Copper forms a rich variety of compounds, usually with oxidation states +1 and +2, which are often called cuprous and cupric, respectively. [1] Copper compounds, whether organic complexes or organometallics, promote or catalyse numerous chemical and biological processes. [2]
As with other elements, the simplest compounds of copper are binary compounds, i.e. those containing only two elements, the principal examples being oxides, sulfides, and halides. Both cuprous and cupric oxides are known. Among the numerous copper sulfides, important examples include copper(I) sulfide and copper(II) sulfide.[ citation needed ]
Cuprous halides with fluorine, chlorine, bromine, and iodine are known, as are cupric halides with fluorine, chlorine, and bromine. Attempts to prepare copper(II) iodide yield only copper(I) iodide and iodine. [1]
Copper forms coordination complexes with ligands. In aqueous solution, copper(II) exists as [Cu(H
2O)
6]2+
. This complex exhibits the fastest water exchange rate (speed of water ligands attaching and detaching) for any transition metal aquo complex. Adding aqueous sodium hydroxide causes the precipitation of light blue solid copper(II) hydroxide. A simplified equation is:
Aqueous ammonia results in the same precipitate. Upon adding excess ammonia, the precipitate dissolves, forming tetraamminecopper(II):
Many other oxyanions form complexes; these include copper(II) acetate, copper(II) nitrate, and copper(II) carbonate. Copper(II) sulfate forms a blue crystalline pentahydrate, the most familiar copper compound in the laboratory. It is used in a fungicide called the Bordeaux mixture. [3]
![Ball-and-stick model of the complex [Cu(NH3)4(H2O)2] , illustrating the octahedral coordination geometry common for copper(II). Tetraamminediaquacopper(II)-3D-balls.png](http://upload.wikimedia.org/wikipedia/commons/thumb/a/a0/Tetraamminediaquacopper%28II%29-3D-balls.png/200px-Tetraamminediaquacopper%28II%29-3D-balls.png)
Polyols, compounds containing more than one alcohol functional group, generally interact with cupric salts. For example, copper salts are used to test for reducing sugars. Specifically, using Benedict's reagent and Fehling's solution the presence of the sugar is signaled by a color change from blue Cu(II) to reddish copper(I) oxide. [4] Schweizer's reagent and related complexes with ethylenediamine and other amines dissolve cellulose. [5] Amino acids such as cystine form very stable chelate complexes with copper(II). [6] [7] [8] Many wet-chemical tests for copper ions exist, one involving potassium ferrocyanide, which gives a brown precipitate with copper(II) salts.[ citation needed ]
Copper also forms complexes with halides. In Cs2CuCl4, CuCl42− exhibits a distorted (flattened) tetrahedral geometry, whereas in [Pt(NH3)4][CuCl4], it adopts a planar configuration. Green CuBr3− and violet CuBr42− are also known. [9] Monovalent copper forms luminescent CunXn clusters (where X=Br, Cl, I), exhibiting diverse optical properties. [10] [11]
Compounds that contain a carbon-copper bond are known as organocopper compounds. They are very reactive towards oxygen to form copper(I) oxide and have many uses in chemistry. They are synthesized by treating copper(I) compounds with Grignard reagents, terminal alkynes or organolithium reagents; [12] in particular, the last reaction described produces a Gilman reagent. These can undergo substitution with alkyl halides to form coupling products; as such, they are important in the field of organic synthesis. Copper(I) acetylide is highly shock-sensitive but is an intermediate in reactions such as the Cadiot-Chodkiewicz coupling [13] and the Sonogashira coupling. [14] Conjugate addition to enones [15] and carbocupration of alkynes [16] can also be achieved with organocopper compounds. Copper(I) forms a variety of weak complexes with alkenes and carbon monoxide, especially in the presence of amine ligands. [17]
Copper(III) is most often found in oxides. A simple example is potassium cuprate, KCuO2, a blue-black solid. [18] The most extensively studied copper(III) compounds are the cuprate superconductors. Yttrium barium copper oxide (YBa2Cu3O7) consists of both Cu(II) and Cu(III) centres. Like oxide, fluoride is a highly basic anion [19] and is known to stabilize metal ions in high oxidation states. Both copper(III) and even copper(IV) fluorides are known, K3CuF6 and Cs2CuF6, respectively. [1]
Some copper proteins form oxo complexes, which also feature copper(III). [20] With tetrapeptides, purple-colored copper(III) complexes are stabilized by the deprotonated amide ligands. [21]
Complexes of copper(III) are also found as intermediates in reactions of organocopper compounds. [22] For example, in the Kharasch–Sosnovsky reaction.[ citation needed ]
A Gilman reagent is a diorganocopper compound with the formula Li[CuR2], where R is an alkyl or aryl. They are colorless solids.
Cuprates are a class of compounds that contain copper (Cu) atom(s) in an anion. They can be broadly categorized into two main types:
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).
