Copper(I) iodide

Last updated
Copper(I) iodide
Copper(I) iodide sample.jpg
Names
IUPAC name
Copper(I) iodide
Other names
Cuprous iodide, marshite
Identifiers
3D model (JSmol)
ChemSpider
ECHA InfoCard 100.028.795 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/Cu.HI/h;1H/q+1;/p-1 Yes check.svgY
    Key: LSXDOTMGLUJQCM-UHFFFAOYSA-M Yes check.svgY
  • InChI=1/Cu.HI/h;1H/q+1;/p-1
    Key: LSXDOTMGLUJQCM-REWHXWOFAV
  • [Cu]I
Properties
CuI
Molar mass 190.45 g/mol
AppearanceWhite solid
Odor odorless
Density 5.67 g/cm3 [1]
Melting point 606 °C (1,123 °F; 879 K)
Boiling point 1,290 °C (2,350 °F; 1,560 K) (decomposes)
0.000042 g/100 mL
1.27 x 10−12 [2]
Solubility soluble in ammonia and iodide solutions
insoluble in dilute acids
Vapor pressure 10 mm Hg (656 °C)
-63.0·10−6 cm3/mol
2.346
Structure
zincblende
Tetrahedral anions and cations
Hazards
GHS labelling:
GHS-pictogram-acid.svg GHS-pictogram-exclam.svg GHS-pictogram-pollu.svg
Danger
H302, H315, H319, H335, H410
P261, P273, P305+P351+P338, P501
NFPA 704 (fire diamond)
1
1
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)Sigma Aldrich [4]
Related compounds
Other anions
Other cations
silver iodide
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Copper(I) iodide is the inorganic compound with the formula CuI. It is also known as cuprous iodide. It is useful in a variety of applications ranging from organic synthesis to cloud seeding.

Contents

Copper(I) iodide is white, but samples often appear tan or even, when found in nature as rare mineral marshite, reddish brown, but such color is due to the presence of impurities. It is common for samples of iodide-containing compounds to become discolored due to the facile aerobic oxidation of the iodide anion to molecular iodine. [5] [6] [7]

Structure

Copper(I) iodide, like most binary (containing only two elements) metal halides, is an inorganic polymer. It has a rich phase diagram, meaning that it exists in several crystalline forms. It adopts a zinc blende structure below 390 °C (γ-CuI), a wurtzite structure between 390 and 440 °C (β-CuI), and a rock salt structure above 440 °C (α-CuI). The ions are tetrahedrally coordinated when in the zinc blende or the wurtzite structure, with a Cu-I distance of 2.338 Å. Copper(I) bromide and copper(I) chloride also transform from the zinc blende structure to the wurtzite structure at 405 and 435 °C, respectively. Therefore, the longer the copper – halide bond length, the lower the temperature needs to be to change the structure from the zinc blende structure to the wurtzite structure. The interatomic distances in copper(I) bromide and copper(I) chloride are 2.173 and 2.051 Å, respectively. [8] Consistent with its covalency, CuI is a p-type semiconductor. [9]

Copper(I)-iodide-unit-cell-3D-balls.png Copper(I)-iodide-(beta)-unit-cell-3D-balls.png Copper(I)-iodide-(alpha)-unit-cell-3D-balls.png
γ-CuIβ-CuIα-CuI

Preparation

Copper(I) iodide can be prepared by heating iodine and copper in concentrated hydriodic acid. [10]

In the laboratory however, copper(I) iodide is prepared by simply mixing an aqueous solution of potassium iodide and a soluble copper(II) salt such copper sulfate. [11]

Cu2+ + 2I → CuI + 0.5 I2

Reactions

Cuprous iodide, which degrades on standing, can be purified by dissolution into concentrated solution of potassium iodide followed by dilution. [5]

CuI + I CuI2

Copper(I) iodide reacts with mercury vapors to form copper tetraiodomercurate:

4 CuI + Hg → Cu2HgI4 + 2 Cu

This reaction can be used for the detection of mercury since the white (CuI) to brown (Cu2HgI4) color change is dramatic.

