VSEPR model structures

Figure 7.5 (page 177) shows the geometries predicted by the VSEPR model for molecules of the types AX2 to AX. The geometries for two and three electron pairs are those associated with species in which the central atom has less than an octet of electrons. Molecules of this type include BeF2 (in the gas state) and BF3, which have the Lewis structures shown below ... 

Geometries of molecules such as these can be predicted by the VSEPR model The results are shown in Figure 7.8 (page 181). The structures listed include those of all types of molecules having five or six electron pairs around the central atom, one or more of which may be unshared. Note that—... 

The Lewis structures encountered in Chapter 2 are two-dimensional representations of the links between atoms—their connectivity—and except in the simplest cases do not depict the arrangement of atoms in space. The valence-shell electron-pair repulsion model (VSEPR model) extends Lewis s theory of bonding to account for molecular shapes by adding rules that account for bond angles. The model starts from the idea that because electrons repel one another, the shapes of simple molecules correspond to arrangements in which pairs of bonding electrons lie as far apart as possible. Specifically ... 

A molecule with only two atoms attached to the central atom is BeCl2. The Lewis structure is CI — Be — CE, and there are no lone pairs on the central atom. To be as far apart as possible, the two bonding pairs lie on opposite sides of the Be atom, and so the electron arrangement is linear. Because a Cl atom is attached by each bonding pair, the VSEPR model predicts a linear shape for the BeCL molecule, with a bond angle of 180° (4). That shape is confirmed by experiment. 

STRATEGY For the electron arrangement, draw the Fewis structure and then use the VSEPR model to decide how the bonding pairs and lone pairs are arranged around the central (nitrogen) atom (consult Fig. 3.2 if necessary). Identify the molecular shape from the layout of atoms, as in Fig. 3.1. 

Consider the structure of p-azoxyanisole (14). (a) Using the VSEPR model, draw a picture that represents the shape of the molecule and predict the CNN bond angles, (b) What features of the bonding of this molecule give rise to its rodlike nature ... 

The cu-bonding model provides a more complete and fundamental description of hypervalent molecules that are often interpreted in terms of the VSEPR model.144 In the present section we examine some MX species that are commonly used to illustrate VSEPR principles, comparing and contrasting the VSEPR mnemonic with general Bent s rule, hybridization, and donor-acceptor concepts for rationalizing molecular geometry. Tables 3.32 and 3.33 summarize geometrical and NBO/NRT descriptors for a variety of normal-valent and hypervalent second-row fluorides to be discussed below, and Fig. 3.87 shows optimized structures of the hypervalent MF species (M = P, S, Cl n = 3-6). 

The most widely used qualitative model for the explanation of the shapes of molecules is the Valence Shell Electron Pair Repulsion (VSEPR) model of Gillespie and Nyholm (25). The orbital correlation diagrams of Walsh (26) are also used for simple systems for which the qualitative form of the MOs may be deduced from symmetry considerations. Attempts have been made to prove that these two approaches are equivalent (27). But this is impossible since Walsh s Rules refer explicitly to (and only have meaning within) the MO model while the VSEPR method does not refer to (is not confined by) any explicitly-stated model of molecular electronic structure. Thus, any proof that the two approaches are equivalent can only prove, at best, that the two are equivalent at the MO level i.e. that Walsh s Rules are contained in the VSEPR model. Of course, the transformation to localised orbitals of an MO determinant provides a convenient picture of VSEPR rules but the VSEPR method itself depends not on the independent-particle model but on the possibility of separating the total electronic structure of a molecule into more or less autonomous electron pairs which interact as separate entities (28). The localised MO description is merely the simplest such separation the general case is our Eq. (6)... 

Incidentally, it may be emphasized that (i) the MYKO-XYL structure constitutes a challenge to group theory in that it has no ternary symmetry and that (ii) the structure of MYKO-CgHg exhibits a tricky counter-example to Gillespie s VSEPR model, the lone pairs of the two exocyclic N atoms on each P being strictly parallel.. . ... 

In this chapter a few simple rules for predicting molecular structures will be investigated. We shall examine first the valence shell electron pair repulsion (VSEPR) model, and then a purely molecular orbital treatment. 

A boron trifluoride molecule, BF3, has the Lewis structure shown in (5). There are three bonding pairs attached to the central atom and no lone pairs. According to the VSEPR model, as illustrated in Fig. 3.4, the three bonding pairs, and the fluorine atoms they link, lie at the corners of an equilateral triangle. Such a structure is trigonal planar, and all three F—B—F angles are 120° (6). 

SOLUTION The Lewis structure of nitrogen trifluoride is shown in (22) we see that the central N atom has four electron pairs. According to the VSEPR model, these four electron-rich regions adopt a tetrahedral arrangement. Because one of the pairs is a lone pair, the molecule is expected to be trigonal pyramidal (23). Spectroscopic measurements confirm this prediction. 

Write a Lewis structure for the orthosilicate anion, Si044 , and deduce the formal charges and oxidation numbers of the atoms. Use the VSEPR model (Chapter 3) to predict the shape of the ion. 

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