. At the end of this process, the photosensitizer returns to its ground state, where it remains chemically intact, poised to absorb more light. One branch of chemistry which frequently utilizes photosensitizers is polymer chemistry, using photosensitizers in reactions such as photopolymerization, photocrosslinking, and photodegradation. Photosensitizers are also used to generate prolonged excited electronic states in organic molecules with uses in photocatalysis, photon upconversion and photodynamic therapy. Generally, photosensitizers absorb electromagnetic radiation consisting of infrared radiation, visible light radiation, and ultraviolet radiation and transfer absorbed energy into neighboring molecules. This absorption of light is made possible by photosensitizers' large de-localized π-systems, which lowers the energy of HOMO and LUMO orbitals to promote photoexcitation. While many photosensitizers are organic or organometallic compounds, there are also examples of using semiconductor quantum dots as photosensitizers.
Triplet oxygen, 3O2, refers to the S = 1 electronic ground state of molecular oxygen (dioxygen). Molecules of triplet oxygen contain two unpaired electrons, making triplet oxygen an unusual example of a stable and commonly encountered diradical: it is more stable as a triplet than a singlet. According to molecular orbital theory, the electron configuration of triplet oxygen has two electrons occupying two π molecular orbitals (MOs) of equal energy (that is, degenerate MOs). In accordance with Hund's rules, they remain unpaired and spin-parallel, which accounts for the paramagnetism of molecular oxygen. These half-filled orbitals are antibonding in character, reducing the overall bond order of the molecule to 2 from the maximum value of 3 that would occur when these antibonding orbitals remain fully unoccupied, as in dinitrogen. The molecular term symbol for triplet oxygen is 3Σ−
g.
Nitroxyl or azanone is the chemical compound HNO. It is well known in the gas phase. Nitroxyl can be formed as a short-lived intermediate in the solution phase. The conjugate base, NO−, nitroxide anion, is the reduced form of nitric oxide (NO) and is isoelectronic with dioxygen. The bond dissociation energy of H−NO is 49.5 kcal/mol (207 kJ/mol), which is unusually weak for a bond to the hydrogen atom.
Spin chemistry is a sub-field of chemistry positioned at the intersection of chemical kinetics, photochemistry, magnetic resonance and free radical chemistry, that deals with magnetic and spin effects in chemical reactions. Spin chemistry concerns phenomena such as chemically induced dynamic nuclear polarization (CIDNP), chemically induced electron polarization (CIDEP), magnetic isotope effects in chemical reactions, and it is hypothesized to be key in the underlying mechanism for avian magnetoreception and consciousness.
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.
Atomic carbon, systematically named carbon and λ0-methane, is a colourless gaseous inorganic chemical with the chemical formula C. It is kinetically unstable at ambient temperature and pressure, being removed through autopolymerisation.
In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron. With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spontaneously dimerize. Most organic radicals have short lifetimes.
Organoiron chemistry is the chemistry of iron compounds containing a carbon-to-iron chemical bond. Organoiron compounds are relevant in organic synthesis as reagents such as iron pentacarbonyl, diiron nonacarbonyl and disodium tetracarbonylferrate. Although iron is generally less active in many catalytic applications, it is less expensive and "greener" than other metals. Organoiron compounds feature a wide range of ligands that support the Fe-C bond; as with other organometals, these supporting ligands prominently include phosphines, carbon monoxide, and cyclopentadienyl, but hard ligands such as amines are employed as well.
Dioxygen complexes are coordination compounds that contain O2 as a ligand. The study of these compounds is inspired by oxygen-carrying proteins such as myoglobin, hemoglobin, hemerythrin, and hemocyanin. Several transition metals form complexes with O2, and many of these complexes form reversibly. The binding of O2 is the first step in many important phenomena, such as cellular respiration, corrosion, and industrial chemistry. The first synthetic oxygen complex was demonstrated in 1938 with cobalt(II) complex reversibly bound O2.
Germylenes are a class of germanium(II) compounds with the general formula :GeR2. They are heavier carbene analogs. However, unlike carbenes, whose ground state can be either singlet or triplet depending on the substituents, germylenes have exclusively a singlet ground state. Unprotected carbene analogs, including germylenes, has a dimerization nature. Free germylenes can be isolated under the stabilization of steric hindrance or electron donation. The synthesis of first stable free dialkyl germylene was reported by Jutzi, et al in 1991.
Methylene is an organic compound with the chemical formula CH
2. It is a colourless gas that fluoresces in the mid-infrared range, and only persists in dilution, or as an adduct.
Cyclopentadienyliron dicarbonyl dimer is an organometallic compound with the formula [(η5-C5H5)Fe(CO)2]2, often abbreviated to Cp2Fe2(CO)4, [CpFe(CO)2]2 or even Fp2, with the colloquial name "fip dimer". It is a dark reddish-purple crystalline solid, which is readily soluble in moderately polar organic solvents such as chloroform and pyridine, but less soluble in carbon tetrachloride and carbon disulfide. Cp2Fe2(CO)4 is insoluble in but stable toward water. Cp2Fe2(CO)4 is reasonably stable to storage under air and serves as a convenient starting material for accessing other Fp (CpFe(CO)2) derivatives (described below).
Phosphenium ions, not to be confused with phosphonium or phosphirenium, are divalent cations of phosphorus of the form [PR2]+. Phosphenium ions have long been proposed as reaction intermediates.
Gallylenes are a class of gallium species which are electronically neutral and in the +1-oxidation state. This broad definition may include many gallium species, such as oligomeric gallium compounds in which the gallium atoms are coordinated to each other, but these classes of compounds are often referred to as gallanes. In recent literature, the term gallylene has mostly been reserved for low valent gallium species which may have a lone pair, analogous to NHC's or terminal borylenes. They are compounds of academic interest because of their distinctive electronic properties which have been achieved for higher main group elements such as borylenes and carbenes.
Tris(cyclooctatetraene)triiron or Fe3(COT)3, also referred to as the Lavallo-Grubbs compound (after its discoverers) is an organoiron compound with the formula Fe3(C8H8)3. It is a pyrophoric, black crystalline solid, which is insoluble in common organic solvents.The compound represents a rare example of a hydrocarbon analogue of the well-known Triiron dodecacarbonyl (Fe3(CO)12), originally prepared by Dewar and Jones in the early 20th century.