Cyanate

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Not to be confused with fulminate.
Space-filling model of the cyanate anion

The cyanate ion is an

anion with the chemical formula OCN−. It is a resonance
of three forms: [O−−C≡N] (61%) ↔ [O=C=N−] (30%) ↔ [O+≡C−N2−] (4%).

Cyanate is the derived anion of isocyanic acid, H−N=C=O, and its lesser tautomer cyanic acid (a.k.a. cyanol), H−O−C≡N.

Any salt containing the ion, such as ammonium cyanate, is called a cyanate.

The cyanate ion is an isomer of the much-less-stable fulminate anion, CNO− or [C−≡N+−O−].[1]

The cyanate ion is an

ambidentate ligand, forming complexes with a metal ion in which either the nitrogen or oxygen atom may be the electron-pair donor. It can also act as a bridging ligand
.

Compounds that contain the cyanate

nitrile oxide
functional group, −CNO or −C≡N+−O−.

Cyanate ion

The three atoms in a cyanate ion lie on a straight line, giving the ion a linear structure. The

electronic structure
is described most simply as

:Ö̤−C≡N:

with a single C−O bond and a triple C≡N bond. (Or more completely as :Ö̤−C≡N: ↔ Ö̤=C=N̤̈ ↔ :O≡C−N̤̈:) The

infrared spectrum of a cyanate salt has a band at ca. 2096 cm−1; such a high frequency is characteristic of a triple bond.[2]

The cyanate ion is a

ambidentate ligand
.

Cyanate salts

Sodium cyanate is isostructural with sodium fulminate, confirming the linear structure of the cyanate ion.[3] It is made industrially by heating a mixture of sodium carbonate and urea.[4]

Na2CO3 + 2 OC(NH2)2 → 2 NaNCO + CO2 + 2 NH3 + H2O

A similar reaction is used to make potassium cyanate. Cyanates are produced when cyanides are oxidized. Use of this fact is made in cyanide decontamination processes where oxidants such as permanganate and hydrogen peroxide are used to convert toxic cyanide into less-toxic cyanate.

Name formula Crystal system Space group Unit cell (Å) volume (Å3) Density (g/cm3) Comment Reference
Ammonium cyanate NH4OCN tetragonal P4/nmm a=5.082 b=5.082 c=5.551 decomposes when heated to urea [5]
Lithium cyanate LiOCN trigonal R3m a = 3.230 b = 14.268 Z=3 128.90 1.895 melts at 475 °C [6]
Sodium cyanate NaOCN hexagonal R3m a = 3.568 c = 15.123 166.72 1.94 melts at 550 °C [7]
Potassium cyanate KOCN tetragonal I4/mcm a = 6.091 c = 7.052 261.6 2.056 melts at 315 °C [8]
Rubidium cyanate RbOCN tetragonal I4/mcm a = 6.35 c = 7.38 297.58 2.85 [9]
Cesium cyanate CsOCN tetragonal I4mcm a = 6.519 c = 7.994 339.68 3.42 [10]
Thallium cyanate TlOCN tetragonal I4mcm a = 6.23 c = 7.32 284.3 5.76 [9]
Silver cyanate AgOCN monoclinic P21/m a = 5.474 b = 6.378 c = 3.417 β = 90.931° 119.29 4.173 melts at 652 °C [11]
Strontium cyanate Sr(OCN)2 orthorhombic Fddd a = 6.151 b = 11.268 c = 11.848 Z = 8 821.1 2.78 [12]

Complexes with the cyanate ion

Cyanate is an

ambidentate ligand which can donate the pair of electrons on the nitrogen atom or the oxygen atom, or both. Structurally the isomers can be distinguished by the geometry of the complex. In N-bonded cyanate complexes the M−NCO unit sometimes has a linear structure, but with O-bonded cyanate the M−O−C unit is bent. Thus, the silver cyanato complex, [Ag(NCO)2]−, has a linear structure as shown by X-ray crystallography.[13] However, the crystal structure of silver cyanate shows zigzag chains of nitrogen atoms and silver atoms.[14]
There also exists a structure 

   NCO
  /   \
Ni    Ni
  \   /
   OCN

in which the Ni-N-C group is bent.[13]

divalent metals are N-bonded. O-Bonding has been suggested for complexes of the type [M(OCN)6]n−, M = Mo(III), Re(IV), and Re(V). The yellow complex Rh(PPh3)3(NCO) and orange complex Rh(PPh3)3(OCN) are linkage isomers and show differences in their infrared spectra which can be used for diagnosis.[15]

The cyanate ion can bridge between two metal atoms by using both its donor atoms. For example, this structure is found in the compound [Ni2(NCO)2(

En)2](BPh4)2. In this compound both the Ni−N−C unit and Ni−O−C unit are bent, even though in the first case donation is through the nitrogen atom.[16]

Cyanate functional group

Compounds that contain the cyanate

Aryl cyanates such are phenyl cyanate, C6H5OCN can be formed by a reaction of phenol with cyanogen chloride
, ClCN, in the presence of a base.

Organic compounds that contain the isocyanate functional group −N=C=O are known as isocyanates. It is conventional in organic chemistry to write isocyanates with two double bonds, which accords with a simplistic valence bond theory of the bonding. In nucleophilic substitution reactions cyanate usually forms an isocyanate. Isocyanates are widely used in the manufacture of polyurethane[17] products and pesticides; methyl isocyanate, used to make pesticides, was a major factor in the Bhopal disaster.

See also

References

  1. doi:10.1080/07370652.2018.1531089
  2. ^ Nakamoto, Part A, p171
  3. ^ Wells, p722.
  4. ^ Greenwood, p324
  5. PMID 14624593
    .
  6. doi:10.1002/zaac.201100081
    .
  7. doi:10.1515/znb-2010-0416
    .
  8. doi:10.1016/S0022-3697(03)00258-0
    .
  9. ^
    doi:10.1039/JR9590002499
  10. doi:10.1515/znb-2019-0168
    .
  11. doi:10.1016/j.physb.2006.05.197
    .
  12. PMID 19444832
    .
  13. ^
    ISBN 978-0-08-037941-8. (click here
    }
  14. doi:10.1107/S0365110X65000944
    .
  15. ^ Nakamoto, Part B, pp 121–123.
  16. ^ Greenwood, Table 8.9
  17. doi:10.1021/ed069p909
    .

External links

Bibliography

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