Bond properties donor-acceptor

Associating fluid mixtures contain not only monomeric molecules but also clusters of like and unlike molecules, for example, hydrogen-bonded and donor-acceptor clusters [24). Since the effective molecular properties of the clusters (size, energy, and shape) are very different from the corresponding monomeric molecules, the bulk fluid properties also differ significantly. One way to account for such association effects is to use statistical mechanics methods, such as perturbation theory, to quantify the relationship between well-defined... 

Haima, M.W (1968) Bonding in donor-acceptor complexes. I. Electrostatic contributions to the ground-state properties of benzene-halogen complexes. J. Am. Chem. Soc., 90, 285-291. 

The contribution of this polar structure to the bonding lowers the energy of the transition state. This may be viewed as a lower activation energy for the addition step and thus a factor which promotes this particular reaction. The effect is clearly larger the greater the difference in the donor-acceptor properties of X and Y. The transition state for the successive addition of the same monomer (whether X or Y substituted) is structure [V] ... 

Cyclic conjugation is continuous in l,2-dihydro-l,2-azaborine with one N-B bond (Scheme 34). The nitrogen atom with a lone pair is donor. The B atom with a vacant p orbital is acceptor. Whether the remaining C=C bonds are donors or accepters, the donors are disposed on one side of the cychc chain while the acceptors are on the other side. The orbital phase property or the number of electrons is important. The phase continuity or the six n electrons predicts that 1,2-dihydro-l-,2-azaborine could be aromatic. 

The force constants of the Ni—P bond in P " nickel carbonyl complexes increase in the order MeaP < PHg < P(OMe)a < PFs. This order is different from that of the donor-acceptor character, as estimated from uco-The lengthening of the P—O bond of triphenylphosphine oxide upon complexation with uranium oxide has been estimated by i.r. spectroscopy. However, A -ray diffraction shows little difference in the P-O bond lengths (see Section 7). Some SCF-MO calculations on the donor-acceptor properties of McaPO and H3PO have been reported. 

It has been shown for many RPLC methods that correlations between log Pod and retention parameters were improved by separating compounds in two classes, i.e. H-bond acceptor and donor compounds. Minick et al. [23] propose to add 0.25% (v/v) of 1-octanol in the organic porhon of the mobile phase (methanol was preferred in this study) and to prepare the aqueous portion with 1-octanol-saturated water to minimize this discriminahon regarding H-bond properties. For a set of heterogenous neutral compounds, the addition of 0.25% (v/v) of 1-octanol in methanol and the use of water-saturated 1-octanol to prepare mobile phase improve the correlahon between log few obtained on the LC-ABZ column and log Poc, [13]. 

The H-bonding in the anhydrous 1 Im (Table 24) has topologic properties (Fig. 46) similar to those in the alcohol coordinatoclathrates of 1 with 1 2 host guest stoichiometry (cf. Fig. 17 a). Assuming a perfectly ordered crystal lattice, the resulting central loop of H-bonds should appear to have homodromic directionality with the donor/acceptor functions separated in space. This contrasts to the behavior in the dihydrated l Im where no such characteristic loops are formed. Involvement of the C—H hydrogen atoms of the imidazole molecule, however, is similar in both cases. 

Meyers F, Marder SR, Pierce BM, Bredas JL (1994) Electric field modulated nonlinear optical properties of donor-acceptor polyenes sum-over-states investigation of the relationship between molecular polarizabilities (a, p, and y ) and bond length alternation. J Am Chem Soc 116 10703-10714... 

Methoxypurine was found to crystallize as a hemihydrate from /V,/V -dimethyl formamide, and as a trihydrate from water [63]. Thermal treatment of the trihydrate could be used to obtain the hemihydrate. Zafirlukast was obtained in the form of monohydrate, methanol, and ethanol solvatomorphs, with the drug substance adopting a similar conformation in all three structures [64], In the isostructural methanol and ethanol solvates, the solvent molecules are hydrogen-bonded to two zafirlukast molecules, while in the monohydrate, the water molecules are hydrogen-bonded to three zafirlukast molecules. The structures of the acetone and isopropanol solvatomorphs of brucine have been reported, where the solvent controlled the self-assembly of brucine on the basis of common donor-acceptor properties [65],... 

Diels-Alder cycloaddition reactions of electron-poor dienophiles to electron-rich dienes, which are generally carried out thermally, afford widespread applications for C—C bond formation. On the basis of their electronic properties, numerous dienes can be characterized as electron donors and dienophiles as electron acceptors. Despite the early suggestions by Woodward,206 the donor/ acceptor association and electron-transfer paradigm are usually not considered as the simplest mechanistic formulation for the Diels-Alder reaction. However, the examples of cycloaddition reactions described below will show that photoirradiation of various D/A pairs leads to efficient cycloaddition reactions via electron-transfer activation. 

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