8/13/2021 Coordinate covalent bond - Wikipedia

Coordinate covalent bond

A coordinate covalent bond,[1] also known as a dative bond,[2] dipolar bond,[3] or
coordinate bond[4] is a kind of two-center, two-electron covalent bond in which the two electrons
derive from the same atom. The bonding of metal ions to ligands involves this kind of interaction.[5]
This type of interaction is central to Lewis theory.

Examples
Coordinate covalent bonding is ubiquitous.[6] In all metal
aquo-complexes [M(H2O)n]m+, the bonding between
water and the metal cation is described as a coordinate
covalent bond. Metal-ligand interactions in most
organometallic compounds and most coordination
compounds are described similarly.

The term dipolar bond is used in organic chemistry for Formation of an adduct of ammonia and boron
compounds such as amine oxides for which the electronic trifluoride, involving formation of a coordinate
structure can be described in terms of the basic amine covalent bond.
donating two electrons to an oxygen atom.

R
3N → O

The arrow → indicates that both electrons in the bond originate from the amine moiety. 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 charges, so the electronic structure may also be
depicted as
+
−

R
3N O

This electronic structure has an electric dipole, hence the name

polar bond. In reality, the atoms carry partial charges; the more
electronegative atom of the two involved in the bond will usually
carry a partial negative charge. One exception to this is carbon
monoxide. 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, a Lewis base with a
Hexamminecobalt(III) chloride
lone pair of electrons on the nitrogen atom, and boron trifluoride,
a Lewis acid by virtue of the boron atom having an incomplete
octet of electrons. In forming the adduct, the boron atom attains
an octet configuration.

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The electronic structure of a coordination complex can be described in terms of the set of ligands each
donating a pair of electrons to a metal centre. For example, in hexamminecobalt(III) chloride, each
ammonia 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, F3B ← O(C2H5)2 ("boron trifluoride (diethyl) etherate") is
prepared from BF3 and :O(C2H5)2, as opposed to the radical species [•BF3]– and [•O(C2H5)2]+. 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 R2S → O is rarely if ever made
by reacting the sulfide R2S 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.[7] The ammonia-borane adduct (H3N → BH3) 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 H3N → BH3 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.[8][9][10]

Some non-obvious examples where dative bonding is claimed to be important include carbon
suboxide (O≡C → C0 ← C≡O), tetraaminoallenes (described using dative bond language as
"carbodicarbenes"; (R2N)2C → C0 ← C(NR2)2), the Ramirez carbodiphosphorane (Ph3P → C0 ←
PPh3), and bis(triphenylphosphine)iminium cation (Ph3P → N+ ← PPh3), 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 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, PPh3, 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.[9][10]

References
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1. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online
corrected version:  (2006–) "dipolar bond (https://goldbook.iupac.org/D01752.html)".
doi:10.1351/goldbook.D01752 (https://doi.org/10.1351%2Fgoldbook.D01752)
2. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online
corrected version:  (2006–) "dative bond (https://goldbook.iupac.org/D01523.html)".
doi:10.1351/goldbook.D01523 (https://doi.org/10.1351%2Fgoldbook.D01523)
3. IUPAC. Compendium of Chemical Terminology, 2nd ed. (the "Gold Book"). Compiled by A. D.
McNaught and A. Wilkinson. Blackwell Scientific Publications, Oxford (1997). Online version
(2019-) created by S. J. Chalk. ISBN 0-9678550-9-8. https://doi.org/10.1351/goldbook.
4. IUPAC, Compendium of Chemical Terminology, 2nd ed. (the "Gold Book") (1997). Online
corrected version:  (2006–) "coordinate bond (https://goldbook.iupac.org/C01329.html)".
doi:10.1351/goldbook.C01329 (https://doi.org/10.1351%2Fgoldbook.C01329)
5. Ariyarathna, Isuru. First Principle Studies on Ground and Excited Electronic States: Chemical
Bonding in Main-Group Molecules, Molecular Systems with Diffuse Electrons, and Water
Activation using Transition Metal Monoxides (https://etd.auburn.edu//handle/10415/7601).
6. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.).
Butterworth-Heinemann. ISBN 978-0-08-037941-8.
7. Haaland, Arne (1989). "Covalent versus Dative Bonds to Main Group Metals, a Useful
Distinction". Angewandte Chemie International Edition in English. 28 (8): 992–1007.
doi:10.1002/anie.198909921 (https://doi.org/10.1002%2Fanie.198909921). ISSN 0570-0833 (http
s://www.worldcat.org/issn/0570-0833).
8. Himmel, Daniel; Krossing, Ingo; Schnepf, Andreas (2014-01-07). "Dative Bonds in Main-Group
Compounds: A Case for Fewer Arrows!". Angewandte Chemie International Edition. 53 (2): 370–
374. doi:10.1002/anie.201300461 (https://doi.org/10.1002%2Fanie.201300461). PMID 24243854
(https://pubmed.ncbi.nlm.nih.gov/24243854).
9. Frenking, Gernot (2014-06-10). "Dative Bonds in Main-Group Compounds: A Case for More
Arrows!". Angewandte Chemie International Edition. 53 (24): 6040–6046.
doi:10.1002/anie.201311022 (https://doi.org/10.1002%2Fanie.201311022).
10. Schmidbaur, Hubert; Schier, Annette (2013-01-02). "Coordination Chemistry at Carbon: The
Patchwork Family Comprising (Ph 3 P) 2 C, (Ph 3 P)C(C 2 H 4 ), and (C 2 H 4 ) 2 C".
Angewandte Chemie International Edition. 52 (1): 176–186. doi:10.1002/anie.201205294 (https://
doi.org/10.1002%2Fanie.201205294).

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