Bonding alkenes and alkynes

In contrast to alkanes, which have only single bonds, alkenes and alkynes have multiple bonds Alkenes are hydrocarbons that contain a carbon-carbon double bond, and alkynes are hydrocarbons that contain a carbon-carbon triple bond. Both groups of compounds are unsaturated, meaning that they have fewer hydrogens per carbon than the related alkanes. Ethylene (H2C = CH2), for example, has the formula C2H4, whereas ethane (CH3CH3) has the formula C2H6. 

Palladium on carbon, Pd/C Acts as a hydrogenation catalyst for reducing carbon-carbon multiple bonds. Alkenes and alkynes are reduced to yield alkanes (Sections 7.7 and 8.5). 

Cleavage of rr-bonded alkenes and alkynes from a metal complex can occur ... 

Key point. Alkenes and alkynes are unsaturated hydrocarbons, which possess a C=C double bond and a C=C triple bond, respectively. As (weak) re-bonds are more reactive than (strong) o-bonds, alkenes and alkynes are more reactive than alkanes. The electron-rich double or triple bond can act as a nucleophile, and most reactions of alkenes/ alkynes involve electrophilic addition reactions. In these reactions, the re-bond attacks an electrophile to generate a carbocation, which then reacts with a nucleophile. Overall, these reactions lead to the addition of two new substituents at the expense of the re-bond. 

Hydrocarbons are compounds containing only carbon and hydrogen. They are classified into aliphatic and aromatic hydrocarbons. Aliphatic hydrocarbons can be divided into three major groups - alkanes, alkenes, and alkynes. Alkanes come under saturated hydrocarbons, because they have carbon-carbon single bonds. Alkenes and alkynes are unsaturated hydrocarbons, since they have carbon-carbon double and triple bonds, respectively. 

There are two main classes of molecules (substrates) that can perform oxidative additions to metal centers non-electrophilic and electrophilic. Oxidative addition reactions with either class of substrates are favored by metal complexes that are more electron rich. Common non-electrophilic substrates are H2, Si-H bonds, P-H bonds, S-H bonds, B-H bonds, N-H bonds, S-S bonds, C-H bonds, alkenes, and alkynes. An important criterion for these non-electrophillic substrates is that they require a sterically accessible open coordination site on the metal (16e configuration or lower) onto which they need to pre-coordinate before initiating the oxidative addition to the metal center. For these substrates, both ligand atoms typically become cisoidally coordinated to the metal center after the oxidative addition as anionic (T-donors (subsequent ligand rearrangements, of course can occur). H2 is the most important and common for catalysis and a well-studied reaction is shown in Equation (5). 

We have seen that the carbon-carbon double and triple bonds of alkenes and alkynes are composed of strong a bonds and weaker tt bonds and that, because of their relatively weak tt bonds, alkenes and alkynes undergo electrophilic addition reactions (Sections 6.0 and 7.5). 

Although NaBH4 does not react on its own with unsaturated carbon— carbon bonds, alkenes and alkynes can now be hydroborated with NaBH4 (or LiBH4). A crown ether is needed with NaBH4, a cheaper but less soluble reagent than LiBH4. 

Alkenes are hydrocarbons containing at least one double bond between carbon atoms. Alkynes contain at least one triple bond. Because of the double or triple bond, alkenes and alkynes have fewer hydrogen atoms than the corresponding alkanes and are therefore called unsaturated hydrocarbons because they are not loaded to capacity with hydrogen. Recall that noncyclic alkenes have the formula C H2 and non-cyclic alkynes have the formula C H2 -2- The simplest alkene is ethene (C2H4), also called ethylene. 

Another feature of the Pd—C bonds is the excellent functional group tolerance. They are inert to many functional groups, except alkenes and alkynes and iodides and bromides attached to sp carbons, and not sensitive to H2O, ROH, and even RCO H. In this sense, they are very different from Grignard reagents, which react with carbonyl groups and are easily protonated. 

Aliphatic hydrocarbons include three major groups alkanes alkenes and alkynes Alkanes are hydrocarbons m which all the bonds are single bonds alkenes contain at least one carbon-carbon double bond and alkynes contain at least one carbon-carbon... 

We will return to the orbital hybridization model to discuss bonding m other aliphatic hydrocarbons—alkenes and alkynes—later m the chapter At this point how ever we 11 turn our attention to alkanes to examine them as a class m more detail... 

We conclude this introduction to hydrocarbons by describing the orbital hybridization model of bonding m ethylene and acetylene parents of the alkene and alkyne families respectively... 

The C—H bonds of hydrocarbons show little tendency to ionize and alkanes alkenes and alkynes are all very weak acids The acid dissociation constant for methane for exam pie IS too small to be measured directly but is estimated to be about 10 ° (pK 60)... 

Dia ene deductions. Olefins, acetylenes, and azo-compounds are reduced by hydrazine in the presence of an oxidizing agent. Stereochemical studies of alkene and alkyne reductions suggest that hydrazine is partially oxidized to the transient diazene [3618-05-1] (diimide, diimine) (9) and that the cis-isomer of diazene is the actual hydrogenating agent, acting by a concerted attack on the unsaturated bond ... 

