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Cyanate

The cyanate (OCN⁻) is a linear, triatomic anion composed of one oxygen, one carbon, and one atom, serving as the conjugate base of cyanic (HOCN) and forming the basis for cyanate salts and esters. It exhibits stabilization across three primary structures—predominantly [O⁻–C≡N] (approximately 61%) and [O=C=N⁻] (30%), with a minor contribution from [O⁺≡C–N²⁻] (4%)—resulting in partial double-bond character along the O–C–N chain and bond lengths of about 1.26 (O–C) and 1.17 (C–N). This ambidentate allows the ion to bind to metals or other species via either the oxygen or nitrogen atom, influencing its reactivity in chemical systems. Cyanates hold historical significance in chemistry, particularly through Friedrich Wöhler's 1828 conversion of (NH₄OCN) to (NH₂CONH₂) by heating, which provided early evidence that organic compounds could be synthesized from inorganic precursors and challenged prevailing vitalistic theories. Common cyanate salts, such as (NaOCN) and (KOCN), are white, crystalline solids soluble in water and used as intermediates in , including the production of herbicides, pharmaceuticals, and cyanate ester resins for high-performance thermosetting polymers in and electronics applications. In biological and environmental contexts, cyanate plays a role as a source for certain microorganisms, including autotrophic oxidizers, and is actively cycled in ecosystems despite its low abundance (typically nanomolar concentrations in ). was investigated in the as a potential therapeutic for sickle cell anemia due to its ability to carbamylate and inhibit sickling, though clinical trials were halted owing to concerns. Additionally, cyanates find industrial use in steel heat treatment to enhance surface properties and in coordination chemistry as pseudohalide ligands in metal complexes.

Cyanate Ion

Structure and Bonding

The cyanate ion, [OCN]⁻, adopts a linear geometry with the carbon atom centrally bonded to oxygen and nitrogen, resulting in an O-C-N bond angle of 180°. This arrangement arises from the sp hybridization of the central carbon atom, minimizing electron repulsion in the triatomic system. Experimental bond lengths, derived from , are approximately 1.23 Å for the C-O bond and 1.19 Å for the C-N bond, reflecting partial double-bond character due to delocalization. The bonding in [OCN]⁻ is characterized by resonance among three canonical structures: [O⁻–C≡N] ↔ [O=C=N⁻] ↔ [O⁺≡C–N²⁻]. The first structure, with the negative charge on oxygen, dominates as the major contributor (approximately 61%), followed by the second (30%), while the third provides a minor contribution (4%), as determined by quantum chemical calculations and consistent with early analyses. This delocalization leads to bond orders intermediate between single/double and double/triple, stabilizing the relative to its localized forms. The [OCN]⁻ ion is a structural isomer of the fulminate ion, [CNO]⁻, which rearranges the atoms as C-N-O and exhibits significantly lower stability, often forming explosive compounds due to weaker resonance stabilization. Both cyanic acid (HOCN) and its tautomer isocyanic acid (HNCO) deprotonate to yield the same [OCN]⁻ anion, highlighting the equivalence of O- and N-bound forms through resonance. Infrared spectroscopy provides a characteristic signature for [OCN]⁻, with the asymmetric C≡N stretching mode appearing at approximately 2096 cm⁻¹ in matrix-isolated samples, indicative of the triple-bond-like character in the dominant resonance form. As an ambidentate ligand, [OCN]⁻ can coordinate to metal centers via either the oxygen or nitrogen atom, a property stemming from the asymmetric charge distribution in its resonance hybrids.

