Organocopper compounds in organometallic chemistry contain carbon to copper chemical bonds. Organocopper chemistry is the science of organocopper compounds describing their physical properties, synthesis and reactions ^{[1] [2] [3]}. They are reagents in organic chemistry. Image File history File links OrganocopperLogo. ... Organometallic chemistry is the study of chemical compounds containing bonds between carbon and a metal. ... General Name, Symbol, Number carbon, C, 6 Chemical series nonmetals Group, Period, Block 14, 2, p Appearance black (graphite) colorless (diamond) Atomic mass 12. ... General Name, Symbol, Number copper, Cu, 29 Chemical series transition metals Group, Period, Block 11, 4, d Appearance metallic pinkish red Atomic mass 63. ... A chemical bond is the physical phenomenon of chemical substances being held together by attraction of atoms to each other through sharing, as well as exchanging, of electrons or electrostatic forces. ... Organic chemistry is a specific discipline within the subject of chemistry. ...

Brief history

The first organocopper compound, the explosive dicopper acetylide Cu₂C₂ was synthesized by Bottger in 1859. Henry Gilman prepared methylcopper in 1936. In 1941 Kharash discovered that reaction of a Grignard reagent with cyclohexenone in presence of Cu(I) resulted in 1,4-addition instead of 1,2-addition. In 1952 Gilman investigated for the first time dialkylcuprates. An acetylide ion is an alkyne that has had a proton (hydrogen) removed from the terminal end. ... Henry Gilman was born in Boston, Massachusetts, on May 19, 1893. ... A Grignard Reagent is an alkyl- or aryl- magnesium halide. ...

Properties

Organocopper compounds are very reactive towards oxygen and water forming copper(I) oxide, tend to be thermally unstable and are generally insoluble in inert solvents. They are therefore difficult to handle and of little practical value. On the other hand organocopper reagents are used very frequently in organic chemistry as alkylating reagents prepared in situ in an inert environment with in general more functional group tolerance than corresponding Grignards or organolithium reagents. The electronegativity of copper is much higher than its next-door neighbour in the group 12 elements, zinc, suggesting less nucleophilicity for carbon. Copper(I) Oxide or Cuprous oxide (Cu2O) is an oxide of copper. ... Organic chemistry is a specific discipline within the subject of chemistry. ... In situ (in place in Latin), a term used in: biology, where it means to examine the phenomenon exactly in place where it occurs (without removing it in some special medium etc. ... In organic chemistry functional groups are specific groups of atoms within molecules, that are responsible for the characteristic chemical reactions of those molecules. ... Electronegativity is a measure of the ability of an atom or molecule to attract electrons in the context of a chemical bond. ... The Group 12 elements are: Zinc (30) Cadmium (48) Mercury (80) Ununbium (112) Color coding for these atomic numbers: At room temperature, all are solid but mercury is liquid; red indicates item is synthetic and does not occur naturally. ... General Name, Symbol, Number zinc, Zn, 30 Chemical series transition metals Group, Period, Block 12, 4, d Appearance bluish pale gray Atomic mass 65. ...

Copper belongs to the group of coinage metals together with silver and gold and their chemistries have many similarities. The oxidation state can be +1 or +2 and intermediates can have oxidation state +3. Monovalent alkylcopper compounds (R-Cu) form divalent cuprates R₂CuLi with organolithium compounds (R-Li) now known as Gilman reagents. Organocopper compounds can be stabilized with organophosphanes (R₃P). The Group 11 Elements (IB) of the periodic table consist of the traditional coinage metals of copper, silver, and gold. ... In chemistry, the oxidation state is a measure of the degree of oxidation of an atom in a chemical compound. ... The term high-temperature superconductor was initially employed to designate the new family of cuprate-perovskite ceramic materials discovered by J.G. Bednorz and K.A. Mueller in 1986. ... An organolithium compound is an organometallic compound containing a carbon-metal bond. ... A Gilman reagent is a lithium and copper (diorganocopper) reagent compound, , where R is an organic radical. ... Organophosphorus compounds are chemical compounds containing carbon phosphorus bonds. ...

The cuprates have complex aggregation states in crystalline form and in solution. Lithium dimethylcuprate is a dimer in diethyl ether forming a 8-membered ring with two lithium atoms coordinating between two methyl groups. Diethyl ether, also known as ether and ethoxyethane, is a clear, colorless, and highly flammable liquid with a low boiling point and a characteristic smell. ...

