Quadruple bond

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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. [1] 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.


The structure of chromium(II) acetate contains a quadruple Cr-Cr bond. Cr2(OAc)4.svg
The structure of chromium(II) acetate contains a quadruple Cr–Cr bond.


Chromium(II) acetate, Cr2(μ-O2CCH3)4(H2O)2, was the first chemical compound containing a quadruple bond to be synthesized. It was described in 1844 by E. Peligot, although its distinctive bonding was not recognized for more than a century. [2]

The first crystallographic study of a compound with a quadruple bond was provided by Soviet chemists for salts of Re
. [3] The very short Re–Re distance was noted. This short distance (and the salt's diamagnetism) indicated Re–Re bonding. These researchers however misformulated the anion as a derivative of Re(II), i.e., Re

Soon thereafter, F. Albert Cotton and C.B. Harris reported the crystal structure of potassium octachlorodirhenate or K2[Re2Cl8]·2H2O. [4] This structural analysis indicated that the previous characterization was mistaken. Cotton and Harris formulated a molecular orbital rationale for the bonding that explicitly indicated a quadruple bond. [2] The rhenium–rhenium bond length in this compound is only 224  pm. In molecular orbital theory, the bonding is described as σ2π4δ2 with one sigma bond, two pi bonds and one delta bond.

Structure and bonding

The octachlorodirhenate(III) anion, [Re2Cl8] , which features a quadruple Re-Re bond Octachlorodirhenate(III)-3D-balls.png
The octachlorodirhenate(III) anion, [Re2Cl8] , which features a quadruple Re–Re bond
Formation of a delta bond by the overlap of two d orbitals Delta-bond-formation-2D.png
Formation of a delta bond by the overlap of two d orbitals

The [Re2Cl8]2− ion adopts an eclipsed conformation as shown at left. The delta bonding orbital is then formed by overlap of the d orbitals on each rhenium atom, which are perpendicular to the Re–Re axis and lie in between the Re–Cl bonds. The d orbitals directed along the Re–Cl bonds are stabilized by interaction with chlorine ligand orbitals and do not contribute to Re–Re bonding. [5] In contrast, the [Os2Cl8]2− ion with two more electrons (σ2π4δ2δ*2) has an Os–Os triple bond and a staggered geometry. [5]

Many other compounds with quadruple bonds between transition metal atoms have been described, often by Cotton and his coworkers. Isoelectronic with the dirhenium compound is the salt K4[Mo2Cl8] (potassium octachlorodimolybdate). [6] An example of a ditungsten compound with a quadruple bond is ditungsten tetra(hpp).

Quadruple bonds between atoms of main-group elements are unknown. Molecular orbital theory shows that there are two sets of paired electrons in the sigma system (one bonding, one antibonding), and two sets of paired electrons in a degenerate π-bonding set of orbitals. This adds up to give a bond order of 2, meaning that there exists a double bond between the two carbon atoms in a dicarbon (C2) molecule. The molecular orbital diagram of diatomic carbon would show that there are two pi bonds and no sigma bonds. However, a recent paper by S. Shaik et al. has suggested that a quadruple bond exists in diatomic carbon, [7] but this is disputed. [8]

See also

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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.

Conjugated system System of connected p orbitals with delocalized electrons increasing molecular stability.

In chemistry, a conjugated system is a system of connected p orbitals with delocalized electrons in a molecule, which in general lowers the overall energy of the molecule and increases stability. It is conventionally represented as having alternating single and multiple bonds. Lone pairs, radicals or carbenium ions may be part of the system, which may be cyclic, acyclic, linear or mixed. The term "conjugated" was coined in 1899 by the German chemist Johannes Thiele.

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.

Octet rule Chemical rule of thumb

The octet rule is a chemical rule of thumb that reflects the theory that main-group elements tend to bond in such a way that each atom has eight electrons in its valence shell, giving it the same electronic configuration as a noble gas. The rule is especially applicable to carbon, nitrogen, oxygen, and the halogens, but also to metals such as sodium or magnesium. Other rules exist for other elements, such as the duplet rule for hydrogen and helium, or the 18-electron rule for transition metals.

Triple bond Chemical bond involving six bonding electrons; one sigma plus two pi bonds

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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.