Copper(II) chloride, also known as cupric chloride, is an inorganic compound with the chemical formula CuCl2. The monoclinic yellowish-brown anhydrous form slowly absorbs moisture to form the orthorhombic blue-green dihydrate CuCl2·2H2O, with two water molecules of hydration. It is industrially produced for use as a co-catalyst in the Wacker process.
The Sandmeyer reaction is a chemical reaction used to synthesize aryl halides from aryl diazonium salts using copper salts as reagents or catalysts. It is an example of a radical-nucleophilic aromatic substitution. The Sandmeyer reaction provides a method through which one can perform unique transformations on benzene, such as halogenation, cyanation, trifluoromethylation, and hydroxylation.
The Hiyama coupling is a palladium-catalyzed cross-coupling reaction of organosilanes with organic halides used in organic chemistry to form carbon–carbon bonds. This reaction was discovered in 1988 by Tamejiro Hiyama and Yasuo Hatanaka as a method to form carbon-carbon bonds synthetically with chemo- and regioselectivity. The Hiyama coupling has been applied to the synthesis of various natural products.
The Corey–House synthesis (also called the Corey–Posner–Whitesides–House reaction and other permutations) 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 reaction or Ullmann coupling, named after Fritz Ullmann, couples two aryl or alkyl groups with the help of copper. The reaction was first reported by Ullmann and his student Bielecki in 1901. It has been later shown that palladium and nickel can also be effectively used.
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.
Diazonium compounds or diazonium salts are a group of organic compounds sharing a common functional group [R−N+≡N]X− where R can be any organic group, such as an alkyl or an aryl, and X is an inorganic or organic anion, such as a halide. The parent compound where R is hydrogen, is diazenylium.
Copper(I) iodide is an inorganic compound with the chemical formula CuI. It is also known as cuprous iodide. It is useful in a variety of applications ranging from organic synthesis to cloud seeding.
Copper(II) acetate, also referred to as cupric acetate, is the chemical compound with the formula Cu(OAc)2 where AcO− is acetate (CH
3CO−
2). The hydrated derivative, Cu2(OAc)4(H2O)2, which contains one molecule of water for each copper atom, is available commercially. Anhydrous copper(II) acetate is a dark green crystalline solid, whereas Cu2(OAc)4(H2O)2 is more bluish-green. Since ancient times, copper acetates of some form have been used as fungicides and green pigments. Today, copper acetates are used as reagents for the synthesis of various inorganic and organic compounds. Copper acetate, like all copper compounds, emits a blue-green glow in a flame.
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.
Silver is a relatively unreactive metal, although it can form several compounds. The common oxidation states of silver are (in order of commonness): +1 (the most stable state; for example, silver nitrate, AgNO3); +2 (highly oxidising; for example, silver(II) fluoride, AgF2); and even very rarely +3 (extreme oxidising; for example, potassium tetrafluoroargentate(III), KAgF4). The +3 state requires very strong oxidising agents to attain, such as fluorine or peroxodisulfate, and some silver(III) compounds react with atmospheric moisture and attack glass. Indeed, silver(III) fluoride is usually obtained by reacting silver or silver monofluoride with the strongest known oxidizing agent, krypton difluoride.
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.
Copper(I) bromide is the chemical compound with the formula CuBr. This white 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.
The Liebeskind–Srogl coupling reaction is an organic reaction forming a new carbon–carbon bond from a thioester and a boronic acid using a metal catalyst. It is a cross-coupling reaction. This reaction was invented by and named after Jiri Srogl from the Academy of Sciences, Czech Republic, and Lanny S. Liebeskind from Emory University, Atlanta, Georgia, USA. There are three generations of this reaction, with the first generation shown below. The original transformation used catalytic Pd(0), TFP = tris(2-furyl)phosphine as an additional ligand and stoichiometric CuTC = copper(I) thiophene-2-carboxylate as a co-metal catalyst. The overall reaction scheme is shown below.
Organobismuth chemistry is the chemistry of organometallic compounds containing a carbon to bismuth chemical bond. Applications are few. The main bismuth oxidation states are Bi(III) and Bi(V) as in all higher group 15 elements. The energy of a bond to carbon in this group decreases in the order P > As > Sb > Bi. The first reported use of bismuth in organic chemistry was in oxidation of alcohols by Frederick Challenger in 1934 (using Ph3Bi(OH)2). Knowledge about methylated species of bismuth in environmental and biological media is limited.
Reactions of organocopper reagents involve species containing copper-carbon bonds acting as nucleophiles in the presence of organic electrophiles. Organocopper reagents are now commonly used in organic synthesis as mild, selective nucleophiles for substitution and conjugate addition reactions.
Transition metal thiolate complexes are metal complexes containing thiolate ligands. Thiolates are ligands that can be classified as soft Lewis bases. Therefore, thiolate ligands coordinate most strongly to metals that behave as soft Lewis acids as opposed to those that behave as hard Lewis acids. Most complexes contain other ligands in addition to thiolate, but many homoleptic complexes are known with only thiolate ligands. The amino acid cysteine has a thiol functional group, consequently many cofactors in proteins and enzymes feature cysteinate-metal cofactors.
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