Copper(I) iodide is used in the synthesis of Cu(I) clusters. [12] which is polymetal complex compounds.

Copper(I) iodide dissolves in acetonitrile, yielding a diverse complexes. Upon crystallization, molecular [13] or polymeric [14] [15] compounds can be isolated. Dissolution is also observed when a solution of the appropriate complexing agent in acetone or chloroform is used. For example, thiourea and its derivatives can be used. Solids that crystallize out of those solutions are composed of hybrid inorganic chains. [16]

Uses

CuI is used as a reagent in organic synthesis. In combination with 1,2- or 1,3 diamine ligands, CuI catalyzes the conversion of aryl-, heteroaryl-, and vinyl-bromides into the corresponding iodides. NaI is the typical iodide source and dioxane is a typical solvent (see aromatic Finkelstein reaction). [17] Aryl halides are used to form carbon–carbon and carbon–heteroatom bonds in process such as the Heck, Stille, Suzuki, Sonogashira and Ullmann type coupling reactions. Aryl iodides, however, are more reactive than the corresponding aryl bromides or aryl chlorides. 2-Bromo-1-octen-3-ol and 1-nonyne are coupled when combined with dichlorobis(triphenylphosphine)palladium(II), CuI, and diethylamine to form 7-methylene-8-hexadecyn-6-ol. [18]

CuI is used in cloud seeding, [19] altering the amount or type of precipitation of a cloud, or their structure by dispersing substances into the atmosphere which increase water's ability to form droplets or crystals. CuI provides a sphere for moisture in the cloud to condense around, causing precipitation to increase and cloud density to decrease.

The structural properties of CuI allow CuI to stabilize heat in nylon in commercial and residential carpet industries, automotive engine accessories, and other markets where durability and weight are a factor.[ citation needed ]

CuI is used as a source of dietary iodine in table salt and animal feed. [19]

Related Research Articles

<span class="mw-page-title-main">Silver iodide</span> Chemical compound

Silver iodide is an inorganic compound with the formula AgI. The compound is a bright yellow solid, but samples almost always contain impurities of metallic silver that give a gray coloration. The silver contamination arises because some samples of AgI can be highly photosensitive. This property is exploited in silver-based photography. Silver iodide is also used as an antiseptic and in cloud seeding.

In organic chemistry, an aryl halide is an aromatic compound in which one or more hydrogen atoms, directly bonded to an aromatic ring are replaced by a halide. The haloarene are different from haloalkanes because they exhibit many differences in methods of preparation and properties. The most important members are the aryl chlorides, but the class of compounds is so broad that there are many derivatives and applications.

The Sonogashira reaction is a cross-coupling reaction used in organic synthesis to form carbon–carbon bonds. It employs a palladium catalyst as well as copper co-catalyst to form a carbon–carbon bond between a terminal alkyne and an aryl or vinyl halide.

<span class="mw-page-title-main">Copper(I) chloride</span> Chemical compound

Copper(I) chloride, commonly called cuprous chloride, is the lower chloride of copper, with the formula CuCl. The substance is a white solid sparingly soluble in water, but very soluble in concentrated hydrochloric acid. Impure samples appear green due to the presence of copper(II) chloride (CuCl2).

The Corey–House synthesis is an organic reaction that involves the reaction of a lithium diorganylcuprate with an organic halide or pseudohalide to form a new alkane, as well as an ill-defined organocopper species and lithium (pseudo)halide as byproducts.

The Ullmann condensation or Ullmann-type reaction is the copper-promoted conversion of aryl halides to aryl ethers, aryl thioethers, aryl nitriles, and aryl amines. These reactions are examples of cross-coupling reactions.

<span class="mw-page-title-main">Copper(I) cyanide</span> Chemical compound

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.

The Finkelstein reaction named after the German chemist Hans Finkelstein, is an SN2 reaction that involves the exchange of one halogen atom for another. It is an equilibrium reaction, but the reaction can be driven to completion by exploiting the differential solubility of halide salts, or by using a large excess of the halide salt.

