Phi bond

Last updated
Phi-bond-f-orbitals-2D.png
Phi-bond-boundary-surface-diagram-2D.png
Suitably-aligned f atomic orbitals can overlap to form a φ molecular orbital (a φ bond)

In chemistry, phi bonds (φ bonds) are covalent chemical bonds, where six lobes of one involved atomic orbital overlap six lobes of the other involved atomic orbital. This overlap leads to the formation of a bonding molecular orbital with three nodal planes which contain the internuclear axis and go through both atoms.

The Greek letter φ in their name refers to f orbitals, since the orbital symmetry of the φ bond is the same as that of the usual (6-lobed) type of f orbital when seen down the bond axis.

There was one possible candidate known in 2005 of a molecule with phi bonding (a U−U bond, in the molecule U2). [1] However, later studies that accounted for spin orbit interactions found that the bonding was only of fourth order. [2] [3] [4] Experimental evidence of existence of phi bonding between a thorium atom and cyclooctatetraene in thorocene has been shown, supported by computational analysis. [5]

Related Research Articles

Chemical bond Lasting attraction between atoms that enables the formation of chemical compounds

A chemical bond is a lasting attraction between atoms, ions or molecules that enables the formation of chemical compounds. The bond may result from the electrostatic force between oppositely charged ions as in ionic bonds or through the sharing of electrons as in covalent bonds. The strength of chemical bonds varies considerably; there are "strong bonds" or "primary bonds" such as covalent, ionic and metallic bonds, and "weak bonds" or "secondary bonds" such as dipole–dipole interactions, the London dispersion force and hydrogen bonding.

Covalent bond Chemical bond that involves the sharing of electron pairs between atoms

A covalent bond is a chemical bond that involves the sharing of electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs, and the stable balance of attractive and repulsive forces between atoms, when they share electrons, is known as covalent bonding. For many molecules, the sharing of electrons allows each atom to attain the equivalent of a full valence shell, corresponding to a stable electronic configuration. In organic chemistry, covalent bonds are much more common than ionic bonds.

Molecule Electrically neutral group of two or more atoms

A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and biochemistry, the distinction from ions is dropped and molecule is often used when referring to polyatomic ions.

Molecular orbital Wave-like behavior of an electron in a molecule

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.

Aromaticity Phenomenon providing chemical stability in resonating hybrids of cyclic organic compounds

In chemistry, aromaticity is a property of cyclic (ring-shaped), typically planar (flat) molecular structures with pi bonds in resonance that gives increased stability compared with other geometric or connective arrangements with the same set of atoms. Aromatic rings are very stable and do not break apart easily. Organic compounds that are not aromatic are classified as aliphatic compounds—they might be cyclic, but only aromatic rings have enhanced stability.

A linear combination of atomic orbitals or LCAO is a quantum superposition of atomic orbitals and a technique for calculating molecular orbitals in quantum chemistry. In quantum mechanics, electron configurations of atoms are described as wavefunctions. In a mathematical sense, these wave functions are the basis set of functions, the basis functions, which describe the electrons of a given atom. In chemical reactions, orbital wavefunctions are modified, i.e. the electron cloud shape is changed, according to the type of atoms participating in the chemical bond.

Pi bond Type of chemical bond

In chemistry, pi bonds are covalent chemical bonds, in each of which two lobes of an orbital overlap with two lobes of an orbital on another atom, and in which this overlap occurs laterally. Each of these atomic orbitals has an electron density of zero at a shared nodal plane that passes through the two bonded nuclei. This plane also is a nodal plane for the molecular orbital of the pi bond. Pi bonds can form in double and triple bonds but do not form in single bonds in most cases.

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.

In chemistry, valence bond (VBT) theory is one of the two basic theories, along with molecular orbital (MO) theory, that were developed to use the methods of quantum mechanics to explain chemical bonding. It focuses on how the atomic orbitals of the dissociated atoms combine to give individual chemical bonds when a molecule is formed. In contrast, molecular orbital theory has orbitals that cover the whole molecule.

Sigma bond Covalent chemical bond

In chemistry, sigma bonds are the strongest type of covalent chemical bond. They are formed by head-on overlapping between atomic orbitals. Sigma bonding is most simply defined for diatomic molecules using the language and tools of symmetry groups. In this formal approach, a σ-bond is symmetrical with respect to rotation about the bond axis. By this definition, common forms of sigma bonds are s+s, pz+pz, s+pz and dz2+dz2 . Quantum theory also indicates that molecular orbitals (MO) of identical symmetry actually mix or hybridize. As a practical consequence of this mixing of diatomic molecules, the wavefunctions s+s and pz+pz molecular orbitals become blended. The extent of this mixing depends on the relative energies of the MOs of like symmetry.

In chemistry, orbital hybridisation is the concept of mixing atomic orbitals to form new hybrid 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. Hybrid orbitals are useful in the explanation of molecular geometry and atomic bonding properties and are symmetrically disposed in space. Usually hybrid orbitals are formed by mixing atomic orbitals of comparable energies.

Delta bond Type of Chemical Bond

In chemistry, delta bonds are covalent chemical bonds, where four lobes of one involved atomic orbital overlap four lobes of the other involved atomic orbital. This overlap leads to the formation of a bonding molecular orbital with two nodal planes which contain the internuclear axis and go through both atoms.

