Copper(I) cyanide

Copper(I) cyanide is an inorganic compound with the formula CuCN. This off-white solid occurs in two polymorphs; impure samples can be green due to the presence of Cu(II) impurities. The compound is useful as a catalyst, in electroplating copper, and as a reagent in the preparation of nitriles.[4]

Copper(I) cyanide
Names
IUPAC name
Copper(I) cyanide
Other names
Cuprous cyanide, copper cyanide, cupricin
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.008.076
EC Number
  • 208-883-6
RTECS number
  • GL7150000
UNII
UN number 1587
  • InChI=1S/CN.Cu/c1-2;/q-1;+1 checkY
    Key: DOBRDRYODQBAMW-UHFFFAOYSA-N checkY
  • InChI=1/CN.Cu/c1-2;/q-1;+1
    Key: DOBRDRYODQBAMW-UHFFFAOYAI
  • [Cu+].[C-]#N
Properties
CuCN
Molar mass 89.563 g/mol
Appearance off-white / pale yellow powder
Density 2.92 g/cm3[1]
Melting point 474 °C (885 °F; 747 K)
negligible
3.47×10−20[2]
Solubility insoluble in ethanol, cold dilute acids;
soluble in NH3, KCN
Structure
monoclinic
Hazards
GHS labelling:
GHS06: ToxicGHS09: Environmental hazard
Danger
H300, H310, H330, H410
P260, P262, P264, P270, P271, P273, P280, P284, P301+P310, P302+P350, P304+P340, P310, P320, P321, P322, P330, P361, P363, P391, P403+P233, P405, P501
NFPA 704 (fire diamond)
NFPA 704 four-colored diamond
4
0
0
Flash point Non-flammable
NIOSH (US health exposure limits):
PEL (Permissible)
 TWA 1 mg/m3 (as Cu)[3]
REL (Recommended)
 TWA 1 mg/m3 (as Cu)[3]
IDLH (Immediate danger)
 TWA 100 mg/m3 (as Cu)[3]
Safety data sheet (SDS) Oxford MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)
Infobox references

Structure

Copper cyanide is a coordination polymer. It exists in two polymorphs both of which contain -[Cu-CN]- chains made from linear copper(I) centres linked by cyanide bridges. In the high-temperature polymorph, HT-CuCN, which is isostructural with AgCN, the linear chains pack on a hexagonal lattice and adjacent chains are off set by +/- 1/3 c, Figure 1.[5] In the low-temperature polymorph, LT-CuCN, the chains deviate from linearity and pack into rippled layers which pack in an AB fashion with chains in adjacent layers rotated by 49 °, Figure 2.[6]

  • Figure 1: The structure of HT-CuCN showing the chains running along the c axis. Key: copper = orange and cyan = head-to-tail disordered cyanide groups.
    Figure 1: The structure of HT-CuCN showing the chains running along the c axis. Key: copper = orange and cyan = head-to-tail disordered cyanide groups.
  • Figure 2: The structure of LT-CuCN showing sheets of chains stacking in an ABAB fashion. Key: copper = orange and cyan = head-to-tail disordered cyanide groups.
    Figure 2: The structure of LT-CuCN showing sheets of chains stacking in an ABAB fashion. Key: copper = orange and cyan = head-to-tail disordered cyanide groups.

LT-CuCN can be converted to HT-CuCN by heating to 563 K in an inert atmosphere. In both polymorphs the copper to carbon and copper to nitrogen bond lengths are ~1.85 Å and bridging cyanide groups show head-to-tail disorder.[7]

Preparation

Cuprous cyanide is commercially available and is supplied as the low-temperature polymorph. It can be prepared by the reduction of copper(II) sulfate with sodium bisulfite at 60 °C, followed by the addition of sodium cyanide to precipitate pure LT-CuCN as a pale yellow powder.[8]

2 CuSO4 + NaHSO3 + H2O + 2 NaCN → 2 CuCN + 3 NaHSO4

On addition of sodium bisulfite the copper sulfate solution turns from blue to green, at which point the sodium cyanide is added. The reaction is performed under mildly acidic conditions. Copper cyanide has historically been prepared by treating copper(II) sulfate with sodium cyanide, in this redox reaction, copper(I) cyanide forms together with cyanogen:[9]

2 CuSO4 + 4 NaCN → 2 CuCN + (CN)2 + 2 Na2SO4

Because this synthetic route produces cyanogen, uses two equivalents of sodium cyanide per equivalent of CuCN made and the resulting copper cyanide is impure it is not the industrial production method. The similarity of this reaction to that between copper sulfate and sodium iodide to form copper(I) iodide is one example of cyanide ions acting as a pseudohalide. It also explains why copper(II) cyanide, Cu(CN)2, has not been synthesised.

Reactions

Copper cyanide is insoluble in water but rapidly dissolves in solutions containing CN− to form [Cu(CN)3]2− and [Cu(CN)4]3−, which exhibit trigonal planar and tetrahedral coordination geometry, respectively. These complexes contrast with those of silver and gold cyanides, which form [M(CN)2]− ions in solution.[10] The coordination polymer KCu(CN)2 contains [Cu(CN)2]− units, which link together forming helical anionic chains.[11]

Copper cyanide is also soluble in concentrated aqueous ammonia, pyridine and N-methylpyrrolidone.

