Bond additivity

Bond-energy schemes in their simplest form involve the assumption that each bond in a molecule contributes a partial AfH29g (bond) to the total Af.//298 (molecule) 

This is easily seen in the stepwise dissociation of the four equivalent bonds in CH4. 

In the unique case of diatomic molecules, however, bond energies and dissociation energies are, in principle, identical and exact (although, there may be disagreement in the literature as to what the exact values are). The enthalpy change for the reaction 

Yet another important concept comes to light when we examine the seemingly simple method of approximating Af//298 of a molecule using 

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There are many ways of presenting a connection table. One is first to label each atom of a molecule arbitrarily and to arrange them in an atom list (Figure 2-20). Then the bond information is stored in a second table with indices of the atoms that are connected by a bond. Additionally, the bond order of the corresponding coimection is stored as an integer code (1 = single bond, 2 = double bond, etc.) in the third column. 

Both tables, the atom and the bond lists, are linked through the atom indices. An alternative coimection table in the form of a redundant CT is shown in Figure 2-21. There, the first two columns give the index of an atom and the corresponding element symbol. The bond list is integrated into a tabular form in which the atoms are defined. Thus, the bond list extends the table behind the first two columns of the atom list. An atom can be bonded to several other atoms the atom with index 1 is connected to the atoms 2, 4, 5, and 6. These can also be written on one line. Then, a given row contains a focused atom in the atom list, followed by the indices of all the atoms to which this atom is bonded. Additionally, the bond orders are inserted directly following the atom in-... 

In order to develop a quantitative interpretation of the effects contributing to heats of atomization, we will introduce other schemes that have been advocated for estimating heats of formation and heats of atomization. We will discuss two schemes and illustrate them with the example of alkanes. Laidler [11] modified a bond additivity scheme by using different bond contributions for C-H bonds, depending on whether hydrogen is bonded to a primary (F(C-H)p), secondary ( (C-H)g), or tertiary ( (C-H)t) carbon atom. Thus, in effect, Laidler also used four different kinds of structure elements to estimate heats of formation of alkanes, in agreement with the four different groups used by Benson. 

Another scheme for estimating thermocheraical data, introduced by Allen [12], accumulated the deviations from simple bond additivity in the carbon skeleton. To achieve this, he introduced, over and beyond a contribution from a C-C and a C-H bond, a contribution G(CCC) every time a consecutive arrangement of three carbon atoms was met, and a contribution D(CCC) whenever three carbon atoms were bonded to a central carbon atom. Table 7-3 shows the substructures, the symbols, and the contributions to the heats of formation and to the heats of atomization. 

Our results are in very good agreement with Benson s simpler bond additivity values (2.5 kcal mol and —3.75 kcal mol Benson and Cohen, 1998), as indeed they must be because they were obtained from the same set of experimental enthalpies of formation. Note that many applications in themiochemishy use energy units of kilocalories per mole, where 1.000 kcal mol =4.184 kJ mol . ... 

For purely alicyclic compounds, the selection process proceeds successively until a decision is reached (a) the maximum number of substituents corresponding to the characteristic group cited earliest in Table 1.7, (b) the maximum number of double and triple bonds considered together, (c) the maximum length of the chain, and (d) the maximum number of double bonds. Additional criteria, if needed for complicated compounds, are given in the lUPAC nomenclature rules. 

Some details of the chain-initiation step have been elucidated. With an oxygen radical-initiator such as the /-butoxyl radical, both double bond addition and hydrogen abstraction are observed. Hydrogen abstraction is observed at the ester alkyl group of methyl acrylate. Double bond addition occurs in both a head-to-head and a head-to-tail manner (80). 

In order to locate items of interest in the book, the subject index lists, in addition to chemical operations, types of compounds rather than specific compounds (with a few exceptions). If, for example, readers do not find what they are looking for under the entry fluoroolefins , they may try olefins , double bonds, additions of , etc. 

Addition reactions — The fullerenes Ceo and C70 react as electron-poor olefins with fairly localized double bonds. Addition occurs preferentially at a double bond common to two annelated 6-membered rings (a 6 6 bond) and a second addition, when it occurs is generally in the opposite hemisphere. The first characteriz-able mono adduct was [C6oOs04(NC5H4Bu )2]. formed by reacting Cgo with an excess of OSO4 in 4-butylpyridine. The structure is shown in... 

