Hydrogen bond acceptance/electron pair donation

The fact that a Lewis acid must be able to accept an electron pair means that it must have either a vacant, low-energy orbital or a polar bond to hydrogen so it can donate H" which has an empty Is orbital). Thus, the Lewis definition of acidity is much broader than the Bronsted-Lowry definition and includes many other species in addition to H. For example, various metal cations such as are Lewis acids because they accept a pair of electrons when they form a bond to a base. In the same way, compounds of group 3A elements such as BF3 and AlCln are Lewis acids because they have unfilled valence orbitals and can accept electron pairs from Lewis bases, as shown in Figure 2.5. Similarly, many transition-metal compounds, such as TiCU, FeCla, ZnCl, and SnCl4, are Lewis acids. 

Our focus in this chapter shall be primarily upon the surface electrostatic potential, specifically its most positive and most negative values, denoted by Vs, max and Vs,min, respectively. There may be several local and absolute maxima and minima on a given surface. They indicate the most positive and negative sites. The former are often associated with hydrogens, especially acidic ones, and the latter with lone pairs, tt electrons of unsaturated molecules and strained bonds. We have demonstrated that Vs niax and Vs nim correlate well with measures of hydrogen bond donating and accepting tendencies . 

The dissolution of a solute in a solvent always affects the solvent-solvent interactions in the vicinity of the solnte particles in addition to the solnte-solvent interactions that take place (Marcus, 1998b). This may be viewed in several stages. First, a cavity in the solvent is formed, to accommodate the solute, which breaks down the cohesive forces of the solvent. Next dispersion forces take effect. They apply to nonpolar and hardly polarizable solutes and solvents, as well as to polar and polarizable ones. Other forces that become active provide contributions from interactions of polar molecnles with polar or polarizable ones and from donor acceptor interactions, such as electron-pair or hydrogen-bond donation and acceptance, whether from or to the solute, the solvent, or both. 

In the same year that Bronsted and Lowry proposed their definition of acids and bases, an American chemist named Gilbert Lewis proposed an alternative definition that not only encompassed Bronsted-Lowry theory but also accounted for acid-base reactions in which a hydrogen ion isn t exchanged. Lewis s definition relies on tracking lone pairs of electrons. Under his theory, a base is any substance that donates a pair of electrons to form a coordinate covalent bond with another substance, while an acid is a substance that accepts that electron pair in such a reaction. As we explain in Chapter 5, a coordinate covalent bond is a covalent bond in which both of the bonding electrons are donated by one of the atoms forming the bond. 

The chemical properties of solvents have obviously a strong bearing on their applicability for various purposes. The solvents should selectively dissolve the desired solutes and not some others, they should be inactive in the chemical reactions undergone by the solutes, but solvate, again selectively, reactants, transition states, intermediates, and products. These aspects of the behaviour can be achieved by the proper blend of the chemical properties of structuredness, polarity, electron-pair and hydrogen bond donation and acceptance ability, softness, acidity and basicity, hydrophilicity or hydrophobicity, and redox properties, among others. Such chemical characteristics can often be derived from physical properties, but in other cases must be obtained from chemical interactions, for instance by the use of chemical probes ( indicators ). 

The solvating ability of solvents depends not only on their general polarity, which is a non-specific property, but in a large part to their ability to interact in a specific manner with the solute. This may take place by the donation of a nonbonding pair of electrons from a donor atom of the solvent towards the formation of a coordinate bond with the solute, therefore exhibiting Lewis basicity, or the acceptance of such a pair from a solute, an exhibition of Lewis acidity of a protic or protogenic solvent towards the formation of a hydrogen bond between it and... 

The term hydrogen-bond acceptor (HBA) refers to the acceptance of the proton of a hydrogen-bond. Therefore, HBA solvents are also electron-pair donor (EPD) solvents. Hydrogen-bond donor (HBD) refers to the donation of the proton. Therefore, HBD solvents behave as protic solvents. 

The Lewis bonding model with its electron pairs can be used to define a more general kind of acid-base behavior of which the Arrhenius and Bronsted-Lowry definitions are special cases. A Lewis base is any species that donates lone-pair electrons, and a Lewis acid is any species that accepts such electron pairs. The Arrhenius acids and bases considered so far fit this description (with the Lewis acid, H, acting as an acceptor toward various Lewis bases such as NH3 and OH , the electron pair donors). Other reactions that do not involve hydrogen ions can still be considered Lewis acid-base reactions. An example is the reaction between electron-deficient BF3 and electron-rich NH3 ... 

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