In
coordination chemistry
A coordination complex consists 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 ...
, a coordinate covalent bond, also known as a dative bond, dipolar bond, or coordinate bond is a kind of two-center, two-electron
covalent bond
A covalent bond is a chemical bond that involves the sharing of electrons to form electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs. The stable balance of attractive and repulsive forces between atoms ...
in which the two
electrons
The electron ( or ) is a subatomic particle with a negative one elementary electric charge. Electrons belong to the first generation of the lepton particle family,
and are generally thought to be elementary particles because they have no ...
derive from the same
atom
Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons.
Every solid, liquid, gas, and ...
. The bonding of
metal
A metal (from Greek μέταλλον ''métallon'', "mine, quarry, metal") is a material that, when freshly prepared, polished, or fractured, shows a lustrous appearance, and conducts electricity and heat relatively well. Metals are typicall ...
ions
An ion () is an atom or molecule with a net electrical charge.
The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
to
ligand
In coordination chemistry, a ligand is an ion or molecule (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 electr ...
s involves this kind of interaction. This type of interaction is central to
Lewis acid–base theory
A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty Non-bonding orbital, orbital which is capable of accepting an electron pair from a Lewis Base (chemistry), base to form a Lewis a ...
.
Coordinate bonds are commonly found in
coordination compounds.
Examples
![NH3-BF3-adduct-bond-lengthening-2D](https://upload.wikimedia.org/wikipedia/commons/6/6c/NH3-BF3-adduct-bond-lengthening-2D.png)
Coordinate covalent bonding is ubiquitous. In all
metal aquo-complexes
2O)''n''">(H2O)''n'''
m''
+, the bonding between water and the metal
cation
An ion () is an atom or molecule with a net electrical charge.
The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by convent ...
is described as a coordinate covalent bond. Metal-ligand interactions in most
organometallic
Organometallic 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 so ...
compounds and most
coordination compound
A coordination complex consists 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 ...
s are described similarly.
The term ''dipolar bond'' is used in
organic chemistry
Organic chemistry is a subdiscipline within chemistry involving the scientific study of the structure, properties, and reactions of organic compounds and organic materials, i.e., matter in its various forms that contain carbon atoms.Clayden, J.; ...
for compounds such as
amine oxide
In chemistry, an amine oxide, also known as an amine ''N''-oxide or simply ''N''-oxide, is a chemical compound that contains the functional group , a nitrogen-oxygen coordinate covalent bond with three additional hydrogen and/or substituent-grou ...
s for which the electronic structure can be described in terms of the basic
amine
In chemistry, amines (, ) are compounds and functional groups that contain a basic nitrogen atom with a lone pair. Amines are formally derivatives of ammonia (), wherein one or more hydrogen atoms have been replaced by a substituen ...
donating two electrons to an oxygen atom.
: → O
The arrow → indicates that both electrons in the bond originate from the amine
moiety
Moiety may refer to:
Chemistry
* Moiety (chemistry), a part or functional group of a molecule
** Moiety conservation, conservation of a subgroup in a chemical species
Anthropology
* Moiety (kinship), either of two groups into which a society is ...
. In a standard covalent bond each atom contributes one electron. Therefore, an alternative description is that the amine gives away one electron to the oxygen atom, which is then used, with the remaining unpaired electron on the nitrogen atom, to form a standard covalent bond. The process of transferring the electron from nitrogen to oxygen creates
formal charge
In chemistry, a formal charge (F.C. or q), in the covalent view of chemical bonding, is the charge assigned to an atom in a molecule, assuming that electrons in all chemical bonds are shared equally between atoms, regardless of relative electroneg ...
s, so the electronic structure may also be depicted as
:
![CoA6Cl3](https://upload.wikimedia.org/wikipedia/commons/f/fd/CoA6Cl3.png)
This electronic structure has an
electric dipole
The electric dipole moment is a measure of the separation of positive and negative electrical charges within a system, that is, a measure of the system's overall polarity. The SI unit for electric dipole moment is the coulomb-meter (C⋅m). The d ...
, hence the name polar bond. In reality, the atoms carry
partial charge A partial charge is a non-integer charge value when measured in elementary charge units. Partial charge is more commonly called net atomic charge. It is represented by the Greek lowercase letter 𝛿, namely 𝛿− or 𝛿+.
Partial charges are c ...
s; the more
electronegative
Electronegativity, symbolized as , is the tendency for an atom of a given chemical element to attract shared electrons (or electron density) when forming a chemical bond. An atom's electronegativity is affected by both its atomic number and the d ...
atom of the two involved in the bond will usually carry a partial negative charge. One exception to this is
carbon monoxide
Carbon monoxide (chemical formula CO) is a colorless, poisonous, odorless, tasteless, flammable gas that is slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simple ...
. In this case, the carbon atom carries the partial negative charge although it is less electronegative than oxygen.
An example of a dative covalent bond is provided by the interaction between a molecule of
ammonia
Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was ...
, a
Lewis base
A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...
with a lone pair of electrons on the nitrogen atom, and
boron trifluoride
Boron trifluoride is the inorganic compound with the formula BF3. This pungent, colourless, and toxic gas forms white fumes in moist air. It is a useful Lewis acid and a versatile building block for other boron compounds.
Structure and bondin ...
