Acetylene , symmetry

The point group is derived from by the inclusion of U , therefore, all linear molecules with a plane of symmetry perpendicular to the axis belong to D f. Acetylene... 

Although we have been able to see on inspection which vibrational fundamentals of water and acetylene are infrared active, in general this is not the case. It is also not the case for vibrational overtone and combination tone transitions. To be able to obtain selection mles for all infrared vibrational transitions in any polyatomic molecule we must resort to symmetry arguments. 

A different synthetic access to a 1 -metallacyclopropene, which can be a versatile organometallic synthon, is displayed in Scheme 33. The mono-alkyne derivatives of W(IV)-calix[4]arene are easily accessible through the thermal displacement of cyclohexene from 32 using the appropriate acetylenes. The reaction led to complexes 34 and 172-174. The proposed 3-metallacyclopropene has been confirmed from the spectroscopic and the X-ray data. The H NMR data reveal a cone conformation of the calixarene with a four-fold symmetry, for which the... 

The normal vibrations, symmetry and force constants of compounds 6 and 7 were deduced from their IR and Raman spectra, in the solid state and solution. The symmetry is Z>3d, with staggered methyl groups. The SnCCSn chain is linear, and the C=C bond longer than in ordinary acetylenic compounds114. 

Recently, we analyzed the role of electron repulsion relative to bond breaking and antiaromaticity effects on a quantitative basis using Natural Bond Orbital (NBO) analysis.24 Two other destabilizing factors were considered at the initial stage of the cyclization in addition to four-electron repulsion between the filled in-plane acetylenic re-orbitals - distortion/breaking of the acetylenic bonds as a result of their bending, and the fact that, at a distance of ca. 3 A, the in-plane re-orbitals become parallel and reach a geometry that resembles the antiaromatic TS of the symmetry forbidden [2S + 2S] cycloaddition (vide infra). 

Fig. 9 illustrates that the two acetylenic systems become nearly parallel at C1-C6 distances close to 3 A where the constructive overlap of the re-orbital with one of the re -nodes is compensated by a destructive overlap with the other rc -node (Fig. 9, bottom). From a conceptual point of view, the properties of the in-plane re-system at the 3 A threshold bear a striking resemblance to the interaction of the two re-bonds in D2h cyclobutadiene where the re-re interaction is zero and the re-re repulsion is considerable, thus accounting for the extreme instability of this antiaromatic molecule.41 Even more relevant is a comparison with the TS of the symmetry forbidden thermal [2S + 2S] cycloaddition (Fig. 10) which prompted us to call this region antiaromatic .42... 

The high shift values for NO+ (474 ppm for 170 and —3 ppm for nitrogen) relative to lower values for X—N=0 compounds is good evidence for differences in chemical shift anisotropy as pertain in 13C NMR for the alkynes relative to alkanes and alkenes64. The higher symmetry of acetylene leads to a high field shift. 

Even more than [6 + 4] and [8 + 2] cycloaddition reactions, the [2 + 2 + 2] cycloaddition reactions require a very well preorganized orientation of the three multiple bonds with respect to each other. In most cases, this kind of cycloaddition reaction is catalyzed by transition metal complexes which preorientate and activate the reacting multiple bonds111,324. The rarity of thermal [2 + 2 + 2] cycloadditions, which are symmetry allowed and usually strongly exothermic, is due to unfavorable entropic factors. High temperatures are required to induce a reaction, as was demonstrated by Berthelot, who described the synthesis of benzene from acetylene in 1866325, and Ullman, who described the reaction between nor-bomadiene and maleic anhydride in 1958326. As a consequence of the limiting scope of this chapter, this section only describes those reactions in which two of the participating multiple bonds are within the same molecule. 

In some cases, steric interactions can prevent unimolecular reactions. Tetrahe-drane (18) has been the subject of a number of studies, and the conclusion is that, if formed, it would rapidly decompose to form two molecules of acetylene. However, tetra-tert-butyltetrahedrane (19) is a quite stable substance, and on heating rearranges to tetra-tert-butylcyclobutadiene. An orbital symmetry " analysis of the cleavage of tetrahedrane to acetylene indicates that it involves a torsional motion that in the case of the tert-butyl substituted derivative would bring the tert-butyl groups very close to each other. As a result, this mode of reaction is not possible, and the compound is relatively stable. 

The coordination of oxygen to transition metal ions which occurs mostly in the side-on fashion on surfaces (Section III,A,2 and Appendix B) can be described following the model of acetylene-metal complexes (467). Both 7tu and 7tg orbitals of molecular oxygen have proper symmetry to interact with the bonding set of s, p, and d orbitals on the metal. The bonding orbitals are shown in Fig. 29. 

Van der Waals complexes of C2v symmetry between 1,2,4,5-tetrazine and a number of light gases (He, Ar, H2) have been observed and characterized by laser spectroscopic studies of free supersonic jet expansion of the tetrazine in the carrier gas (84CHEC-(3)53l). In these complexes, one equivalent of noble gas sits on top of the aromatic TT-system of the heterocycle. 1,2,4,5-Tetrazine, its 3-methyl, and 3,6-dimethyl derivative as well as aminotetrazine have all been used as heterocycles with noble gases, water, HC1, benzene, and acetylene, playing the role of the second partner. 

Alkynes have two v and two it orbitals that can potentially interact with metal orbitals, and in some instances, it is thought that all of these are involved at the same time in a mononuclear complex. An extended Hiickel calculation on Mofmexo-tetra-p-tolylporphyrinXHC=CH) supports this view (Fig. I5.25).8" Thus both bonding orbitals of the alkyne (6, and at) can donate electron density to molybdenum to form (he 16, and lo, MOs. and both anti bonding orbitals (b2 and a2) can accept electron density to form the lf>2 and Ui2 MOs. Notice that both it bonding orbitals (a, and bt) of acetylene interact significantly with metal d orbitals of the same symmetry. 

The a orbital has of course the occupation number 1.00, since any excitation to or from this orbital leads to configurations of the wrong symmetry. We notice especially the strong occupation of the orbital 3n which is bonding in the region between the acetylene and the cyano bond. This occupation results in an increased conjugation of the two triple bonds. 

The reactions of sydnones with acetylenic esters are generally thermally induced concerted processes which are allowed on orbital symmetry considerations.8 On the basis of Huisgen s mechanistic study,805 the conversion of 71 into 73 proceeds through the formation of 72 in a slow rate-determining step, followed by rapid loss of carbon dioxide, giving the pyrazole 73. 

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