Properties

The cyanate ion (OCN⁻) appears colorless in aqueous solution due to its absorption in the ultraviolet region. It exhibits moderate stability in alkaline aqueous media, with a hydrolysis rate of approximately 0.01% per hour at neutral to basic pH, but decomposes rapidly below pH 4.5. The conjugate acid, cyanic acid (HOCN), is a weak acid with a pKa of approximately 3.5, indicating the ion's basic character in water. Chemically, the cyanate ion is reactive toward in acidic conditions, yielding and via the overall OCN⁻ + 2H₂O → NH₃ + HCO₃⁻ (which further equilibrates to CO₃²⁻ and NH₄⁺ depending on ). As an ambidentate , it can coordinate to acids through either the oxygen atom (forming cyanato linkages) or the nitrogen atom (forming isocyanato linkages), a attributable to its structures. Spectroscopically, OCN⁻ displays a characteristic UV-Vis band at approximately 298 nm in solution, corresponding to an electronic transition energy of 4.16 . In ¹³C NMR spectra, the central carbon resonates at around 120 ppm in , reflecting the ion's linear structure and partial double-bond character. Thermodynamically, the (ΔH_f°) for the gas-phase cyanate ion is -221.4 ± 0.5 kJ/mol at 298 K, underscoring its energetic stability relative to constituent atoms.

Inorganic Cyanates

Salts

Cyanate salts are ionic compounds composed of metal or cations paired with the cyanate anion (OCN⁻), which adopts a linear due to its structure. Common examples include (NaOCN), a white crystalline solid with a rhombohedral lattice ( R3m) and a of 550 °C, potassium cyanate (KOCN), which forms colorless tetragonal crystals ( I4/mcm), and (NH₄OCN), known for its isomerization to upon heating in the , a pivotal demonstration that organic compounds could be synthesized from inorganic precursors. These salts exhibit ionic structures where the linear OCN⁻ anions are arranged in ordered lattices alongside the cations, facilitating their in and characteristic behaviors. A standard laboratory preparation of cyanate salts involves heating with the corresponding metal , typically in a 2:1 molar ratio of urea to carbonate, to produce the cyanate salt and as a . For , the reaction proceeds as follows: $2 \ce{CO(NH2)2 + Na2CO3 -> 2 NaOCN + (NH4)2CO3} The ammonium carbonate subsequently decomposes to ammonia, water, and carbon dioxide upon further heating. Cyanate salts decompose thermally at high temperatures (above ~600 °C), typically yielding metal carbonates, carbon dioxide, and nitrogen. For example, sodium cyanate decomposes to sodium carbonate, CO₂, and N₂. To produce cyanides, reducing conditions are required, such as heating with carbon: \ce{2 NaOCN + C -> 2 NaCN + CO2}.

Coordination Complexes

The cyanate ion functions as an ambidentate in coordination complexes, capable of binding to metal centers via either the or oxygen . In the N-bound (isocyanato) mode, the ligand adopts a linear M–N=C=O , whereas the O-bound (cyanato) mode features a bent M–O–C≡N arrangement. The ion can also bridge two metal centers in a μ₂-N,O fashion, with the and oxygen atoms each coordinating to a different metal. These bonding modes depend on factors such as the metal's , charge, and coordination environment, as established through structural and spectroscopic analyses. Representative examples include the linear [Ag(NCO)₂]⁻ complex, where silver(I) coordinates exclusively through nitrogen atoms in a straight N–Ag–N arrangement. In contrast, [Co(NH₃)₅(OCN)]²⁺ exemplifies O-bound coordination in a classic case of linkage isomerism. Linkage isomers of cyanate are readily distinguished by infrared spectroscopy, with N-bound complexes exhibiting the asymmetric NCO stretch at approximately 2190 cm⁻¹ and O-bound at around 2090 cm⁻¹, reflecting differences in bond strengths and electronic distribution. Bridging modes occur in dinuclear species, such as certain nickel(II) complexes where μ₂-N,O-cyanate links two metals, influencing magnetic and electronic properties. The stability of these isomers varies, with N-binding often favored for soft metals and O-binding for hard ones, allowing interconversion under specific conditions like heating or . Studies of cyanate complexes advanced significantly after the , driven by and techniques that enabled precise characterization of bonding modes and isomerism.

