Carbon divalent

Carbon, like several other elements, exhibits a variable valency in its compounds. Thus it is tetravalent in the greater number of organic compounds, trivalent in triphenylmethyl, and pentaphenylethyl, etc., and divalent in carbon monoxide, fulminic acid and its derivatives, in the halogenated compounds of acetylene, etc. 

Substances containing a divalent carbon atom have in general the following properties  

Among these substances, carbon monoxide merits special attention. According to some authorities it will play a great part in future warfare. 

Several possible methods of using it are at present in the suggestion stage, but the methods suggested do not seem to have found practical application.  

The method of applying carbon monoxide which was first thought of, was in the form of the metal carbonyls—iron-pentacarbonyl and nickel tetracarbonyl—which in the presence of catalysts such as the activated carbon used in anti-gas filters evolve carbon monoxide. 

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Divalent carbon species first received attention with the work of the Swiss American chemist J U Nef in the late nineteenth century they were then largely ignored until the 1950s... 

Isomtriles are stable often naturally occumng compounds that contain a divalent carbon An example is axisonitnle 3 which can be isolated from a species of sponge and possesses anti malanal activity Write a resonance form for axisonitnle 3 that satisfies the octet rule Don t for get to include formal charges... 

Ecample Suzuki et. al. used a reaction strategy to expand the Cgo molecule, buckminsterfullerene, by adding divalent carbon equivalents. Adding phenyl diazomethane to Cgo. (I)> followed by the loss of molecular nitrogen, results in a Cgi compound. 

By analogy to additions of divalent carbon to the Cio aromatic framework, the molecule Cgi was expected to have the norcaradi-ene (II) or the cycloheptatriene (III) structure. Although an X-ray structure was not available, the UV-visible spectrum, NMR spectrum, and cyclic voltammetry supported the cycloheptatriene (III) structure. The researchers then calculated the relative molecular mechanics energies of II and III and found the cycloheptatriene structure stabilized by 31 kcal/mol with respect to the norcaradi-ene structure. Although the calculations do not confirm the structures, they provide additional supporting evidence. 

Other non-oxidative procedures have also been used to deaminate aziridines. For example, aziridines react with carbenes to yield ylides which subsequently decompose to the alkene. Dichlorocarbene and ethoxycarbonylcarbene have served as the divalent carbon source. The former gives dichioroisocyanides, e.g. (281), as by-products (72TL3827) and the latter yields imines (72TL4659). This procedure has also been applied to aziridines unsubstituted on the nitrogen atom although the decomposition step, in this case, is not totally stereospecific (72TL3827). 

The products of a eliminations are unstable divalent carbon species called carbenes. They will be discussed in Chapter 10 of Part B. In this chapter, attention will be focused on fi-elimination reactions. Some representative examples of -elimination reactions are given in Scheme 6.1. 

A rather rare perfluoroalkyl iodide addition to divalent carbon atom has been performed in the case of isocyanides under thermal or copper catalyzed conditions [14I (equation 122)... 

Section 14.13 Carbenes aie species that contain a divalent carbon that is, a caibon with only two bonds. One of the chaiacteiistic reactions of caibenes is with alkenes to give cyclopropane derivatives. 

D. Reactions of Enamines with Divalent Carbon and Related Reactions. ... 

In this review an attempt is made to discuss all the important interactions of highly reactive divalent carbon derivatives (carbenes, methylenes) and heterocyclic compounds and the accompanying molecular rearrangements. The most widely studied reactions have been those of dihalocarbenes, particularly dichlorocarbene, and the a-ketocarbenes obtained by photolytic or copper-catalyzed decomposition of diazo compounds such as diazoacetic ester or diazoacetone. The reactions of diazomethane with heterocyclic compounds have already been reviewed in this series. ... 

During the next fifty years the interest in derivatives of divalent carbon was mainly confined to methylene (CHg) and substituted methylenes obtained by decomposition of the corresponding diazo compounds this phase has been fully reviewed by Huisgen. The first convincing evidence for the formation of dichlorocarbene from chloroform was presented by Hine in 1950. Kinetic studies of the basic hydrolysis of chloroform in aqueous dioxane led to the suggestion that the rate-determining step was loss of chloride ion from the tri-chloromethyl anion which is formed in a rapid pre-equilibrium with hydroxide ions ... 

The neutral divalent carbon atom of a carbene, CX2, with its six valency electrons is electron deficient and hence electrophilic. The... 

J. Mine, Divalent Carbon. Ronald Press, New York, 1964 W. Kirmse, Carbene Chemistry. Academic Press, New York, 1964. 

Divalent carbon species called carbenes are capable of fleeting existence. For example, methylene, CH2, is the simplest carbene. The two unshared electrons in methylene can be either spin-paired in a single orbital or unpaired in different orbitals. Predict the type of hybridization you expect carbon to adopt in singlet (spin-paired) methylene and triplet (spin-unpaired) methylene. Draw a picture of each, and identify the valence orbitals on carbon. 

A great deal of evidence has shown that carbocations are planar. The divalent carbon is 5p2-hybridized, and the three substituents are oriented to the corners of an equilateral triangle, as indicated in Figure 6.9. Because there are only six valence electrons on carbon and all six are used in the three a bonds, the p orbital extending above and below the plane is unoccupied. 

Yet another kind of alkene addition is the reaction of a carbene with an alkene to yield a cyclopropane. A carbene, R2C , is a neutral molecule containing a divalent carbon with only six electrons in its valence shell. It is therefore highly reactive and is generated only as a reaction intermediate, rather than as an isolable molecule. Because they re electron-deficient, carbenes behave as electrophiles and react with nucieophiiic C=C bonds. The reaction occurs in a single step without intermediates. 