<span class="mw-page-title-main">Aluminium iodide</span> Chemical compound

Aluminium iodide is a chemical compound containing aluminium and iodine. Invariably, the name refers to a compound of the composition AlI
3
, formed by the reaction of aluminium and iodine or the action of HI on Al metal. The hexahydrate is obtained from a reaction between metallic aluminum or aluminum hydroxide with hydrogen iodide or hydroiodic acid. Like the related chloride and bromide, AlI
3
is a strong Lewis acid and will absorb water from the atmosphere. It is employed as a reagent for the scission of certain kinds of C-O and N-O bonds. It cleaves aryl ethers and deoxygenates epoxides.

<span class="mw-page-title-main">Organozinc chemistry</span>

Organozinc chemistry is the study of the physical properties, synthesis, and reactions of organozinc compounds, which are organometallic compounds that contain carbon (C) to zinc (Zn) chemical bonds.

<span class="mw-page-title-main">Organocopper chemistry</span> Compound with carbon to copper bonds

Organocopper chemistry is the study of the physical properties, reactions, and synthesis of organocopper compounds, which are organometallic compounds containing a carbon to copper chemical bond. They are reagents in organic chemistry.

<span class="mw-page-title-main">Copper(I) bromide</span> Chemical compound

Copper(I) bromide is the chemical compound with the formula CuBr. This diamagnetic solid adopts a polymeric structure akin to that for zinc sulfide. The compound is widely used in the synthesis of organic compounds and as a lasing medium in copper bromide lasers.

<span class="mw-page-title-main">Group 2 organometallic chemistry</span>

Group 2 organometallic chemistry refers to the chemistry of compounds containing carbon bonded to any group 2 element. By far the most common group 2 organometallic compounds are the magnesium-containing Grignard reagents which are widely used in organic chemistry. Other organmetallic group 2 compounds are rare and are typically limited to academic interests.

<span class="mw-page-title-main">Bromopentacarbonylrhenium(I)</span> Chemical compound

Bromopentacarbonylrhenium(I) is an inorganic compound of rhenium, commonly used for the syntheses of other rhenium complexes.

Organorhenium chemistry describes the compounds with Re−C bonds. Because rhenium is a rare element, relatively few applications exist, but the area has been a rich source of concepts and a few useful catalysts.

In organometallic chemistry, metal–halogen exchange is a fundamental reaction that converts an organic halide into an organometallic product. The reaction commonly involves the use of electropositive metals and organochlorides, bromides, and iodides. Particularly well-developed is the use of metal–halogen exchange for the preparation of organolithium compounds.

Phosphide iodides or iodide phosphides are compounds containing anions composed of iodide (I) and phosphide (P3−). They can be considered as mixed anion compounds. They are in the category of pnictidehalides. Related compounds include the phosphide chlorides, arsenide iodides antimonide iodides and phosphide bromides.

<span class="mw-page-title-main">Copper compounds</span> Chemical compounds containing copper

Copper forms a rich variety of compounds, usually with oxidation states +1 and +2, which are often called cuprous and cupric, respectively. Copper compounds, whether organic complexes or organometallics, promote or catalyse numerous chemical and biological processes.

Rhenium compounds are compounds formed by the transition metal rhenium (Re). Rhenium can form in many oxidation states, and compounds are known for every oxidation state from -3 to +7 except -2, although the oxidation states +7, +6, +4, and +2 are the most common. Rhenium is most available commercially as salts of perrhenate, including sodium and ammonium perrhenates. These are white, water-soluble compounds. Tetrathioperrhenate anion [ReS4] is possible.

<span class="mw-page-title-main">Hafnium(III) iodide</span> Chemical compound

Hafnium(III) iodide is an inorganic compound of hafnium and iodine with the formula HfI3. It is a black solid.

