Ethyne structure

COT is prepared by the polymerization of ethyne at moderate temperature and pressure in the presence of nickel salts. The molecule is non-planar and behaves as a typical cyclic olefin, having no aromatic properties. It may be catalytically hydrogenated to cyclo-octene, but with Zn and dil. sulphuric acid gives 1,3,6-cyclooclairiene. It reacts with maleic anhydride to give an adduct, m.p. 166 C, derived from the isomeric structure bicyclo-4,2,0-octa-2,4,7-triene(I) ... 

A single shared pair of electrons is called a single bond. Two electron pairs shared between two atoms constitute a double bond, and three shared electron pairs constitute a triple bond. A double bond, such as C 0, is written C=0 in a Lewis structure. Similarly, a triple bond, such as C C, is written G C. Double and triple bonds are collectively called multiple bonds. The bond order is the number of bonds that link a specific pair of atoms. The bond order in H, is 1 in the group C=0, it is 2 and, for O C in a molecule such as ethyne, C2H2, the bond order is 3. 

Self-Test 3.7B Suggest a structure in terms of hybrid orbitals for each carbon atom in ethyne, C2H2. 

Now consider the alkynes, hydrocarbons with carbon-carbon triple bonds. The Lewis structure of the linear molecule ethyne (acetylene) is H—O C- H. To describe the bonding in a linear molecule, we need a hybridization scheme that produces two equivalent orbitals at 180° from each other this is sp hybridization. Each C atom has one electron in each of its two sp hybrid orbitals and one electron in each of its two perpendicular unhybridized 2p-orbitals (43). The electrons in the sp hybrid orbitals on the two carbon atoms pair and form a carbon—carbon tr-bond. The electrons in the remaining sp hybrid orbitals pair with hydrogen Ls-elec-trons to form two carbon—hydrogen o-bonds. The electrons in the two perpendicular sets of 2/z-orbitals pair with a side-by-side overlap, forming two ir-honds at 90° to each other. As in the N2 molecule, the electron density in the o-bonds forms a cylinder about the C—C bond axis. The resulting bonding pattern is shown in Fig. 3.23. 

Acetylene (ethyne), C2H2, can be polymerized, (a) Draw the Lewis structure for acetylene and draw a Lewis structure for the polymer that results when acetylene is polymerized. The polymer has formula (CH), where n is large, (b) Consider the polymers polyacetylene and polyethylene. The latter has the formula (CH2)W and is an insulating material (plastic wrap is made of polyethylene), whereas polyacetylene is a darkly colored material that can conduct electricity when properly treated. On the basis of your answer to part (a), suggest an explanation for the difference in the two polymers. 

Jeong, H. Y., Han, Y., Comment on A Computational Study of the Structures of Van der Waals and Hydrogen Bonded Complexes of Ethene and Ethyne Chem. Phys. Lett., 263, 345. 

The zinc chloride complex of l-(2-pyridyl)-2-(2-thienyl)ethyne has been structurally characterized by single crystal X-ray diffraction showing the ligand is a monodentate nitrogen donor. The N2Q2 tetrahedral coordination geometry reveals little apparent influence of the acetylene or thiophene groups.110... 

Figure 1.12 Structures of ethene and ethyne, based on the tetrahedral arrangement of four electron pairs around each carbon atom.

Bond paths are observed between bonded atoms in a molecule and only between these atoms. They are usually consistent with the bonds as defined by the Lewis structure and by experiment. There are, however, differences. There is only a single bond path between atoms that are multiply bonded in a Lewis structure because the electron density is always a maximum along the internuclear axis even in a Lewis multiple bond. The value of pb does, however, increase with increasing Lewis bond order, as is shown by the values for ethane (0.249 au), ethene (0.356 au), and ethyne (0.427 au), which indicate, as expected, an increasing amount of electron density in the bonding region. 

Figure 1.29 (a) The structure of ethyne (acetylene) showing the sigma bond... 

The same arsenal of preparative methods has been applied successfully for the corresponding dinuclear derivatives of ethyne HC CH and dialkynes HC C-X-C CH, where X can be virtually any spacer unit.50-52,54 55 57 61 62 71 76-83 As mentioned in the introduction to this chapter, ethyne is readily converted into polymeric explosive AuC=CAu and its complexes (L)AuC=CAu(L), of which the families with L = R3P84 and L = RNC are particularly large (Chapter 7). With the unit X in (L)AuC=CXC=CAu(L) being an alkylidene spacer, flexible complexes are obtained, while with alkenylidene, alkynylidene, or arylidene units,57 rigid molecules (L)AuC=CXC=GA11(L) are generated. Specific examples are presented below in the context with the structural patterns of extended systems. 

Microwave-induced, catalytic gas-phase reactions have primary been pursued by Wan [63, 64], Wan et al. [65] have used pulsed-microwave radiation (millisecond high-energy pulses) to study the reaction of methane in the absence of oxygen. The reaction was performed by use of a series of nickel catalysts. The structure of the products seemed to be function of both the catalyst and the power and frequency of microwave pulses. A Ni/Si02 catalyst has been reported to produce 93% ethyne, whereas under the same irradiation conditions a Ni powder catalyst produced 83% ethene and 8.5 % ethane, but no ethyne. 

Despite the undeniable synthetic value of the benzannulation reaction of aryl and alkenyl Fischer carbene complexes, the details of its mechanism at the molecular level remain to be ascertained. Indeed, although a relatively large number of theoretical studies have been directed to the study of the molecular and electronic structure of Fischer carbene complexes [22], few studies have been devoted to the analysis of the reaction mechanisms of processes involving this kind of complexes [23-30]. The aim of this work is to present a summary of our theoretical research on the reaction mechanism of the Dotz reaction between ethyne and vinyl-substituted hydroxycarbene species to yield p-hydroxyphenol. 

Most carbon-containing molecules are three-dimensional. In methane, the bonds of C make equal angles of 109.5° with each other, and each of the four H s is at a vertex of a regular tetrahedron whose center is occupied by the C atom. The spatial relationship is indicated as in Fig. l-2(a) (Newman projeetion) or in Fig. l-2(ft) ( wedge projection). Except for ethene, which is planar, and ethyne, which is linear, the structures in Fig. 1-1 are all three-dimensional. 

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 (CsC). The name prefixes are exactly the same as for the alkanes with the same number of carbons, but the endings are -one for compounds widr double bonds and their derivatives and -yne for compounds with triple bonds and their derivatives. Ethene (ethylene) and propene (propylene) are alkenes. Ethyne (acetylene) is an alkyne. 

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