, a
Lewis acid
A Lewis acid (named for the American physical chemist Gilbert N. Lewis) is a chemical species that contains an empty orbital which is capable of accepting an electron pair from a Lewis base to form a Lewis adduct. A Lewis base, then, is any sp ...
by virtue of the boron atom having an incomplete
octet
Octet may refer to:
Music
* Octet (music), ensemble consisting of eight instruments or voices, or composition written for such an ensemble
** String octet, a piece of music written for eight string instruments
*** Octet (Mendelssohn), 1825 compos ...
of electrons. In forming the adduct, the boron atom attains an octet configuration.
The electronic structure of a
coordination complex
A coordination complex consists 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 ...
can be described in terms of the set of
ligand
In coordination chemistry, a ligand is an ion or molecule (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 electr ...
s each donating a pair of electrons to a metal centre. For example, in
hexamminecobalt(III) chloride
Hexaamminecobalt(III) chloride is the chemical compound with the formula o(NH3)6l3. It is the chloride salt of the coordination complex o(NH3)6sup>3+, which is considered an archetypal "Werner complex", named after the pioneer of coordination c ...
, each
ammonia
Ammonia is an inorganic compound of nitrogen and hydrogen with the formula . A stable binary hydride, and the simplest pnictogen hydride, ammonia is a colourless gas with a distinct pungent smell. Biologically, it is a common nitrogenous was ...
ligand donates its lone pair of electrons to the cobalt(III) ion. In this case, the bonds formed are described as coordinate bonds.
Comparison with other electron-sharing modes
In all cases, the bond, whether dative or "normal" electron-sharing, is a covalent bond. In common usage, the prefix dipolar, dative or coordinate merely serves to indicate the origin of the electrons used in creating the bond. For example, F
3B ← O(C
2H
5)
2 ("
boron trifluoride (diethyl) etherate") is prepared from BF
3 and :O(C
2H
5)
2, as opposed to the radical species
3">BF3sup>– and
2H5)2">O(C2H5)2sup>+. The dative bond is also a convenience in terms of notation, as formal charges are avoided: we can write D: + ()A ⇌ D → A rather than D
+–A
– (here : and () represent the lone-pair and empty orbital on the electron-pair donor D and acceptor A, respectively). The notation is sometimes used even when the Lewis acid-base reaction involved is only notional (e.g., the sulfoxide R
2S → O is rarely if ever made by reacting the sulfide R
2S with atomic oxygen O). Thus, most chemists ''do not'' make any claim with respect to the properties of the bond when choosing one notation over the other (formal charges vs. arrow bond).
It is generally true, however, that bonds depicted this way are polar covalent, sometimes strongly so, and some authors claim that there are genuine differences in the properties of a dative bond and electron-sharing bond and suggest that showing a dative bond is more appropriate in particular situations. As far back as 1989, Haaland characterized dative bonds as bonds that are (i) weak and long; (ii) with only a small degree of charge-transfer taking place during bond formation; and (iii) whose preferred mode of dissociation in the gas phase (or low ε inert solvent) is heterolytic rather than homolytic. The ammonia-borane adduct (H
3N → BH
3) is given as a classic example: the bond is weak, with a dissociation energy of 31 kcal/mol (cf. 90 kcal/mol for ethane), and long, at 166 pm (cf. 153 pm for ethane), and the molecule possesses a dipole moment of 5.2 D that implies a transfer of only 0.2 ''e''
– from nitrogen to boron. The heterolytic dissociation of H
3N → BH
3 is estimated to require 27 kcal/mol, confirming that heterolysis into ammonia and borane is more favorable than homolysis into radical cation and radical anion. However, aside from clear-cut examples, there is considerable dispute as to when a particular compound qualifies and, thus, the overall prevalence of dative bonding (with respect to an author's preferred definition). Computational chemists have suggested quantitative criteria to distinguish between the two "types" of bonding.
Some non-obvious examples where dative bonding is claimed to be important include
carbon suboxide
Carbon suboxide, or tricarbon dioxide, is an organic, oxygen-containing chemical compound with formula and structure . Its four cumulative double bonds make it a cumulene. It is one of the stable members of the series of linear oxocarbons , whi ...
(O≡C → C
0 ← C≡O), tetraaminoallenes (described using dative bond language as "carbodicarbenes"; (R
2N)
2C → C
0 ← C(NR
2)
2), the Ramirez
carbodiphosphorane (Ph
3P → C
0 ← PPh
3), and
bis(triphenylphosphine)iminium cation (Ph
3P → N
+ ← PPh
3), all of which exhibit considerably bent equilibrium geometries, though with a shallow barrier to bending. Simple application of the normal rules for drawing Lewis structures by maximizing bonding (using electron-sharing bonds) and minimizing formal charges would predict
heterocumulene A heterocumulene is a molecule or ion containing a chain of at least three double bonds between consecutive atoms, in which one or more atoms in the doubly bonded chain is a heteroatom. Such species are analogous to a cumulene in which the chain of ...
structures, and therefore linear geometries, for each of these compounds. Thus, these molecules are claimed to be better modeled as coordination complexes of :C: (carbon(0) or
carbone) or :N:
+ (mononitrogen cation) with CO, PPh
3, or ''N-''heterocycliccarbenes as ligands, the lone-pairs on the central atom accounting for the bent geometry. However, the usefulness of this view is disputed.
References
{{Authority control
Chemical bonding
Acid–base chemistry
Coordination chemistry