The first ever crystal structure was determined in 1972 by Lappert for CuCH₂SiMe₃. This compound is relatively stable because the bulky trimethylsilyl groups provide steric protection. It is a tetramer forming a 8-membered ring with alternating Cu-C bonds. In addition the four copper atoms form a planar Cu₄ ring based on three-center two-electron bonds. The copper to copper bond length is 242 pm compared to 256 pm in bulk copper. In pentamesitylpentacopper a 5-membered copper ring is formed and pentafluorophenylcopper is a tetramer ^[4]. Image File history File links Download high-resolution version (1058x482, 12 KB) Summary Organocopper Aggregates Licensing I, the creator of this work, hereby grant the permission to copy, distribute and/or modify this document under the terms of the GNU Free Documentation License, Version 1. ... Chemical structure of Tetramethylsilane Chemical structure of a Trimethylsilyl group The name Tetramethylsilane stands for a chemical compound whose molecular structure is essentially like a silane (SiH4) molecule with four methyl groups substituted for the four hydrogen atoms in it. ... A three-center two-electron bond is an electron deficient chemical bond where three atoms share two electrons. ... Bond length or bond distance in molecular geometry is the distance between two bonded atoms in a molecule. ... Picometre (American spelling: picometer) is an SI measure of length that is equal to 10−12 of a metre. ...

With carbon monoxide copper forms a non-classical metal carbonyl. Carbon monoxide, chemical formula CO, is a colorless, odorless, tasteless, and highly toxic gas. ...

Synthesis

• Copper halides react with organolithium reagents to the organocopper compound. Phenyl copper is prepared by reaction of phenyllithium with copper(I) bromide in diethyl ether.
• Reaction with a second equivalent of R-Li to R-Cu gives the lithium diorganocopper compound.
• Copper halides also react with Grignard reagents. The compound pentamesitylpentacopper is prepared from mesityl magnesium bromide and copper(I) chloride.
• Copper salts add to terminal alkynes to copper acetylides
• The copper metallocene (η-cyclopentadienyl triethylphosphine) copper can be prepared by reaction of copper(II) oxide with cyclopentadiene and triethylphosphine in pentane at reflux.

An organolithium reagent is an organometallic compound with a direct bond between a carbon and a lithium atom. ... An organolithium reagent is any organic compound with a direct bond between a carbon and a lithium atom. ... Copper(I) bromide (CuBr) is a chemical compound. ... Diethyl ether, also known as ether and ethoxyethane, is a clear, colorless, and highly flammable liquid with a low boiling point and a characteristic smell. ... A Grignard Reagent is an alkyl- or aryl- magnesium halide. ... In organic chemistry, mesitylene or 1,3,5-trimethylbenzene (C9H12) is an aromatic hydrocarbon with three methyl substituents attached to the benzene ring. ... Copper(I) chloride (quite commonly called cuprous chloride), is the lower chloride of copper, with the formula CuCl. ... Alkynes are hydrocarbons that have at least one triple bond between two carbon atoms. ... An acetylide ion is an alkyne that has had a proton (hydrogen) removed from the terminal end. ... In chemistry, and in particular, in organometallic chemistry, a metallocene is a compound consisting of an aromatic organic ligand bound to a metal. ... Copper(II) oxide Copper(II) oxide or cupric oxide (CuO) is the higher oxide of copper. ... Cyclopentadiene, with molecular formula C5H6, is a clear, colorless, liquid organic chemical, with an odor reminiscent of turpentine or camphor. ... Pentane (also known as amyl hydride or skellysolve) is an alkane hydrocarbon with the chemical formula CH3(CH2)3CH3. ... Diagram of typical reflux apparatus. ...

Reactions

Organocopper reactions are classified in a number of reaction types:

• Substitution reactions of cuprates R₂CuLi to alkyl halides R'-X gives the alkylcopper compound R'-Cu, the coupling product R-R and the lithium halide. The reaction mechanism is based on oxidative addition of the alkyl halide to Cu(I) elevating it to a planar Cu(III) intermediate followed by reductive elimination.

Many electrophiles will do with an approximate order of reactivity acid chlorides ^[5] > aldehydes > tosylates ~ epoxides > iodides > bromides > chlorides > ketones > esters > nitriles >> alkenes

• Oxidative coupling: coupling of copper acetylides to conjugated alkynes in the Glaser coupling, for example in the synthesis of cyclooctadecanonaene
• Reductive coupling: coupling reaction of aryl halides with copper metal in the Ullmann reaction
• Redox neutral coupling: the coupling of terminal alkynes with halo-alkynes with a copper(I) salt in the Cadiot-Chodkiewicz coupling
• Thermal coupling of organocopper compounds
• Michael additions to enones where a Grignard would react in a 1,2-addition ^[6].
• Carbocupration is a nucleophilic addition of organocopper reagents (R-Cu) to acetylene or terminal alkynes resulting in a alkenylcopper compound (RC=C-Cu) ^[7]. The presence of magnesium(I) bromide is generally required.