Organic Cyanates

Functional Group

In , the cyanate is defined as -O-C≡N, present in organic cyanates with the general formula ROCN, where R is an alkyl or ; these compounds are esters derived from cyanic acid (HOCN). This features a linear arrangement of the O-C≡N atoms, with a between carbon and , and the oxygen-carbon bond exhibiting due to oxygen's higher , rendering the oxygen atom partially negative. The cyanate group must be distinguished from the structurally similar but chemically distinct group (-N=C=O), found in compounds of the form RNCO, where the is directly bonded to the residue R rather than the oxygen. cyanates relate briefly to the inorganic cyanate [OCN]⁻ by sharing the OCN , but in contexts, the group is covalently linked via oxygen to an organic framework. Representative examples of organic cyanates include ethyl cyanate (CH₃CH₂OCN), a simple alkyl derivative, and phenyl cyanate (C₆H₅OCN), an example. In nomenclature, these compounds are commonly named by prefixing the alkyl or aryl group to "cyanate," yielding names like ethyl cyanate or phenyl cyanate; systematic IUPAC naming treats them as derivatives of cyanic acid, such as "cyanic acid ethyl ester," though the substitutive name "alkoxy cyanide" is also acceptable for simple cases. Organic cyanates exhibit physical properties typical of polar, low-molecular-weight compounds, often appearing as colorless, volatile liquids that can be distilled, though they are prone to or upon storage. They are moisture-sensitive and undergo in aqueous environments to yield the corresponding (ROH) and cyanic acid (HOCN), reflecting the reversible ester-like nature of the O-C bond.

Synthesis and Reactions

Organic cyanates are synthesized in the laboratory primarily through the reaction of alcohols with in the presence of a , which proceeds according to the equation \ce{ROH + ClCN ->[base] ROCN + HCl} This allows for the preparation of simple alkyl cyanates from primary, secondary, or even bridgehead alcohols, though the latter are challenging due to steric hindrance. Key reactions of cyanates include their to form carbamates, as depicted in \ce{ROCN + NH3 -> RNH-COOR} This transformation involves of followed by alkyl group migration from oxygen to , providing a route to unsymmetrical carbamates. Cyanates also undergo cyclization with amines, particularly amino alcohols, to yield heterocycles such as oxazolidinones; for example, reaction with leads to 2-oxazolidinone derivatives via intramolecular attack and rearrangement. A prominent reaction is the thermal rearrangement of alkyl cyanates to the thermodynamically more stable , occurring above 100°C via an ion-pair or : \ce{ROCN ->[\Delta] RNCO} This is rapid for simple alkyl derivatives upon heating to , often proceeding exothermically. Organic cyanates play an intermediate role in variants of the , where photochemical decomposition of acyl azides can generate cyanates (R-OCN) as minor byproducts alongside the primary products.

Production and Applications

Industrial Methods

The primary industrial method for producing is the thermal of with , typically conducted in a continuous to achieve high yields. The balanced proceeds as follows: $2 \ce{(NH2)2CO} + \ce{Na2CO3} \rightarrow 2 \ce{NaOCN} + 2 \ce{NH3} + \ce{H2O} + \ce{CO2} This involves heating the reactants in a molar ratio of approximately 2:1 ( to ) at temperatures of 500–600°C for a short duration, often less than 4 minutes in the fused state, using nickel-lined equipment to prevent contamination. Yields reach 85–96%, resulting in a product with 85–95% purity directly from the , containing minimal (<1%) and some residual . An alternative industrial route involves the hydrolysis of with aqueous sodium hydroxide, which generates sodium cyanate alongside sodium chloride as a byproduct: \ce{ClCN + 2 NaOH -> NaOCN + NaCl + H2O} This exothermic reaction is carried out at moderate temperatures (0–50°C) in concentrated NaOH solutions (>15% by weight), often in a continuous setup where cyanate precipitates while other components remain in solution. While less common than the urea-based method due to the toxicity and handling challenges of , it offers high purity (>99%) and yields (>97%) after separation. Production of occurs on a relatively small industrial scale compared to related compounds like , with one major producer in reporting an annual capacity of 10,000 tons as of 2024. Purification typically involves recrystallization from aqueous or water-alcohol mixtures under controlled conditions to minimize to and , ensuring the final product meets technical grade specifications (≥98% purity). Ammonium cyanate, formed as an intermediate in some processes, can be thermally decomposed to but is not a primary industrial route for cyanate salts.