Quintuple bond

A quintuple bond in chemistry is an unusual type of chemical bond, first reported in 2005 for a dichromium compound. Single bonds, double bonds, and triple bonds are commonplace in chemistry. Quadruple bonds are rarer but are currently known only among the transition metals, especially for Cr, Mo, W, and Re, e.g. [Mo2Cl8]4− and [Re2Cl8]2−. In a quintuple bond, ten electrons participate in bonding between the two metal centers, allocated as σ2π4δ4.

Quadruple bond Chemical bond involving eight electrons; has one sigma, two pi, and one delta bond

A quadruple bond is a type of chemical bond between two atoms involving eight electrons. This bond is an extension of the more familiar types double bonds and triple bonds. Stable quadruple bonds are most common among the transition metals in the middle of the d-block, such as rhenium, tungsten, technetium, molybdenum and chromium. Typically the ligands that support quadruple bonds are π-donors, not π-acceptors.

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.

Diatomic carbon Chemical compound

Diatomic carbon (systematically named dicarbon and 2,2λ2-ethene), is a green, gaseous inorganic chemical with the chemical formula C=C (also written [C2] or C2). It is kinetically unstable at ambient temperature and pressure, being removed through autopolymerisation. It occurs in carbon vapor, for example in electric arcs; in comets, stellar atmospheres, and the interstellar medium; and in blue hydrocarbon flames. Diatomic carbon is the second simplest form of carbon after atomic carbon, and is an intermediate participator in the genesis of fullerenes.

Localized molecular orbitals are molecular orbitals which are concentrated in a limited spatial region of a molecule, such as a specific bond or lone pair on a specific atom. They can be used to relate molecular orbital calculations to simple bonding theories, and also to speed up post-Hartree–Fock electronic structure calculations by taking advantage of the local nature of electron correlation. Localized orbitals in systems with periodic boundary conditions are known as Wannier functions.

Sextuple bond Covalent bond involving 12 bonding electrons

A sextuple bond is a type of covalent bond involving 12 bonding electrons and in which the bond order is 6. The only known molecules with true sextuple bonds are the diatomic dimolybdenum (Mo2) and ditungsten (W2), which exist in the gaseous phase and have boiling points of 4,639 °C (8,382 °F) and 5,930 °C (10,710 °F). There is strong evidence to believe that there is no element with atomic number below about 100 that can form a bond with a greater order than 6 between its atoms, but the question of possibility of such a bond between two atoms of different elements remains open. Bonds between heteronuclear systems with two atoms of different elements may not necessarily have the same limit.

In chemical bonds, an orbital overlap is the concentration of orbitals on adjacent atoms in the same regions of space. Orbital overlap can lead to bond formation. Linus Pauling explained the importance of orbital overlap in the molecular bond angles observed through experimentation; it is the basis for orbital hybridization. As s orbitals are spherical (and have no directionality) and p orbitals are oriented 90° to each other, a theory was needed to explain why molecules such as methane (CH4) had observed bond angles of 109.5°. Pauling proposed that s and p orbitals on the carbon atom can combine to form hybrids (sp3 in the case of methane) which are directed toward the hydrogen atoms. The carbon hybrid orbitals have greater overlap with the hydrogen orbitals, and can therefore form stronger C–H bonds.

The charge-shift bond has been proposed as a new class of chemical bond that sits alongside the three familiar families of covalent, ionic bonds, and metallic bonds where electrons are shared or transferred respectively. The charge shift bond derives its stability from the resonance of ionic forms rather than the covalent sharing of electrons which are often depicted as having electron density between the bonded atoms. A feature of the charge shift bond is that the predicted electron density between the bonded atoms is low. It has long been known from experiment that the accumulation of electronic charge between the bonded atoms is not necessarily a feature of covalent bonds. An example where charge shift bonding has been used to explain the low electron density found experimentally is in the central bond between the inverted tetrahedral carbons in [1.1.1]propellanes. Theoretical calculations on a range of molecules have indicated that a charge shift bond is present, a striking example being fluorine, F2, which is normally described as having a typical covalent bond. The Charge Shift Bond(CSB) has also been shown to exist at the cation-anion interface of Protic Ionic Liquids(PILs). The authors have also shown how CSB character in PILs correlates with their physicochemical properties.

References

  1. Gagliardi, Laura; Roos, Björn O. (2005). "Quantum chemical calculations show that the uranium molecule U2 has a quintuple bond". Nature. 433 (7028): 848–851. Bibcode:2005Natur.433..848G. doi:10.1038/nature03249. PMID   15729337. S2CID   421380.
  2. T. A. Manz (2017). "Introducing DDEC6 atomic population analysis: part 3. Comprehensive method to compute bond orders". RSC Adv. 7 (72): 45552–45581. Bibcode:2017RSCAd...745552M. doi: 10.1039/c7ra07400j .
  3. "The diuranium molecule has a quadruple bond". chab.ethz.ch. Retrieved 2020-03-21.
  4. Knecht, Stefan; Jensen, Hans Jørgen Aa; Saue, Trond (January 2019). "Relativistic quantum chemical calculations show that the uranium molecule U 2 has a quadruple bond". Nature Chemistry. 11 (1): 40–44. doi:10.1038/s41557-018-0158-9. ISSN   1755-4349. PMID   30374039. S2CID   53112083.
  5. Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Clark, David L.; Kozimor, Stosh A.; Martin, Richard L.; Shuh, David K.; Tyliszczak, Tolek (2014). "New evidence for 5f covalency in actinocenes determined from carbon K-edge XAS and electronic structure theory". Chem. Sci. 5 (1): 351–359. doi:10.1039/C3SC52030G. ISSN   2041-6520.