Unsaturated hydrocarbon

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Delocalized electron Electrons that are not associated with a single atom or covalent bond

In chemistry, delocalized electrons are electrons in a molecule, ion or solid metal that are not associated with a single atom or a covalent bond.

Pi backbonding Movement of electrons from one atoms orbital to a symmetric antibonding orbital on another

In 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. IUPAC offers the following definition for backbonding:

A description of the bonding of π-conjugated ligands to a transition metal which involves a synergic process with donation of electrons from the filled π-orbital or lone electron pair orbital of the ligand into an empty orbital of the metal (donor–acceptor bond), together with release (back donation) of electrons from an nd orbital of the metal (which is of π-symmetry with respect to the metal–ligand axis) into the empty π*-antibonding orbital of the ligand.

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.

A three-center two-electron (3c–2e) bond is an electron-deficient chemical bond where three atoms share two electrons. The combination of three atomic orbitals form three molecular orbitals: one bonding, one non-bonding, and one anti-bonding. The two electrons go into the bonding orbital, resulting in a net bonding effect and constituting a chemical bond among all three atoms. In many common bonds of this type, the bonding orbital is shifted towards two of the three atoms instead of being spread equally among all three. Example molecules with 3c–2e bonds are the trihydrogen cation H+
) and diborane. In these two structures, the three atoms in each 3c-2e bond form an angular geometry, leading to a bent bond.

A non-covalent interaction differs from a covalent bond in that it does not involve the sharing of electrons, but rather involves more dispersed variations of electromagnetic interactions between molecules or within a molecule. The chemical energy released in the formation of non-covalent interactions is typically on the order of 1–5 kcal/mol (1000–5000 calories per 6.02 × 1023 molecules). Non-covalent interactions can be classified into different categories, such as electrostatic, π-effects, van der Waals forces, and hydrophobic effects.

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.

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 one s orbital, three p orbitals, and five d orbitals which can collectively accommodate 18 electrons as either bonding or nonbonding 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. The rule is not helpful for complexes of metals that are not transition metals, and interesting or useful transition metal complexes will violate the rule because of the consequences deviating from the rule bears on reactivity. The rule was first proposed by American chemist Irving Langmuir in 1921.

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.

Molybdenum(II) acetate Chemical compound

Molybdenum(II) acetate is a coordination compound with the formula Mo2(O2CCH3)4. It is a yellow, diamagnetic, air-stable solid that is slightly soluble in organic solvents. Molybdenum(II) acetate is an iconic example of a compound with a metal-metal quadruple bond.

Potassium octachlorodirhenate(III) is an inorganic compound with the formula K2Re2Cl8. This dark blue salt is well known as an early example of a compound featuring quadruple bond between its metal centers. Although the compound has no practical value, its characterization was significant in opening a new field of research into complexes with quadruple 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.

Metal–metal bond

In inorganic chemistry, metal–metal bonds describe attractive interactions between metal centers. The simplest examples are found in bimetallic complexes. Metal–metal bonds can be "supported", i.e. be accompanied by one or more bridging ligands, or "unsupported". They can also vary according to bond order. The topic of metal–metal bonding is usually discussed within the framework of coordination chemistry, but the topic is related to extended metallic bonding, which describes interactions between metals in extended solids such as bulk metals and metal subhalides.


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  5. 1 2 Miessler, G. L.; Tarr, D. A. (1999). Inorganic Chemistry (2nd ed.). Prentice-Hall. p. 531. ISBN   0-13-841891-8.
  6. Girolami, G. S.; Rauchfuss, T. B.; Angelici, R. J. (1999). Synthesis and Technique in Inorganic Chemistry. Mill Valley, CA: University Science Books. ISBN   0935702482.
  7. Shaik, Sason; Danovich, David; Wu, Wei; Su, Peifeng; Rzepa, Henry S.; Hiberty, Philippe C. (2012). "Quadruple bonding in C2 and analogous eight-valence electron species". Nature Chemistry . 4: 195–200. Bibcode:2012NatCh...4..195S. doi:10.1038/nchem.1263.
  8. Grunenberg, Jörg (2012). "Quantum chemistry: Quadruply bonded carbon". Nature Chemistry . 4 (3): 154–155. Bibcode:2012NatCh...4..154G. doi:10.1038/nchem.1274. PMID   22354425.

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