Uses and Toxicology

Cyanates find applications in both inorganic and organic forms across various industries. , an inorganic cyanate salt, is utilized as an intermediate in the of herbicides, where it contributes to the production of compounds effective against annual weeds in crop and fields. For instance, it plays a role in pathways involving derivatives for . Organic cyanates, particularly cyanate monomers, serve as precursors for high-performance resins used in advanced composites. These resins are valued in and for their high stability and low constant, forming tough, lightweight materials through cyclotrimerization. Curing typically occurs at temperatures around 200°C, enabling the creation of matrices for structural components that withstand elevated service conditions. In the medical field, gained attention in the 1970s as a potential therapeutic agent for sickle cell . Clinical trials demonstrated that it could carbamylate , reducing the polymerization of deoxyhemoglobin S and thereby alleviating and painful crises. However, long-term administration led to significant toxicity, including cataracts, , and reproductive effects, prompting discontinuation of its use by the late 1970s. Toxicologically, cyanates pose risks primarily through ingestion, inhalation, and contact. Sodium cyanate is harmful if swallowed, with an oral LD50 of 1,500 mg/kg in rats, indicating moderate acute toxicity. It acts as an irritant to skin and eyes, potentially causing redness, pain, and corneal damage upon exposure. In vivo, cyanate can carbamylate proteins, leading to neurological effects such as convulsions and paralysis, as well as liver alterations in animal models. While not classified as a carcinogen by major agencies, chronic exposure may contribute to hepatotoxicity and reproductive toxicity. Regulatory frameworks address cyanate-related hazards, particularly through intermediates like used in their production. The (OSHA) establishes a limit of 0.3 ppm (0.6 mg/m³) for cyanogen chloride to prevent acute respiratory and systemic effects. For cyanides (as CN), including cyanate precursors, OSHA sets a of 5 mg/m³. Environmentally, cyanates exhibit low persistence due to rapid in aqueous conditions, breaking down into and , which minimizes long-term accumulation in or .