Applications

Cuprous cyanide is used for electroplating copper.[4]

Organic synthesis

CuCN is a prominent reagent in organocopper chemistry. It reacts with organolithium reagents to form "mixed cuprates" with the formulas Li[RCuCN] and Li2[R2CuCN]. The use of CuCN revolutionized the deployment of simpler organocopper reagents of the type CuR and LiCuR2, the so-called Gilman reagents. In the presence of cyanide, these mixed cuprates are more readily purified and more stable.

The mixed cuprates Li[RCuCN] and Li2[R2CuCN] function as sources of the carbanions R−, but with diminished reactivity compared to the parent organolithium reagent. Thus they are useful for conjugate additions and some displacement reactions.

CuCN also forms silyl and stannyl reagents, which are used as sources of R3Si− and R3Sn−.[12]

CuCN is used in the conversion of aryl halides to nitriles in the Rosenmund–von Braun reaction.[13]

CuCN has also been introduced as a mild electrophilic source of nitrile under oxidative conditions, for instance secondary amines[14] as well as sulfides and disulfides[15] have been efficiently cyanated using this methodology. This last methodology has been then introduced in a domino 3 component reaction, leading to 2-aminobenthiazoles.[16]

References
  1. Lide, David R., ed. (2006). CRC Handbook of Chemistry and Physics (87th ed.). Boca Raton, FL: CRC Press. ISBN 0-8493-0487-3.
  2. John Rumble (June 18, 2018). CRC Handbook of Chemistry and Physics (99 ed.). CRC Press. pp. 5–188. ISBN 978-1138561632.
  3. NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
  4. H. Wayne Richardson "Copper Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. doi:10.1002/14356007.a07_567
  5. S. J. Hibble; S. M. Cheyne; A. C. Hannon; S. G. Eversfield (2002). "CuCN: A Polymorphic Matirial. Structure of One Form from Total Neutron Diffraction". Inorg. Chem. 41 (20): 8040–8048. doi:10.1021/ic0257569. PMID 12354028.
  6. S. J. Hibble; S. G. Eversfield; A. R. Cowley; A. M. Chippindale (2004). "Copper(I) Cyanide: A Simple Compound with a complicated Structure and Surprising Room-Temperature Reactivity". Angew. Chem. Int. Ed. 43 (5): 628–630. doi:10.1002/anie.200352844. PMID 14743423.
  7. S. Kroeker; R. E. Wasylishen; J. V. Hanna (1999). "The Structure of Solid Copper(I) Cyanide: A Multinuclear Magnetic and Quadrupole Resonance Study". Journal of the American Chemical Society. 121 (7): 1582–1590. doi:10.1021/ja983253p.
  8. H. J. Barber (1943). "Cuprous Cyanide: A Note on its Preparation and Use". J. Chem. Soc.: 79. doi:10.1039/JR9430000079.
  9. J. V. Supniewski and P. L. Salzberg (1941). "Allyl Cyanide". Organic Syntheses.; Collective Volume, vol. 1, p. 46
  10. Sharpe, A. G. (1976). The Chemistry of Cyano Complexes of the Transition Metals. Academic Press. p. 265. ISBN 0-12-638450-9.
  11. Housecroft, Catherine E.; Sharpe, Alan G. (2008) Inorganic Chemistry (3rd ed.), Pearson: Prentice Hall. ISBN 978-0-13-175553-6.
  12. Dieter, R. K. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH: Mörlenback, Germany, 2002; Chapter 3.
  13. Steven H. Bertz, Edward H. Fairchild, Karl Dieter, "Copper(I) Cyanide" in Encyclopedia of Reagents for Organic Synthesis 2005, John Wiley & Sons. doi:10.1002/047084289X.rc224.pub2
  14. Teng, Fan; Yu, Jin-Tao; Jiang, Yan; Yang, Haitao; Cheng, Jiang (2014). "A copper-mediated oxidative N-cyanation reaction". Chemical Communications. 50 (61): 8412–8415. doi:10.1039/c4cc03439b. ISSN 1364-548X. PMID 24948488.
  15. Castanheiro, Thomas; Gulea, Mihaela; Donnard, Morgan; Suffert, Jean (2014). "Practical Access to Aromatic Thiocyanates by CuCN-Mediated Direct Aerobic Oxidative Cyanation of Thiophenols and Diaryl Disulfides". European Journal of Organic Chemistry. 2014 (35): 7814–7817. doi:10.1002/ejoc.201403279. ISSN 1099-0690. S2CID 98786803.
  16. Castanheiro, Thomas; Suffert, Jean; Gulea, Mihaela; Donnard, Morgan (2016). "Aerobic Copper-Mediated Domino Three-Component Approach to 2-Aminobenzothiazole Derivatives". Organic Letters. 18 (11): 2588–2591. doi:10.1021/acs.orglett.6b00967. ISSN 1523-7060. PMID 27192105.
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