Electronic structure alkynes

The electronic structure of benzyne, shown in Figure 16.19, is that of a highly distorted alkyne. Although a typical alkyne triple bond uses sp-hybridized carbon atoms, the benzyne triple bond uses sp2-hybridized carbons. Furthermore, a typical alkyne triple bond has two mutually perpendicular it bonds formed bv p-p overlap, but the benzyne triple bond has one tt bond formed by p-p overlap and one tt bond formed by sp2 sp2 overlap. The latter tt bond is in the plane of the ring and is very weak. 

Interaction of a carbonyl group with an electrophilic metal carbene would be expected to lead to a carbonyl ylide. In fact, such compounds have been isolated in recent years 14) the strategy comprises intramolecular generation of a carbonyl ylide whose substituent pattern guarantees efficient stabilization of the dipolar electronic structure. The highly reactive 1,3-dipolar species are usually characterized by [3 + 2] cycloaddition to alkynes and activated alkenes. Furthermore, cycloaddition to ketones and aldehydes has been reported for l-methoxy-2-benzopyrylium-4-olate 286, which was generated by Cu(acac)2-catalyzed decomposition of o-methoxycarbonyl-m-diazoacetophenone 285 2681... 

Alkynes (acetylenesl are like alkenes in that their electronic structure can be described fairly simply in terms of only o and n bonding and anti-bonding orbitals, but they are different in that the vertical (jt.ji )... 

A theoretical approach addresses the question of alkynes bonded to PtL2 fragments in both parallel and perpendicular geometries. With each mode of alkyne coordination there is required a different coordination geometry at platinum. The authors use the isolobal analogy to calculate the electronic structures of complexes, and propose several unknown complexes to be stable.842... 

Numerous structures containing the thiocarbonyl ylide dipole are conceivable. Incorporation of the thiocarbonyl ylide dipole into a bicyclic heterocyclic system is possible by the conversion of the cyclic thione (203) into the ring-fused mesoionic system (204). The thiocarbonyl ylide dipole (205) undergoes cycloaddition with both alkenic and alkynic electron-poor dipolarophiles in refluxing benzene or xylene so that, after extrusion of hydrogen sulfide or sulfur, respectively, from the initial 1 1 cycloadducts (206) and (207), a ring-fused pyridinone is formed. The method has been used for the annelation of pyridinones to the imidazole, 1,2,4-triazole, thiazole and 1,3,4-thiadiazole systems... 

Introduction 392 9-2 Nomenclature of Alkynes 393 9-3 Physical Properties of Alkynes 394 9-4 Commercial Importance of Alkynes 395 9-5 Electronic Structure of Alkynes 396 9-6 Acidity of Alkynes Formation of Acetylide Ions 397 9-7 Synthesis of Alkynes from Acetylides 399 9-8 Synthesis of Alkynes by Elimination Reactions 403 Summary Syntheses of Alkynes 404 9-9 Addition Reactions of Alkynes 405... 

Benzyne has the electronic structure of a distorted alkyne and has one very weak n bond. 

The electronic structure of alkynes is related to that of alkenes, and the photochemistry of the two classes of compound reflects this similarity. Because the photochemistry of alkenes has received greater attention and has already been described in systematic form - it is not unexpected that the present account should point out the ways in which alkyne photochemistry parallels, or is markedly different from, that of alkenes. There is a considerable difference, however, in the range of compounds which has been studied in each class. Reports of photochemical reactions of alkynes very often refer to mono- or disubstituted acetylenes in which the substituents are alkyl, aryl or alkoxycarbonyl. There have been studies on diyne and enyne systems, but as yet there has emerged nothing in alkyne chemistry to match the wealth of photochemistry reported for dienes and polyenes. This reflects in part the greater tendency of the compounds containing the C=C bond to undergo photopolymerization rather than any other reaction on irradiation. Within this limitation there is a wide variety of reactions open to the excited states of alkynes, and quite a number of the processes have synthetic application or potential. 

All these observations can be accounted for by considering the electronic structure of a carbene. Carbenes have 2-coordinate carbon atoms you might therefore expect them to have a linear (diagonal) structure—like that of an alkyne—with an sp hybridized carbon atom. 

In this section we report our experimental findings relatively to three different reactions of CN radicals with simple alkynes, namely acetylene, methyl-acetylene and dimethyl-acetylene. We have selected these reactive systems for different reasons the reactions with C2H2 is the prototype for the class of reactions CN +- alkynes/polyynes, thus is expected to reveal key concepts for reactions with the higher members of the same series the reactions with methylacetylene and dimethylacetylene were selected to observe the effect of the H substitution with one or two alkyl groups. In all cases, the experimental results are discussed in the light of the ab initio electronic structure calculations for the stationary points of the relevant potential energy surfaces. 

Conjugation of the alkyne units into the porphyrin or phthalocyanine backbone electronic structure leads to absorptivity enhancements and large red-shifts in their electronic spectra that have been sought for nonlinear optics, dyes, photonic materials, and photodynamic therapy types of applications. 

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