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 (99th ed.). CRC Press. pp. 4–47. ISBN   978-1138561632.
  3. 1 2 3 NIOSH Pocket Guide to Chemical Hazards. "#0150". National Institute for Occupational Safety and Health (NIOSH).
  4. Sigma-Aldrich Co., Copper(I) iodide.
  5. 1 2 George B. Kauffman, Robert P. Pinnell (1960). "Purification of Copper(I) Iodide". Inorganic Syntheses. 6: 3. doi:10.1002/9780470132371.ch2.
  6. "Verification".
  7. "List of Minerals". 21 March 2011.
  8. Wells AF (1984). Structural Inorganic Chemistry (5th ed.). Oxford: Oxford University Press. pp. 410 and 444.
  9. Bidikoudi, Maria; Kymakis, Emmanuel (2019). "Novel approaches and scalability prospects of copper based hole transporting materials for planar perovskite solar cells". Journal of Materials Chemistry C. 7 (44): 13680–13708. doi: 10.1039/c9tc04009a .
  10. Holleman AF, Wiberg E (2001). Inorganic Chemistry. San Diego: Academic Press. ISBN   0-12-352651-5.
  11. George B. Kauffman, Lawrence W. Fang (1983). "Copper(I) Iodide". Inorganic Syntheses. 22: 101. doi:10.1002/9780470132531.ch20.
  12. Yu M, Chen L, Jiang F, Zhou K, Liu C, Sun C, Li X, Yang Y, Hong M (2017). "Cation-Induced Strategy toward an Hourglass-Shaped Cu6I7– Cluster and its Color-Tunable Luminescence". Chemistry of Materials. 29 (19): 8093–8099. doi:10.1021/acs.chemmater.7b01790.
  13. Barth ER, Golz C, Knorr M, Strohmann C (November 2015). "Crystal structure of di-μ-iodido-bis-[bis(aceto-nitrile-κN)copper(I)]". Acta Crystallographica Section E. 71 (Pt 11): m189-90. doi:10.1107/S2056989015018149. PMC   4645014 . PMID   26594527.
  14. Healy PC, Kildea JD, Skelton BW, White AH (1989). "Lewis-Base Adducts of Group 11 Metal(I) Compounds. XL. Conformational Systematics of [(N-base)1(CuX)1]∞ Orthogonal' Stair' Polymers (N-base = 'One-Dimensional Aceto-nitrile, Benzo-nitrile Ligand)". Australian Journal of Chemistry. 42 (1): 79. doi:10.1071/CH9890079. ISSN   0004-9425.
  15. Arkhireeva TM, Bulychev BM, Sizov AI, Sokolova TA, Belsky VK, Soloveichik GL (1990). "Copper(I) complexes with metal-metal (d10–d10) bond. Crystal and molecular structures of adducts of tantalocene trihydride with copper(I) iodide of composition: (η5-C5H5)2TaH[(μ2-H)Cu(μ2-I)2Cu(μ2-H)]2HTa(η5-C5H5)2, (η5-C5H4But)2TaH(μ2-H)2Cu(μ2-I)2Cu(μ2-H)2HTa(η5-C5H4But)2·CH3CN and {Cu(μ3-I)·P[N(CH3)2]3}4". Inorganica Chimica Acta. 169 (1): 109–118. doi:10.1016/S0020-1693(00)82043-5.
  16. Rosiak D, Okuniewski A, Chojnacki J (December 2018). "Copper(I) iodide ribbons coordinated with thiourea derivatives". Acta Crystallographica Section C. 74 (Pt 12): 1650–1655. doi:10.1107/S2053229618015620. PMID   30516149. S2CID   54615309.
  17. Klapars A, Buchwald SL (December 2002). "Copper-catalyzed halogen exchange in aryl halides: an aromatic Finkelstein reaction". Journal of the American Chemical Society. 124 (50): 14844–5. doi:10.1021/ja028865v. PMID   12475315.
  18. Marshall JA, Sehon CA. "Isomerization of Β-Alkynyl Allylic Alcohols to Furans Catalyzed by Silver Nitrate on Silica Gel: 2-Pentyl-3-methyl-5-heptylfuran". Organic Syntheses . 76: 263.
  19. 1 2 Zhang J, Richardson HW (June 2000). "Copper compounds". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. pp. 1–31. doi:10.1002/14356007.a07_567. ISBN   3527306730.

Further reading