Naphthalene and other polycyclic aromatic hydrocarbons show many of the chemical properties associated with aromaticity. Thus, measurement of its heat of hydrogenation shows an aromatic stabilization energy of approximately 250 kj/mol (60 kcal/mol). Furthermore, naphthalene reacts slowly with electrophiles such as Br2 to give substitution products rather than double-bond addition products. 

Despite the lability of the N — O bond, addition of organomctallic reagents to 5-substituted isoxa-zolines provides a potential route for stereoselective synthesis of substituted 3-amino alcohols1. 

Structures have been determined for a number of these compounds, showing that the Rh-P bonds are little affected by the m-ligands (Figure 2.22). The shorter Rh-C distance in the thiocarbonyl is probably a result of greater Rh=C back-bonding. Addition of S02 results in the formation of a 5-coordinate (sp) adduct with the expected lengthening in all bonds. 

Radicals can be classified according to their tendency to give aromatic substitution, abstraction, double bond addition, or (3-scission and further classified in terms of the specificity of these reactions (see 3.4). With this knowledge, it should be possible to choose an initiator according to its suitability for use with a given monomer or monomer system so as to avoid the formation of undesirable end groups or, alternatively, to achieve a desired functionality. 

The relative amounts of double bond addition, hydrogen abstraction and 13-scission observed are dependent on the reactivity and concentration of the particular monomer(s) employed and the reaction conditions. Higher reaction temperatures are reported to favor abstraction over addition in the reaction of t-butoxy radicals with AMS413 and cyclopentadiene 417 However, the opposite trend is seen with isobutylene.2 1 24... 

Isopropoxycarbonyloxy radicals undergo facile reaction with aromatic substrates (e.g. toluene) by reversible aromatic substitution. 94 Isopropoxycarbonyloxy radicals react with S to give ring substitution (ca 1%) as well as the expected double bond addition.40 ... 

In Part 2 of this book, we shall be directly concerned with organic reactions and their mechanisms. The reactions have been classified into 10 chapters, based primarily on reaction type substitutions, additions to multiple bonds, eliminations, rearrangements, and oxidation-reduction reactions. Five chapters are devoted to substitutions these are classified on the basis of mechanism as well as substrate. Chapters 10 and 13 include nucleophilic substitutions at aliphatic and aromatic substrates, respectively, Chapters 12 and 11 deal with electrophilic substitutions at aliphatic and aromatic substrates, respectively. All free-radical substitutions are discussed in Chapter 14. Additions to multiple bonds are classified not according to mechanism, but according to the type of multiple bond. Additions to carbon-carbon multiple bonds are dealt with in Chapter 15 additions to other multiple bonds in Chapter 16. One chapter is devoted to each of the three remaining reaction types Chapter 17, eliminations Chapter 18, rearrangements Chapter 19, oxidation-reduction reactions. This last chapter covers only those oxidation-reduction reactions that could not be conveniently treated in any of the other categories (except for oxidative eliminations). 

Halogenation of Double and Triple Bonds (Addition of Halogen, Halogen)... 

Addition of HOBr or HOCl to triple bonds addition of chlorine... 

Addition of unsaturated boranes to methyl vinyl ketones Hydrocarboxylation of triple bonds Addition of acyl halides to triple bonds 1,4-Addition of acetals to dienes... 

Tamao K, Miyaura N (2002) Introduction to Cross-Coupling Reactions. 219 1-9 Tanaka M (2003) Homogeneous Catalysis for H-P Bond Addition Reactions. 232 25-54 Tanner PA (2004) Spectra, Energy Levels and Energy Transfer in High Symmetry Lanthanide Compounds. 241 167-278 ten Cate MGJ, see Crego-Calama M (2005) 249 in press ten Holte P,see Zwanenburg B (2001) 216 93-124 Thiem J,see Werschkun B (2001) 215 293-325... 

Collagen triple helices are stabilized by hydrogen bonds between residues in dijferent polypeptide chains. The hydroxyl groups of hydroxyprolyl residues also participate in interchain hydrogen bonding. Additional stability is provided by covalent cross-links formed between modified lysyl residues both within and between polypeptide chains. 

The onward metabohsm of succinate, leading to the regeneration of oxaloacetate, is the same sequence of chemical reactions as occurs in the P-oxidation of fatty acids dehydrogenation to form a carbon-carbon double bond, addition of water to form a hydroxyl group, and a hirther dehydrogenation to yield the oxo- group of oxaloacetate. 

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