In a substitution reaction, a group of a particular compound is replaced by another group. ... In chemistry, an alkyl halide is an organic molecule of the form R_X, where X is a halide and R contains a carbon atom bonded to other functional groups or hydrogens. ... In chemistry, a reaction mechanism is the step by step sequence of elementary reactions by which overall chemical change occurs. ... Oxidative addition and reductive elimination are two important classes of reactions in organometallic chemistry. ... ǃǁɚɵ A generic trigonal planar molecule showing ideal bond angle. ... Oxidative addition and reductive elimination are two important classes of reactions in organometallic chemistry. ... Image File history File links Download high-resolution version (1061x207, 3 KB) Summary Organocopper Nucleophilic Substitution Licensing I, the creator of this work, hereby grant the permission to copy, distribute and/or modify this document under the terms of the GNU Free Documentation License, Version 1. ... In organic chemistry, an acid chloride (or acyl chloride) is very reactive derivative of a carboxylic acid. ... An aldehyde is either a functional group consisting of a terminal carbonyl group or a compound containing a terminal carbonyl group. ... The tosylate group with a generic R group attached (where R can be anything, typically a carbon). ... An epoxide is a cyclic ether with only three ring atoms. ... In chemistry, an alkyl halide is an organic molecule of the form R_X, where X is a halide and R contains a carbon atom bonded to other functional groups or hydrogens. ... In chemistry, an alkyl halide is an organic molecule of the form R_X, where X is a halide and R contains a carbon atom bonded to other functional groups or hydrogens. ... In chemistry, an alkyl halide is an organic molecule of the form R_X, where X is a halide and R contains a carbon atom bonded to other functional groups or hydrogens. ... Ketone group A ketone is either the functional group characterized by a carbonyl group linked to two other carbon atoms or a chemical compound that contains this functional group. ... General formula of a carboxylate ester. ... A nitrile is any organic compound which has a -C≡N functional group. ... An alkene in organic chemistry is an unsaturated hydrocarbon containing at least one carbon to carbon double bond. ... [18]annulene [18]annulene is an annulene with chemical formula C18H18. ... A coupling reaction in organic chemistry is a catch-all for a range of reactions in Organometallic chemistry where two hydrocarbon radicals are coupled with the aid of a metal containing catalyst. ... The Ullmann reaction or Ullmann coupling is a coupling reaction between aryl halides with copper 1. ... The Cadiot-Chodkiewicz coupling in organic chemistry is a coupling reaction between a terminal alkyne and a haloalkyne catalyzed by a copper(I) salt such as copper(I) bromide and an amine base [1] [2]. The reaction product is a di-acetylene or di-alkyne. ... // Definition The Michael reaction, as commonly defined, is the 1,4-addition of a stabilized carbon nucleophile to an alpha,beta-unsaturated carbonyl compound. ... An enone is an unsaturated chemical compound or functional group consisting of a conjugated system of an alkene and a ketone. ... In organic chemistry, a nucleophilic addition reaction is an addition reaction where in a chemical compound a pi bond is removed by the creation of two new covalent bonds by the addition of a nucleophile. ... Acetylene (IUPAC name: ethyne) is the simplest alkyne hydrocarbon, consisting of two hydrogen atoms and two carbon atoms connected by a triple bond. ... Alkynes are hydrocarbons that have at least one triple bond between carbon atoms. ...

See also

• Other chemistries of carbon with other Period 4 elements: organotitanium compounds, organovanadium compounds, organochromium compounds, organomanganese compounds, organoiron compounds,organocobalt compounds, organonickel compounds, organocopper compounds, organozinc compounds, organogallium compounds, organogermanium compounds, organoarsenic compounds and organoselenium compounds.

A period 4 element is one of the chemical elements in the fourth row (or period) of the periodic table of the elements. ... Organozinc compounds in organic chemistry contain carbon to zinc chemical bonds. ... Organogermanium compounds are organometallic compounds containing a carbon to germanium or hydrogen to germanium chemical bond. ... Organoselenium chemistry is the corresponding science exploring the properties and reactivity of organoselenium compounds – chemical compounds containing carbon to selenium bonds. ...

References