Bonding components

The potential energy of a molecular system in a force field is the sum of individnal components of the potential, such as bond, angle, and van der Waals potentials (equation H). The energies of the individual bonding components (bonds, angles, and dihedrals) are function s of th e deviation of a molecule from a h ypo-thetical compound that has bonded in teraction s at minimum val-n es. 

The triple bond of acetylene has a cr bond component and two tt bonds the two TT bonds are shown here and are perpendicular to each other... 

Strictly speaking Eq. (8-51) should be applied only to reacting systems whose molecular properties are consistent with the assumptions of regular solution theory. This essentially restricts the approach to the reactions of nonpolar species in nonpolar solvents. Even in these systems, which we recall do not exhibit a marked solvent dependence, correlations with tend to be poor. - pp Nevertheless, the solubility parameter and its partitioning into dispersion, polar, and H-bonding components provide some insight into solvent behavior that is different from the information given by other properties such as those in Tables 8-2 and 8-3. 

The Pauson-Khand reaction was originally developed using strained cyclic alkenes, and gives good yields with such substrates. Alkenes with sterically demanding substituents and acyclic as well as unstrained cyclic alkenes often are less suitable substrates. An exception to this is ethylene, which reacts well. Acetylene as well as simple terminal alkynes and aryl acetylenes can be used as triple-bond component. 

The formulated principals correlating crystal structure features with the X Nb(Ta) ratio do not take into account the impact of the second cation. Nevertheless, substitution of a second cation in compounds of similar types can change the character of the bonds within complex ions. Specifically, the decrease in the ionic radius of the second (outer-sphere) cation leads not only to a decrease in its coordination number but also to a decrease in the ionic bond component of the complex [277]. 

Several transition metal complexes can catalyze the exchange of partners of two double bonds. Known as the olefin metathesis reaction, this process can be used to close or open rings, as well to interchange double-bond components. 

The catalysts are metal-carbene complexes that react with the alkene to form a metal-locyclobutane intermediate.290 If the metallocyclobutane breaks down in the alternative path from its formation, an exchange of the double-bond components occurs. 

Methanol and other alcohols also add across the silicon-carbon double bond component of silaallenes. Thus, when (Me3Si)PhC=C=Si(Si Me3)Mes was generated at 140°C in the presence of methanol, the adduct (Me3Si)PhC=CHSi(OMe)(SiMe3)Mes was obtained, among other products.72... 

Compounds of types i, 2, and 3 were deduced to have planar, trigonal configurations from kinetic and stereochemical observations71 however, confirmation of this postulate was provided only a few years ago by the X-ray structure analysis of (bistrimethylsilyl)aminobis(trimethylsilylimino)phosphorane8). The P/N(imine) bonds were found to be relatively short, which was attributed to a high rc-bonding component in the planar system of coordinatively unsaturated phosphorus. 

Our discussion has so far ignored the effect of relaxation, namely spin flip of electrons in a time comparable to the Larmor precession period ( 1 ). The apparent low field (weak bonding) component in the analysis above might be the result of relaxation. However, the decrease in relaxation time is also considered to reflect the decrease in the strength of chemical bonds between the adsorbed metal species and the substrate. Therefore, the conclusion described above is considered to remain valid. 

The enthalpies of formation AHi of the components AH" " and A are however made up of the bonding enthalpies, so that they can be separated into a- and ir-bonding components. One then finds ... 

Transition metal-catalyzed intermolecular [2 + 2 + 2] cyclotrimerization of alkynes to benzene derivatives has been extensively studied. In this section, the focus is on the cyclo-trimerizations of the substrates bearing three independent unsaturated bond components. The key issue with this type of process usually involves the challenge of controlling regioselectivity [1—1]. However, 1,3,5-trisubstituted benzene 44 can be obtained as the sole product in good yield when 3-butyn-2-one 43 is used as the substrate for the cyclotrimerization catalyzed by Rh2(pfb)4 (pfb=perfluorobutyrate) in the presence of EtsSiH under a CO atmosphere (Eq. 11) [30]. 

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