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{{chembox |
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{{chembox |
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| verifiedrevid = 446081114 |
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| verifiedrevid = 455355523 |
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| ImageFile = Alpha-CuCN-unit-cell-CM-3D-balls.png |
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| ImageFile = Alpha-CuCN-unit-cell-CM-3D-balls.png |
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| ImageFile1 = Copper(I) cyanide A.jpg |
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| ImageSize = |
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| ImageSize = |
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| IUPACName = Copper(I) cyanide |
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| IUPACName = Copper(I) cyanide |
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| OtherNames = Cuprous cyanide, copper cyanide, cupricin |
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| OtherNames = Cuprous cyanide, copper cyanide, cupricin |
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| Section1 = {{Chembox Identifiers |
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| Section1 = {{Chembox Identifiers |
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| CASNo = 544-92-3 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| UNII_Ref = {{fdacite|correct|FDA}} |
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| UNII = 534K22856J |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| ChemSpiderID = 10543 |
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| ChemSpiderID = 10543 |
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| EINECS = 208-883-6 |
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| PubChem = 11009 |
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| RTECS = GL7150000 |
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| UNNumber = 1587 |
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| InChI = 1/CN.Cu/c1-2;/q-1;+1 |
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| InChI = 1/CN.Cu/c1-2;/q-1;+1 |
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| SMILES = .#N |
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| InChIKey = DOBRDRYODQBAMW-UHFFFAOYAI |
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| InChIKey = DOBRDRYODQBAMW-UHFFFAOYAI |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChIKey = DOBRDRYODQBAMW-UHFFFAOYSA-N |
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| StdInChIKey = DOBRDRYODQBAMW-UHFFFAOYSA-N |
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| CASNo = 544-92-3 |
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| SMILES = .#N |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| ⚫ |
| EINECS = 208-883-6 |
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| ⚫ |
| PubChem = 11009 |
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| ⚫ |
| RTECS = GL7150000 |
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}} |
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}} |
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| Section2 = {{Chembox Properties |
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| Section2 = {{Chembox Properties |
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| Formula = CuCN |
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| Formula = CuCN |
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| MolarMass = 89.563 g/mol |
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| MolarMass = 89.563 g/mol |
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| Appearance = off-white / pale yellow powder |
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| Appearance = off-white / pale yellow powder |
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| Density = 2.92 g/cm<sup>3</sup><ref>{{RubberBible87th}}</ref> |
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| Density = 2.92 g/cm<sup>3</sup><ref>{{RubberBible87th}}</ref> |
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| MeltingPtC = 474 |
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| MeltingPtC = 474 |
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| BoilingPtC = |
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| BoilingPtC = |
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| Solubility = negligible |
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| Solubility = negligible |
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| SolubleOther = insoluble in ], cold dilute ]; <br> soluble in ], ] |
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| SolubleOther = insoluble in ], cold dilute ]; <br> soluble in ], ] |
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| SolubilityProduct = 3.47{{e|−20}}<ref name="crc">{{cite book |author1=John Rumble |title=CRC Handbook of Chemistry and Physics |date=June 18, 2018 |publisher=CRC Press |isbn=978-1138561632 |pages=5–188|edition=99 |language=English}}</ref> |
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}} |
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}} |
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| Section3 = {{Chembox Hazards |
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| Section3 = {{Chembox Structure |
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| CrystalStruct = monoclinic |
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| EUIndex = 006-007-00-5 |
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}} |
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| NFPA-H = 4 |
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| Section4 = {{Chembox Hazards |
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| NFPA-R = 0 |
