Carbon bonding types

The classification of amorphous carbon films according to carbon bond type and hydrogen content can be represented in a triangular diagram, Fig. 6 [e.g., 70]. The comers at the base of the triangle correspond to graphite (100% sp carbon) and diamond (100% sp carbon). The apex represents 100% H, but the upper limit for formation of solid films is defined by the tie line between the compositions of polyethene, -(CH2) -, and polyethyne, -(CH) -. 

Reactions via Insertion to the Palladium-sp2 Carbon Bond (Type I)... 

Gutman, 1. (1985) Topological properties of benzenoid systems. XLl. Carbon-carbon bond types and connectivity indices of benzenoid hydrocarbons./. Serb. Chem. Soc., 50, 451-455. 

Which of the four carbon-carbon bond types in naphthalene would you predict to be the shortest Refer to Fig. 9-33. 

Gutman I (1985) Topolo cal Properties of Benzenoid Systems — XLI — Carbon—Carbon Bond Types ana Connectivity In(hces of Benzenoid Hydrocarbons. J Serb Chem Soc 50 451... 

Since the phenyl group is linked, in both reactants and products, to a saturated carbon atom, the intervening bonds are localized and should have similar bond energies. The heats of reaction should therefore be the same in both cases. However, the central carbon atom in the transition state has sp hybridization and forms part of a delocalized allyl-like structure. The transition state in equation (5.100) is therefore stabilized both by the change in phenyl-carbon bond type (to sp -sp ) and by the conjugative interaction between phenyl and the delocalized system in the transition state. Therefore benzyl chloride reacts faster with iodide ion than does a simple primary alkyl chloride, although the heats of reaction are similar. 

Once the atoms arc defined, the bonds between them arc specified in a bond block. Each line of this block specifies which two atoms are bonded, the multiplicity of the bond (the bond type entry) and the stereo configuration of the bond (there arc also three additional fields that arc unused in Molfiles and usually set to 0). The indices of the atoms reflect the order of their appearance in the atom block. In the example analyzed, V relates to the first carbon atom (see also Figure 2-24). "2" to the second one, 3" to oxygen atom, etc. Then the two first lines of the bond block of the analyzed file (Figure 2-29) describe the single bond between the two carbon atoms C1-C2 and the double bond C2=0-5, respectively. 

Unit reactions at each carbon atom are then composed of unit exchanges of one bond type against another. There are 16 such exchanges possible at one carbon atom, each denoted by two letters, the first one for the bond made and the second for the bond broken. Figure 3-10 shows an example and Table 3-2 gives all the possible unit exchanges. 

There are two different types of carbon-carbon bonds m propene CH3CH=CH2 The double bond is of the ct + tt type and the bond to the methyl group is a ct bond formed by sp -sp overlap... 

Hydroboration is a reaction m which a boron hydride a compound of the type R2BH adds to a carbon-carbon bond A carbon-hydrogen bond and a carbon-boron bond result... 

Converting aldehydes and ketones to cyanohydrins is of synthetic value for two reasons (1) a new carbon-carbon bond is formed and (2) the cyano group in the prod uct can be converted to a carboxylic acid function (CO2H) by hydrolysis (to be discussed in Section 19 12) or to an amine of the type CH2NH2 by reduction (to be discussed m Section 22 9)... 

Resonance theory can also account for the stability of the allyl radical. For example, to form an ethylene radical from ethylene requites a bond dissociation energy of 410 kj/mol (98 kcal/mol), whereas the bond dissociation energy to form an allyl radical from propylene requites 368 kj/mol (88 kcal/mol). This difference results entirely from resonance stabilization. The electron spin resonance spectmm of the allyl radical shows three, not four, types of hydrogen signals. The infrared spectmm shows one type, not two, of carbon—carbon bonds. These data imply the existence, at least on the time scale probed, of a symmetric molecule. The two equivalent resonance stmctures for the allyl radical are as follows ... 

Heat resistance is iafluenced by both the type and extent of cure. The greater the strength of the chemical bonds ia the cross-link, the better is the compound s heat resistance. Peroxide cure systems, which result ia carbon—carbon bonds, result ia a range of sulfur cross-links varyiag from 1 to > 30 sulfur atoms per cross-link, and heat resistance improves as the number of more thermally stable short cross-links predominates. This is an important factor ia designing the desired cure system. 

Three different types of chemical mechanisms have evolved as attempts to simplify organic atmospheric chemistry surrogate (58,59), lumped (60—63), and carbon bond (64—66). These mechanisms were developed primarily to study the formation of and NO2 in photochemical smog, but can be extended to compute the concentrations of other pollutants, such as those leading to acid deposition (40,42). 

Sihcon carbide is comparatively stable. The only violent reaction occurs when SiC is heated with a mixture of potassium dichromate and lead chromate. Chemical reactions do, however, take place between sihcon carbide and a variety of compounds at relatively high temperatures. Sodium sihcate attacks SiC above 1300°C, and SiC reacts with calcium and magnesium oxides above 1000°C and with copper oxide at 800°C to form the metal sihcide. Sihcon carbide decomposes in fused alkahes such as potassium chromate or sodium chromate and in fused borax or cryohte, and reacts with carbon dioxide, hydrogen, ak, and steam. Sihcon carbide, resistant to chlorine below 700°C, reacts to form carbon and sihcon tetrachloride at high temperature. SiC dissociates in molten kon and the sihcon reacts with oxides present in the melt, a reaction of use in the metallurgy of kon and steel (qv). The dense, self-bonded type of SiC has good resistance to aluminum up to about 800°C, to bismuth and zinc at 600°C, and to tin up to 400°C a new sihcon nitride-bonded type exhibits improved resistance to cryohte. 

With an appropriately substituted precursor, photochemical carbon-carbon bond formation is a convenient method for the synthesis of ring-fused systems of the type under discussion. 

Cracking, a rupturing of carbon-carbon bonds—for example, of gas oils to gasohne—is favored by sihca-alumina, zeolites, and acid types generally. Zeohtes have pores with small and narrow size distribution. They crack only molecules small enough to enter the pores. To restrain the undesirable formation of carbon and C3-C4 hydrocarbons, zeolite activity is reduced by dilution to 10 to 15 percent in silica-alumina. 

The alkyl-bridged structures can also be described as comer-protonated cyclopropanes, since if the bridging C—C bonds are considered to be fully formed, there is an extra proton on the bridging carbon. In another possible type of structure, called edge-protonated cyclopropanes, the carbon-carbon bonds are depicted as fully formed, with the extra proton associated with one of the bent bonds. MO calculations, structural studies under stable-ion conditions, and product and mechanistic studies of reactions in solution have all been applied to understanding the nature of the intermediates involved in carbocation rearrangements. 

Coupling reactions and related fluoroalkylations with polytTuoioalkyl halides are induced by vanous reagents, among them metals such as copper and zinc, or by an electrochemical cell. More recently, examples of carbon-carbon bond forma tion by coupling of unsaturated fluorides have been reported Both acyclic and cyclic fluoroolefins of the type (Rp)2C=CFRp undergo reducUve dimerization on treatment with phosphines [42] (equation 33) The reaction shown in equation 33 IS also accompbshed electrocheimcally but less cleanly [43]... 

The addition of halogenated aliphatics to carbon-carbon double bonds is the most useful type of carbon-carbon bond forming synthetic method for highly halogenated substrates Numerous synthetic procedures have been developed for these types of reactions, particularly for the addition of perfluoroalkyl iodides to alkenes using thermal or photolytic initiators of free radical reactions such as organic peroxides and azo compounds [/]... 

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