References

  1. [1]
    Sodium Cyanate | CNNaO | CID 517096 - PubChem
    Sodium cyanate is a cyanate salt and a one-carbon compound. ChEBI. used in treatment of sickle cell anemia; RN given refers to cyanic acid, Na ...
  2. [2]
    Historical and Recent Developments in the Chemistry of Cyanate ...
    Jun 11, 2025 · In general, several different resonance forms can be formulated for all cyanate congeners, and the most important ones are depicted in the ...
  3. [3]
    Cyanate | McGraw Hill's AccessScience
    A compound containing the OCN group, typically a salt or ester of cyanic acid (HOCN). The cyanate ion is ambidentate, that is, it has two reactive sites, ...
  4. [4]
    Friedrich Wöhler - MSU Chemistry
    The formation of the known organic compound urea by heating the inorganic ammonium cyanate, about which Wöhler wrote (1828) to his mentor Berzelius (see ...Missing: synthesis | Show results with:synthesis
  5. [5]
    Historical and Recent Developments in the Chemistry of Cyanate ...
    Jun 11, 2025 · Being archetypical pseudohalogens, cyanates have a long history of element exchange reactions. Historically, the chalcogen atoms were the first ...Introduction · Results and Discussion · Conclusion and Future... · Biographies
  6. [6]
    Cyanate is a low abundance but actively cycled nitrogen compound ...
    Aug 13, 2021 · Cyanate can serve as a nitrogen and/or carbon source for different microorganisms and as an energy source for autotrophic ammonia oxidizers.
  7. [7]
    Sodium cyanate as a potential treatment for sickle-cell disease
    Sodium cyanate as a potential treatment for sickle-cell disease.
  8. [8]
    First Laboratory Detection of N13CO– and Semiexperimental ...
    Mar 14, 2022 · The cyanate anion (NCO–) is a species of considerable astrophysical relevance. It is widely believed to be embedded in interstellar ices ...
  9. [9]
    Kinetics of the OCN− and HOCN formation from the HNCO + H2O ...
    The cyanate ion OCN− is an intermediate in the isomerization process of isocyanic acid HNCO into cyanic acid HOCN in water ice. Methods.
  10. [10]
    Coordination Chemistry of the Cyanate, Thiocyanate, and ...
    Coordination Chemistry of the Cyanate, Thiocyanate, and Selenocyanate Ions ... Applications in Coordination, Organometallic, and Bioinorganic Chemistry.
  11. [11]
    Cyanate ion - Science made alive: Chemistry/Experiments
    Cyanate ion reacts with strong acids, giving mainly isocyanic acid, O=C=N-H. This tautomerizes to cyanic acid H-O-C≡N in an equilibrium reaction. Approximately ...
  12. [12]
    Some observations on cyanic acid and cyanates - ResearchGate
    Aug 6, 2025 · ... Cyanate is relatively stable in alkaline solution (hydrolysis rate of 0.01% h Ϫ1 ) but rapidly decomposes to CO 2 and NH 3 below about pH 4.5 ...
  13. [13]
    Ka Table - Acid
    Cyanic acid HOCN 3.5×10–4. Dichloroacetic acid HC2HCl2O2 5.5×10–2. Diethylammonium ion (C2H5)2NH2+ 1.4×10–11. Dimethylammonium ion (CH3)2NH2+ 1.7×10 ...
  14. [14]
    Kinetics of the Hydrolysis of Cyanic Acid - ACS Publications
    Ultrafast Protonation of Cyanate Anion in Aqueous Solution. Israel Journal of Chemistry 2009, 49 (2) , 217-225. https://doi.org/10.1560/IJC.49.2.217. William ...
  15. [15]
    Ionisation of cyanate ions in solution - ScienceDirect
    In acetonitrile solution, the N-methylpyridazinium salts possess UV/visible absorption bands at 4.16 (OCN−), 3.64 (SCN−) and 3.37 eV (SeCN−); these are assigned ...
  16. [16]
    Electrophilic C(sp2)−H Cyanation with Inorganic Cyanate (OCN ...
    Jul 1, 2024 · Furthermore, numerous functionals predicted the 13C NMR chemical shift δ(NCO) of the [P1 ⋅ NCO]+ isomer in the range 126 ppm<δ<131 ppm ...
  17. [17]
    Cyanate Enthalpy of Formation
    ### Summary of Thermodynamic Data for [NCO]- (g) (Cyanate Ion)
  18. [18]
  19. [19]
    Ethyl cyanate
    ### Summary of Cyanate Functional Group Information from PubChem (Ethyl Cyanate)
  20. [20]
    Cyanic Acid - an overview | ScienceDirect Topics
    ... alkyl cyanates. ... Since the publication of COFGT (1995), there have been few developments in the use of cyanic acid salts to prepare organic cyanates.
  21. [21]
    Phenyl cyanate
    ### Summary of Cyanate Functional Group (Focusing on Organic Cyanates ROCN)
  22. [22]
    Cyanate ester / isocyanate - LookChem
    Cyanate esters are characterized by the presence of an -OCN functional group ... Isocyanates, on the other hand, feature an -NCO functional group, where ...