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| NFPA-F = 0 |
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| NFPA-H = 4 |
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| NFPA-O = |
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| NFPA-R = 0 |
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| NFPA-F = 0 |
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| RPhrases = {{R26/27/28}}, {{R32}}, {{R50/53}} |
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| NFPA-S = |
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| SPhrases = {{S1/2}}, {{S7}}, {{S28}}, {{S29}}, {{S45}}, {{S60}}, {{S61}} |
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| GHSPictograms = {{GHS06}}{{GHS09}} |
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| ExternalMSDS = |
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| GHSSignalWord = Danger |
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| EUClass = Very toxic ('''T+''')<br/>Dangerous for the environment ('''N''') |
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| HPhrases = {{H-phrases|300|310|330|410}} |
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| PPhrases = {{P-phrases|260|262|264|270|271|273|280|284|301+310|302+350|304+340|310|320|321|322|330|361|363|391|403+233|405|501}} |
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| ExternalSDS = |
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| FlashPt = Non-flammable |
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| FlashPt = Non-flammable |
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| PEL = TWA 1 mg/m<sup>3</sup> (as Cu)<ref name=PGCH>{{PGCH|0150}}</ref> |
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| REL = TWA 1 mg/m<sup>3</sup> (as Cu)<ref name=PGCH/> |
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| IDLH = TWA 100 mg/m<sup>3</sup> (as Cu)<ref name=PGCH/> |
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'''Copper(I) cyanide''' in an ] with the formula CuCN. This off-white solid occurs in two ]s; impure samples can be green due to the presence of Cu(II) impurities. The compound is useful as a ], in electroplating copper, and as a ] in the preparation of ]s.<ref name=Ullmann>H. Wayne Richardson "Copper Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. {{DOI|10.1002/14356007.a07_567}}</ref> |
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'''Copper(I) cyanide''' ('''cuprous cyanide''') is an ] with the formula CuCN. This off-white solid occurs in two ]s; impure samples can be green due to the presence of Cu(II) impurities. The compound is useful as a ], in electroplating copper, and as a ] in the preparation of ]s.<ref name=Ullmann>H. Wayne Richardson "Copper Compounds" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2005. {{doi|10.1002/14356007.a07_567}}</ref> |
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==Structure== |
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==Structure== |
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Copper cyanide is a ]. It exists in two polymorphs both of which contain -- chains made from linear copper(I) centres linked by ] ]. In the high-temperature polymorph, HT-CuCN, which is isostructural with ], the linear chains pack on a hexagonal lattice and adjacent chains are off set by +/- 1/3 ''c'', Figure 1.<ref>{{cite journal | author = S. J. Hibble, S. M. Cheyne, A. C. Hannon and S. G. Eversfield | title = CuCN: A Polymorphic Matirial. Structure of One Form from Total Neutron Diffraction | journal = ] | year = 2002 | volume = 41 | issue = 20 | pages = 8040–8048 | doi = 10.1021/ic0257569}}</ref> 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.<ref>{{cite journal | author = S. J. Hibble, S. G. Eversfield, A. R. Cowley and A. M. Chippindale | title = Copper(I) Cyanide: A Simple Compound with a complicated Structure and Surprising Room-Temperature Reactivity | journal = ] | year = 2004 | volume = 43 | issue = 5 | pages = 628–630 | doi = 10.1002/anie.200352844}}</ref> |
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Copper cyanide is a ]. It exists in two polymorphs both of which contain -- chains made from linear copper(I) centres linked by ] ]. In the high-temperature polymorph, HT-CuCN, which is isostructural with ], the linear chains pack on a hexagonal lattice and adjacent chains are off set by +/- 1/3 ''c'', Figure 1.<ref>{{cite journal |author1=S. J. Hibble |author2=S. M. Cheyne |author3=A. C. Hannon |author4=S. G. Eversfield | title = CuCN: A Polymorphic Matirial. Structure of One Form from Total Neutron Diffraction | journal = ] | year = 2002 | volume = 41 | issue = 20 | pages = 8040–8048 | doi = 10.1021/ic0257569|pmid=12354028 }}</ref> 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.<ref>{{cite journal |author1=S. J. Hibble |author2=S. G. Eversfield |author3=A. R. Cowley |author4=A. M. Chippindale | title = Copper(I) Cyanide: A Simple Compound with a complicated Structure and Surprising Room-Temperature Reactivity | journal = ] | year = 2004 | volume = 43 | issue = 5 | pages = 628–630 | doi = 10.1002/anie.200352844|pmid=14743423 }}</ref> |
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<gallery> |
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<gallery> |
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File:Structure of HT-CuCN (dissorderd CN).jpg|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. |
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File:Structure of HT-CuCN (dissorderd CN).jpg|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. |
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File:Structure of LT-CuCN (dissorderd CN).jpg|Figure 2: The structure of LT-CuCN showing sheets of chains staking in an ABAB fashion. Key copper = orange and cyan = head-to-tail disordered cyanide groups. |