Dibromoborane—dimethyl sulfide is a more convenient reagent. It reacts directly with alkenes and alkynes to give the corresponding alkyl- and alkenyldibromoboranes (120—123). Dibromoborane differentiates between alkenes and alkynes hydroborating internal alkynes preferentially to terminal double and triple bonds (123). Unlike other substituted boranes it is more reactive toward 1,1-disubstituted than monosubstituted alkenes (124). 

In the case of vinylfurans and vinylpyrroles there is the possibility of cycloaddition involving either the cyclic diene system or the diene system including the double bond. 2-Vinylfuran reacts in high yield with maleic anhydride in ether at room temperature to form the adduct involving the exocyclic double bond. Similarly, 2- and 3-vinylpyrroles react with 7T-electron-deficient alkenes and alkynes under relatively mild conditions to give the corresponding tetrahydro- and dihydro-indoles (Scheme 51) (80JOC4515). 

Reactions of alkynes with electrophiles are generally similar to those of alkenes. Because the HOMO of alkynes (acetylenes) is also of n type, it is not surprising that there IS a good deal of similarity between alkenes and alkynes in their reactivity toward electrophilic reagents. The fundamental questions about additions to alkynes include the following. How reactive are alkynes in comparison with alkenes What is the stereochemistry of additions to alkynes And what is the regiochemistry of additions to alkynes The important role of halonium ions and mercurinium ions in addition reactions of alkenes raises the question of whether similar species can be involved with alkynes, where the ring would have to include a double bond ... 

Alkenes and alkynes are similar in structure to the alkanes except the alkenes contain a carbon-to-carbon double bond (C=C) and the alkynes contain a carbon-to-carbon triple bond (C=C). The name prefixes are exactly the same as for the alkanes with the same number of carbons, but the endings are -one for compounds with double bonds and their derivatives and -yne for compounds with triple bonds... 

Intramolecular and intermolecular 1,3-dipolar cycloadditions of aziridine-2-car-boxylic esters with alkenes and alkynes have been investigated [131, 132]. Upon heating, aziridine-2-carboxylates undergo C-2-C-3 bond cleavage to form azome-... 

For reactions of A-acyliminium ions with alkenes and alkynes one has to distinguish between A-acyliminium ions locked in an s-trans conformation and those which (can) adopt an s-cis conformation. The former type reacts as a (nitrogen stabilized) carbocation with a C —C multiple bond. Although there are some exceptions, the intramolecular reaction of this type is regarded as an anti addition to the 7t-nucleophile, with (nearly) synchronous bond formation, the conformation of the transition state determining the product configuration. 

Saturated hydrocarbons have only single bonds unsaturated Ihydrocarbons have one or more multiple bonds. Alkanes are saturated hydrocarbons. Alkenes and alkynes are unsaturated hydrocarbons the former have carbon-carbon double bonds and the latter have triple bonds. 

The syntheses and spectroscopic and electrochemical characterization of the rhodium and iridium porphyrin complexes (Por)IVI(R) and (Por)M(R)(L) have been summarized in three review articles.The classical syntheses involve Rh(Por)X with RLi or RMgBr, and [Rh(Por) with RX. In addition, reactions of the rhodium and iridium dimers have led to a wide variety of rhodium a-bonded complexes. For example, Rh(OEP)]2 reacts with benzyl bromide to give benzyl rhodium complexes, and with monosubstituted alkenes and alkynes to give a-alkyl and fT-vinyl products, respectively. More recent synthetic methods are summarized below. Although the development of iridium porphyrin chemistry has lagged behind that of rhodium, there have been few surprises and reactions of [IrfPorih and lr(Por)H parallel those of the rhodium congeners quite closely.Selected structural data for rr-bonded rhodium and iridium porphyrin complexes are collected in Table VI, and several examples are shown in Fig. 7. ... 

Carbon forms a huge number of binary compounds with hydrogen. Three major categories of these compounds are alkanes, alkenes, and alkynes. An alkane has only single bonds between carbon atoms. The four simplest alkanes, which are shown in Figure 3-7. are methane, ethane, propane, and butane. An alkene, on the other hand, contains one or more double bonds between carbons, and an alkyne has one or more triple bonds between carbon atoms. Figure shows the structures of ethylene, the simplest alkene, and acetylene, the simplest alkyne. 

The metal catalysed hydroboration and diboration of alkenes and alkynes (addition of H-B and B-B bonds, respectively) gives rise to alkyl- or alkenyl-boronate or diboronate esters, which are important intermediates for further catalytic transformations, or can be converted to useful organic compounds by established stoichiometric methodologies. The iyn-diboration of alkynes catalysed by Pt phosphine complexes is well-established [58]. However, in alkene diborations, challenging problems of chemo- and stereo-selectivity control stiU need to be solved, with the most successful current systems being based on Pt, Rh and An complexes [59-61]. There have been some recent advances in the area by using NHC complexes of Ir, Pd, Pt, Cu, Ag and Au as catalysts under mild conditions, which present important advantages in terms of activity and selectivity over the established catalysts. 

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