  23. [23]
  24. [24]
    [PDF] ichikawa@kochi-u.ac.jp - Semantic Scholar
    In 1964, four papers describing the synthesis of aryl and alkyl cyanates were published simultaneously (Scheme 4). In one, the German chemists Grigat and ...<|control11|><|separator|>
  25. [25]
    [PDF] The Chemistry of Phosgene - Sciencemadness
    Phosgene reacts with primary alkyl and aryl amines or their salts to yield carbamoyl chlorides which can be readily dehydrohalogenated to isocyanates (eq 1).
  26. [26]
    Organic Carbamates in Drug Design and Medicinal Chemistry
    Jan 7, 2015 · Fast hydrolysis of carbamate-bearing drugs may result in weak or shortened activity. On the contrary, carbamate-based prodrugs must undergo ...
  27. [27]
    N-Boc Amines to Oxazolidinones via Pd(II)/Bis-sulfoxide/Brønsted ...
    Jul 7, 2014 · A Pd(II)/bis-sulfoxide/Brønsted acid catalyzed allylic C–H oxidation reaction for the synthesis of oxazolidinones from simple N-Boc amines is reported.Missing: cyanate | Show results with:cyanate
  28. [28]
    [PDF] Alkyl Cyanates - Acta Chemica Scandinavica
    On heating propyl, butyl, and isobutyl cyanate to boiling they isomerise to the isocyanates in an exothermal reaction (as described for ethyl cyanate ¹).Missing: thermal isomerization
  29. [29]
    [3,3]-Sigmatropic Shifts and Retro-ene Rearrangements in Cyanates ...
    A similar comparison can be made for the reactions of alkyl cyanates and isocyanates in Schemes 3 and 4. While the retro-ene reaction is favored in all cases, ...
  30. [30]
    The Curtius Rearrangement of Acyl Azides Revisited – Formation of ...
    Oct 17, 2005 · The Curtius rearrangement is a synthesis of isocyanates (R–N=C=O) by thermal or photochemical rearrangement of acyl acides and/or ...Missing: cyanates | Show results with:cyanates<|control11|><|separator|>
  31. [31]
    US2690956A - Process of making sodium cyanate - Google Patents
    The method of manufacturing sodium cyanate which comprises heating urea and a carbonate of soda admixed in the molar ratio of about 2.3 moles of urea to one ...
  32. [32]
    reaction of urea with sodium carbonate; single route, at producer
    Urea react with sodium carbonate (soda) into sodium cyanate, ammonia and CO2. The reaction takes place between 500 and 600°C.
  33. [33]
    US3803294A - Process for the production of sodium cyanate
    In the above described urea method (2) using urea and sodium carbonate as raw materials, one mole of ammonium carbonate is produced per two moles of the desired ...<|separator|>
  34. [34]
    Detoxification of Bombing Solution Wastes Containing Cyanide Ion
    Cyanogen chloride produced in reaction (2) undergoes hydrolysis in an alkaline solution to produce cyanate ion according to reaction (3). ClCN + 2OH CNO + H2 ...
  35. [35]
    Introduction for Shanghai Yiji Chemical Co., Ltd, - ChemNet
    The annual production scale is 10,000 tons of sodium cyanate and 2,000 tons ... production of sodium cyanate and octanoyl chlorid intermediates.
  36. [36]
    SU831729A1 - Method of purifying sodium cyanate from impurities
    A known method of purification of sodium cyanate by recrystallization from water-alcohol solutions with soda neutralization with acetic acid U-l.
  37. [37]
    Sodium Cyanate in Pesticide Synthesis: Creating Effective Herbicides
    Oct 20, 2025 · Sodium Cyanate (CAS 917-61-3) plays a vital role in the pesticide industry, primarily as an intermediate in the synthesis of herbicides. Its ...
  38. [38]
    Thermal and mechanical evaluation of cyanate ester composites ...
    Cyanate esters are part of a group of polymers used in structural composites called high-temperature thermosetting matrices, a group loosely classified as ...
  39. [39]
    [PDF] Preparation, Cure, and Characterization of Cyanate Ester-Epoxy ...
    Homopolymerization of cyanate ester monomers proceeds readily at high temperature (>200 °C), but catalysts are often used to reduce the cure temperature.
  40. [40]
    [PDF] Sodium cyanate - Safety Data Sheet - ChemicalBook
    Feb 22, 2025 · SECTION 11: Toxicological information. Information on toxicological effects. Acute toxicity. LD50 Oral - Rat - 1.500 mg/kg. Skin corrosion ...
  41. [41]
  42. [42]
    CYANOGEN CHLORIDE | Occupational Safety and Health ... - OSHA
    Dec 22, 2020 · Specific gravity, 1.22 (liquid at 32°F) ; Ionization potential, 12.49 eV ; Lower explosive limit (LEL), Upper explosive limit (UEL) ; NFPA health ...
  43. [43]
  44. [44]