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File:Structure of LT-CuCN (dissorderd CN).jpg|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. |
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</gallery> |
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</gallery> |
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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.<ref>{{cite journal | author = S. Kroeker, R. E. Wasylishen and J. V. Hanna | title = The Structure of Solid Copper(I) Cyanide: A Multinuclear Magnetic and Quadrupole Resonance Study. | journal = Journal of the American Chemical Society | year = 1999 | volume = 121 | issue = 7 | pages = 1582–1590 | doi = 10.1021/ja983253p}}</ref> |
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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.<ref>{{cite journal |author1=S. Kroeker |author2=R. E. Wasylishen |author3=J. V. Hanna | title = The Structure of Solid Copper(I) Cyanide: A Multinuclear Magnetic and Quadrupole Resonance Study. | journal = Journal of the American Chemical Society | year = 1999 | volume = 121 | issue = 7 | pages = 1582–1590 | doi = 10.1021/ja983253p}}</ref> |
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==Preparation== |
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==Preparation== |
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Cuprous cyanide is commercially available and is supplied as the low-temperature polymorph. It can be prepared by the reduction of ] with sodium bisulphite at 60 °C, followed by the addition of ] to precipitate pure LT-CuCN as a pale yellow powder.<ref>{{cite journal | author = H. J. Barber | title = Cuprous Cyanide: A Note on its Preparation and Use | journal = ] | year = 1943 | page = 79 | doi=10.1039/JR9430000079 }}</ref> |
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Cuprous cyanide is commercially available and is supplied as the low-temperature polymorph. It can be prepared by the reduction of ] with sodium bisulfite at 60 °C, followed by the addition of ] to precipitate pure LT-CuCN as a pale yellow powder.<ref>{{cite journal | author = H. J. Barber | title = Cuprous Cyanide: A Note on its Preparation and Use | journal = ] | year = 1943 | page = 79 | doi=10.1039/JR9430000079 }}</ref> |
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: 2 CuSO<sub>4</sub> + NaHSO<sub>3</sub> + H<sub>2</sub>O + 2 NaCN → 2 CuCN + 3 NaHSO<sub>4</sub> |
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: 2 CuSO<sub>4</sub> + NaHSO<sub>3</sub> + H<sub>2</sub>O + 2 NaCN → 2 CuCN + 3 NaHSO<sub>4</sub> |
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On addition of sodium bisulphite the copper sulphate 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 ] with ], in this redox reaction, copper(I) cyanide forms togther with ]:<ref>{{OrgSynth | author = J. V. Supniewski and P. L. Salzberg | title = Allyl Cyanide | collvol = 1 | collvolpages = 46 | year = 1941 | prep = CV1P0046}}</ref> |
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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 ] with ], in this redox reaction, copper(I) cyanide forms together with ]:<ref>{{OrgSynth | author = J. V. Supniewski and P. L. Salzberg | title = Allyl Cyanide | collvol = 1 | collvolpages = 46 | year = 1941 | prep = CV1P0046}}</ref> |
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: 2 CuSO<sub>4</sub> + 4 NaCN → 2 CuCN + (CN)<sub>2</sub> + 2 Na<sub>2</sub>SO<sub>4</sub> |
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: 2 CuSO<sub>4</sub> + 4 NaCN → 2 CuCN + (CN)<sub>2</sub> + 2 Na<sub>2</sub>SO<sub>4</sub> |
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Because this synthetic route produces ], 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 sulphate and sodium iodide to form copper(I) iodide is one example of cyanide ions acting as a pseudo halide. It also explains why copper(II) cyanide, Cu(CN)<sub>2</sub>, has not been synthesised. |
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Because this synthetic route produces ], 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 ]. It also explains why '''cupric cyanide''' (copper(II) cyanide, Cu(CN)<sub>2</sub>), has not been synthesised. |
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==Reactions== |
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==Reactions== |
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Copper cyanide is insoluble in water but rapidly dissolves in solutions containing CN<sup>-</sup> to form <sup>2-</sup> and <sup>3-</sup>, these ions are trigonal planar and tetrahedral respectively. This is in contrast to both silver and gold cyanides which form <sup>-</sup> ions in solution. <ref>{{cite book|last=Sharpe|first=A. G.|title=The Chemistry of Cyano Complexes of the Transition Metals|year=1976|publisher=Academic Press|isbn=0126384509|pages=265}}</ref> The coordination polymer KCu(CN)<sub>2</sub> contains <sup>-</sup> units |
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Copper cyanide is insoluble in water but rapidly dissolves in solutions containing CN<sup>−</sup> to form <sup>2−</sup> and <sup>3−</sup>, which exhibit trigonal planar and tetrahedral coordination geometry, respectively. These complexes contrast with those of silver and gold cyanides, which form <sup>−</sup> ions in solution.<ref>{{cite book|last=Sharpe|first=A. G.|title=The Chemistry of Cyano Complexes of the Transition Metals|year=1976|publisher=Academic Press|isbn=0-12-638450-9|pages=265}}</ref> The coordination polymer KCu(CN)<sub>2</sub> contains <sup>−</sup> units, which link together forming helical anionic chains.<ref name="housecroft">Housecroft, Catherine E.; Sharpe, Alan G. (2008) Inorganic Chemistry (3rd ed.), Pearson: Prentice Hall. ISBN 978-0-13-175553-6.</ref> |
