Sp2-bonded carbon

Amorphous carbon films may be broadly classified as (i) amorphous carbon films, a-C films, deposited from carbon-containing gases with low or zero hydrogen content [72] and (ii) hydrogenated carbon films, a-C H films, formed from hydrocarbon-containing gases [73,74]. Both types of film contain different amounts of sp2 and sp3 bonded carbon. The amount of sp2 bonded carbon can be estimated from X-ray absorption near edge spectroscopy,... 

P. Ruffieux et al., Hydrogen adsorption on sp2-bonded carbon Influence of the local curvature. Phys. Rev. B 66, 245416 (2002)... 

Single planar sheet of sp2-bonded carbon atoms corresponds to one hexagonal basal plane of graphite and is termed graphene. Recently, a successful attempt to isolate such a graphene layer has been reported [3], and apparently, it becomes possible to produce... 

For an sp2 -bonded carbon, as for example, the carbonyl carbon in acetaldehyde, 42, another kind of prochirality exists, termed sp2 prochirality. 

The synthesis of molecular carbon structures in the form of C q and other fullerenes stimulated an intense interest in mesoscopic carbon structures. In this respect, the discovery of carbon nanotubes (CNTs) [1] in the deposit of an arc discharge was a major break through. In the early days, many theoretical efforts have focused on the electronic properties of these novel quasi-one-dimensional structures [2-5]. Like graphite, these mesoscopic systems are essentially sp2 bonded. However, the curvature and the cylindrical symmetry cause important modifications compared with planar graphite. 

When two sp2-hybridized carbons approach each other, they form a cr bond by sp2-sp2 head-on overlap. At the same time, the unhybridized p orbitals approach with the correct geometry for sideways overlap, leading to the formation of what is called a pi (ir) bond. The combination of an >p2-sp2 a bond and a 2p-2p 77 bond results iii the sharing of four electrons and the formation of a carbon-carbon double bond (Figure 1.14). Note that the electrons in then-bond occupy the region centered between nuclei, while the electrons in the 77 bond occupy regions on either side of a line drawn between nuclei. 

A second factor that contributes to alkene stability involves bond strengths. A bond between an sp2 carbon and an sp3 carbon is somewhat stronger than a bond between two sp3 carbons. Thus, in comparing 1-butene and 2-butene, the monosubstituted isomer has one sp -.sp3 bond and one sp3-sp2 bond, while... 

Pyrrole (two r s, one /) and imidazole are /ive-membered heterocycles, yet both have six tt electrons and are aromatic. In pyrrole, each of the four. sp2-hybridized carbons contributes one tt electron, and the sp2-hybridized nitrogen atom contributes the two from its lone pair, which occupies a p orbital (Figure 15.9). Imidazole, also shown in Figure 15.9, is an analog of pyrrole that has two nitrogen atoms in a five-membered, unsaturated ring. Both nitrogens are sp2-hybridized, but one is in a double bond and contributes only one electron to the aromatic tt system, while the other is not in a double bond and contributes two from its lone pair. 

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. 

A conjugated polyene, as we saw in Section 14.1, is one with alternating double and single bonds. According to molecular orbital (MO) theory, the p orbitals on the sp2-hybridized carbons of a conjugated polyene interact to form a set of... 

The CH3 carbon is sp3 the double-bond carbons are sp2 the C=C—C and C=C-H bond angles are approximately 120° other bond angles are near 109°,... 

Graphite, the most important component of the lead of pencils, is a black, lustrous, electrically conducting solid that vaporizes at 1700°C. It consists of flat sheets of sp2 hybridized carbon atoms bonded covalently into hexagons like chicken wire (Fig. 5.22). There are also weak bonds between the sheets. In the commercially available forms of graphite, there are many impurity atoms trapped between the sheets these atoms weaken the already weak intersheet bonds and let... 

Although no 73Ge NMR spectra of stable doubly bonded germanium compounds have been recorded, NMR chemical shift data for the heteroatom of the double bond are available these are listed in Table II. The chemical shift of the, sp2-hybridized carbon atom of dimesitylneopentylger-mene (entry 1, Table II), without any polar substituents, falls at 8 124.2.26 The chemical shifts of the boron-substituted sp2-hybridized carbon atoms of two stable germenes (entry 2, Table II) fall in the upfield region of the... 

The rule in carbon-13 NMR is that sp2-hybridized carbons (carbonyl, aromatic, olefinic) absorb at lowest field, followed by sp-hybridized (acetylenic, nitrile) and sp3 (aliphatic). A first glance leads us to believe we have seven signals, but we must remember that the methine carbon is directly bonded to phosphorus, so that we shall expect a relatively large C-P coupling. The other C-P couplings will probably be very much smaller. 

The change is also pronounced with C=0, for not only is the nitrogen atom, with its electron pair, bonded to an electron-withdrawing group through an sp2 hybridised carbon atom (c/ p. 59), but an electron-withdrawing mesomeric effect can also operate ... 

The exact reverse of the above is seen with aniline (13), which is a very weak base (pKa = 4-62) compared with ammonia (pKa = 9-25) or cyclohexylamine (pKa = 10-68). In aniline the nitrogen atom is again bonded to an sp2 hybridised carbon atom but, more significantly, the unshared electron pair on nitrogen can interact with the delocalised 7r orbitals of the nucleus ... 

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