Carbene (Section 7.6) A neutral substance that contains a divalent carbon atom having only six electrons in its outer shell (R C ). 

AT-heterocyclic carbenes show a pure donor nature. Comparing them to other monodentate ligands such as phosphines and amines on several metal-carbonyl complexes showed the significantly increased donor capacity relative to phosphines, even to trialkylphosphines, while the 7r-acceptor capability of the NHCs is in the order of those of nitriles and pyridine [29]. This was used to synthesize the metathesis catalysts discussed in the next section. Experimental evidence comes from the fact that it has been shown for several metals that an exchange of phosphines versus NHCs proceeds rapidly and without the need of an excess quantity of the NHC. X-ray structures of the NHC complexes show exceptionally long metal-carbon bonds indicating a different type of bond compared to the Schrock-type carbene double bond. As a result, the reactivity of these NHC complexes is also unique. They are relatively resistant towards an attack by nucleophiles and electrophiles at the divalent carbon atom. 

The mechanism is generally regarded as involving formation of a carbene. It is the divalent carbon that has the open sextet and to which the migrating group brings its electron pair ... 

M-heterocyclic carbenes are neutral compounds with a divalent carbon atom located between the two nitrogens. The four types of stable diaminocarbenes used for the synthesis of chiral complexes are listed below (Fig. 2) ... 

The simplest diazo compound, diazomethane, undergoes loss of nitrogen in the gas or solution phase to yield a divalent carbon compound, methylene ... 

In 1963 Breslow published a synthesis of cyclopropenones, which approached formation of the three-ring without the use of divalent carbon species41-45, a, a -Dibromo ketones 36, in general readily available from ketones R-CH2—CO—CH2—R, are de-... 

An elegant method for the preparation of some cyclopropenone imines reported by Krebs118 is the (1 + 2) cycloaddition of isonitriles (as divalent carbon species) to activated triple bond of ynamines and certain cycloalkynes, e.g. ... 

The elimination of carbon monoxide, ie. the (formal) reversal of cyclopropenone formation from divalent carbon species and alkynes, takes place when cyclopropenones are heated to higher temperatures (130—250 °C) or when subjected to photolysis or electron impact191 ... 

The reaction of carbenes with alcohols can proceed by various pathways, which are most readily distinguished if the divalent carbon is conjugated to a tt system (Scheme 5). Both the ylide mechanism (a) and concerted O-H insertion (b) introduce the alkoxy group at the originally divalent site. On the other hand, carbene protonation (c) gives rise to allylic cations, which will accept nucleophiles at C-l and C-3 to give mixtures of isomeric ethers. In the case of R1 = R2, deuterated alcohols will afford mixtures of isotopomers. 

Vinylcarbenes. The use of diazoalkenes as vinylcarbene precursors is often precluded by rapid cyclization, with formation of pyrazoles. However, on photochemical generation of the diazoalkenes in situ, cyclization and nitrogen extrusion can proceed competitively. Photolysis of 1,3-diphenylpropenone to-sylhydrazone sodium salt (5) in MeOD afforded 3,5-diphenylpyrazole (9) and l,3-diphenyl-3-methoxypropene (10) in similar amounts.17 If 10 is formed by way of the 1,3-diphenylallyl cation (8), the deuterium should be distributed between C-l and C-3 of 10 (Scheme 6). The observed ratio of 10a to 10b was 66 34 the methoxy group is bound preferentially to the deuterated site, which originates from the divalent carbon of 7 (for a discussion of this effect, see below). 

Bicycloalkenylidenes. The vacant p orbitals of 5-norbomen-2-ylidene (91) and of 2-norbomen-7-ylidene (100) interact with the 7t bonds, thus enhancing the nucleophilicity of the divalent carbon.40 Protonation of these carbenes leads... 

Carbenes as divalent carbon species and their analogue carbenoids can form two bonds on a single carbon atom center introducing two different groups at one time or consecutively.1 This is due to the ambiphilic character of singlet carbenes or triplet biradical character, which can be controlled by changing the... 

Beginning as chemical curiosities, carbenes are now solidly established as reactive intermediates with fascinating and productive research areas of their own. Six decades of divalent carbon chemistry have provided us with a vast repertoire of new, unusual, and surprising reactions. Some of those reactions, once classified as exotic, have become standard methods in organic synthesis. These highly reactive carbene species have been harnessed and put to work to achieve difficult synthetic tasks other reactive intermediates cannot easily perform. 

The properties of carbenes are also expected to depend very greatly on the electronic characteristics of substituents bound to the divalent carbon. For example, many carbenes with heteroatomic elements attached directly to the central carbon are calculated to have single ground states (Mueller et al., 1981). The early, pioneering work on the stereochemistry of the reaction of carbenes with olefins was done with dibromocarbene (Skell and Garner,... 

A relatively unique type of reactive metabolite is carbene, i.e., a divalent carbon, which is a proposed intermediate in the oxidation of methylene dioxy-containing compounds. A methylenedioxy group in aromatic compounds is subject to O-dealkylation, e.g., 3,4-methylenedioxyamphetamine, as shown in Figure 8.20. The process generates formic acid and the catechol metabolite as final products. However, in the course of the reaction, a... 

In the 1890s, Nef mentioned that the functional group —NC of the isocyanides contains a divalent carbon atom C° and therefore there is a large difference between their chemistry and that of the other chemical compounds that contain only tetravalent carbon atoms Any synthesis of isocyanides corresponds to a conversion of into and all chemical reactions of isocyanides correspond to transitions of the carbon atoms C into... 

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