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which link together forming helical anionic chains.<ref name="housecroft">Housecroft, Catherine E.; Sharpe, Alan G. (2008) Inorganic Chemistry (3rd ed.), Pearson: Prentice Hall. ISBN 978-0-13-175553-6.</ref> |
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Copper cyanide is also soluble in 0.88 aqueous ammonia, pyridine and N-methylpyrrolidone. |
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Copper cyanide is also soluble in concentrated aqueous ammonia, pyridine and N-methylpyrrolidone. |
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==Applications== |
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==Applications== |
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Cuprous cyanide is used for ].<ref name=Ullmann/> |
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Cuprous cyanide is used for electroplating copper.<ref name=Ullmann/> The compound is useful reagent in ], for example in the regioselective and stereoselective allylation and conjugate addition of N-Boc-2-lithiopyrrolidine and N-Boc-2-lithiopiperidine,<ref>{{cite journal|last=Coldham|first=Iain|coauthors=Daniele Leonori|title=Regioselective and Stereoselective Copper(I)-Promoted Allylation and Conjugate Addition of N-Boc-2-lithiopyrrolidine and N-Boc-2-lithiopiperidine|journal=The Journal of Organic Chemistry|date=May 14, 2010|year=2010|volume=75|issue=12|pmid=20469892|pages=4069–4077|doi=10.1021/jo100415x|url=http://pubs.acs.org.dblibweb.rdg.ac.uk:4000/doi/abs/10.1021/jo100415x}}</ref> or the copper cyanide catalyzed palladium coupling of α-lithio amines and aryl iodides.<ref>{{cite journal|doi=10.1016/0040-4039(95)00577-Y|last=Dieter|first=R. K.|coauthors=ShengJian Li|title=Copper Cyanide Catalyzed Palladium Coupling of α-Lithio Amines and Aryl Iodides|journal=Tetrahedron Letters|year=1995|volume=36|issue=21|pages=3613–3616}}</ref> |
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===Organic synthesis=== |
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CuCN is a prominent reagent in ]. It reacts with ]s to form "mixed cuprates" with the formulas Li and Li<sub>2</sub>. The use of CuCN revolutionized the deployment of simpler organocopper reagents of the type CuR and LiCuR<sub>2</sub>, the so-called ]s. In the presence of cyanide, these mixed cuprates are more readily purified and more stable. |
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The mixed cuprates Li and Li<sub>2</sub> function as sources of the carbanions R<sup>−</sup>, but with diminished reactivity compared to the parent organolithium reagent. Thus they are useful for conjugate additions and some displacement reactions. |
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CuCN also forms silyl and stannyl reagents, which are used as sources of R<sub>3</sub>Si<sup>−</sup> and R<sub>3</sub>Sn<sup>−</sup>.<ref>Dieter, R. K. In Modern Organocopper Chemistry; Krause, N., Ed.; Wiley-VCH: Mörlenback, Germany, 2002; Chapter 3.</ref> |
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CuCN is used in the conversion of aryl halides to nitriles in the ].<ref name="eEROS">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}}</ref> |
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CuCN has also been introduced as a mild electrophilic source of nitrile under oxidative conditions, for instance secondary amines<ref>{{Cite journal|last1=Teng|first1=Fan|last2=Yu|first2=Jin-Tao|last3=Jiang|first3=Yan|last4=Yang|first4=Haitao|last5=Cheng|first5=Jiang|date=2014|title=A copper-mediated oxidative N-cyanation reaction|url=http://xlink.rsc.org/?DOI=c4cc03439b|journal=Chemical Communications|language=en|volume=50|issue=61|pages=8412–8415|doi=10.1039/c4cc03439b|pmid=24948488|issn=1364-548X}}</ref> as well as sulfides and disulfides<ref>{{Cite journal|last1=Castanheiro|first1=Thomas|last2=Gulea|first2=Mihaela|last3=Donnard|first3=Morgan|last4=Suffert|first4=Jean|date=2014|title=Practical Access to Aromatic Thiocyanates by CuCN-Mediated Direct Aerobic Oxidative Cyanation of Thiophenols and Diaryl Disulfides|url=http://onlinelibrary.wiley.com/doi/10.1002/ejoc.201403279/abstract|journal=European Journal of Organic Chemistry|language=en|volume=2014|issue=35|pages=7814–7817|doi=10.1002/ejoc.201403279|s2cid=98786803 |issn=1099-0690}}</ref> have been efficiently cyanated using this methodology. This last methodology has been then introduced in a domino 3 component reaction, leading to 2-aminobenthiazoles.<ref>{{Cite journal|last1=Castanheiro|first1=Thomas|last2=Suffert|first2=Jean|last3=Gulea|first3=Mihaela|last4=Donnard|first4=Morgan|date=2016|title=Aerobic Copper-Mediated Domino Three-Component Approach to 2-Aminobenzothiazole Derivatives|journal=Organic Letters|volume=18|issue=11|pages=2588–2591|doi=10.1021/acs.orglett.6b00967|pmid=27192105|issn=1523-7060|doi-access=free}}</ref> |
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==References== |
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==References== |
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{{Reflist|30em}} |
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<references/> |
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==External links== |
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==External links== |
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{{Commons cat|Copper(I) cyanide}} |
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{{Commons category|Copper(I) cyanide}} |
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{{Copper compounds}} |
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