Molecular geometry pairs

The major features of molecular geometry can be predicted on the basis of a quite simple principle—electron-pair repulsion. This principle is the essence of the valence-shell electron-pair repulsion (VSEPR) model, first suggested by N. V. Sidgwick and H. M. Powell in 1940. It was developed and expanded later by R. J. Gillespie and R. S. Nyholm. According to the VSEPR model, the valence electron pairs surrounding an atom repel one another. Consequently, the orbitals containing those electron pairs are oriented to be as far apart as possible. 

Molecular geometries for molecules with two to six electron-pair bonds around a central atom (A). 

The molecular geometry is quite different when one or more unshared pairs are present. In describing molecular geometry, we refer only to the positions of the bonded atoms. These positions can be determined experimentally positions of unshared pairs cannot be established by experiment. Hence, the locations of unshared pairs are not specified in describing molecular geometry. 

Table 7.3 summarizes the molecular geometries of species in which a central atom is surrounded by two, three, or four electron pairs. The table is organized in terms of the number of terminal atoms, X, and unshared pairs, E, surrounding the central atom, A. 

The VSEPR model is readly extended to species in which double or triple bonds are present A simple principle applies Insofar as molecular geometry is concerned, a multiple bond behaves like a single bond. This makes sense. The four electrons in a double bond, or the six electrons in a triple bond, must be located between the two atoms, as are the two electrons in a single bond. This means that the electron pairs in a multiple bond must occupy the same region of space as those in a single bond. Hence the extra electron pairs in a multiple bond have no effect on geometry. 

Molecular geometries for molecules with expanded octets and unshared electron pairs. The gray spheres represent terminal atoms (X), and the open ellipses represent unshared electron pairs (E). For example. AX4E represents a molecule in which the central atom is surrounded by four covalent bonds and one unshared electron pair. 

We have noted that the extra electron pairs in a multiple bond are not hybridized and have no effect on molecular geometry. At this point, you may well wonder what happened to those electrons. Where are they in molecules like C2H4 and C2H2 ... 

In Chapter 7, we used valence bond theory to explain bonding in molecules. It accounts, at least qualitatively, for the stability of the covalent bond in terms of the overlap of atomic orbitals. By invoking hybridization, valence bond theory can account for the molecular geometries predicted by electron-pair repulsion. Where Lewis structures are inadequate, as in S02, the concept of resonance allows us to explain the observed properties. 

Expanded octet More than four electron pairs about a central atom, 173-174 and hybridization, 187 and molecular geometry, 181 Expansion, 339-340... 

Mole-mass, 55,70-72q Molecular formula A formula in which the number of atoms of each type in a molecule is indicated as a subscript after the symbol of the atom, 34,59-60 Molecular geometry The shape of a molecule, describing the relative positions of atoms, 175 193q electron pairs, 179t major features, 175-176 molecules with expanded octets, 181t molecules with unshared electron pairs, 181t... 

VSEPR model Valence Shell Electron Pair Repulsion model, used to predict molecular geometry states that electron pairs around a central atom tend to be as far apart as possible, 180-182... 

We are now ready to account for the bonding in methane. In the promoted, hybridized atom each of the electrons in the four sp3 hybrid orbitals can pair with an electron in a hydrogen ls-orbital. Their overlapping orbitals form four o-bonds that point toward the corners of a tetrahedron (Fig. 3.14). The valence-bond description is now consistent with experimental data on molecular geometry. 

Because equatorial and axial positions differ, two molecular geometries are possible for SF4. As Figure 9-22 shows, placing the lone pair in an axial position gives a trigonal pyramid, whereas placing the lone pair in an equatorial position gives a seesaw shape. 

The Lewis stmeture of SFg, shown in Figure 9-24a. indicates that sulfur has six S—F bonds and no lone pairs. The molecular geometry that keeps the six fluorine atoms as far apart as possible is octahedral in shape, as Figure 9-24Z) shows. Figure 9-24c shows that an octahedron has eight triangular faces. 

C09-0109. Species with chemical formula X I4 can have the following shapes. For each, name the molecular geometry, identify the ideal VSEPR bond angles, tell how many lone pairs are present in the structure, and give a specific example. 

Tetrahedral molecular geometry, with 109.5° bond angles, minimizes repulsion among the bonding electron pairs of methane. ... 

The molecular geometry of a complex depends on the coordination number, which is the number of ligand atoms bonded to the metal. The most common coordination number is 6, and almost all metal complexes with coordination number 6 adopt octahedral geometry. This preferred geometry can be traced to the valence shell electron pair repulsion (VSEPR) model Introduced In Chapter 9. The ligands space themselves around the metal as far apart as possible, to minimize electron-electron repulsion. 

The other approach to molecular geometry is the valence shell electron-pair repulsion (VSEPR) theory. This theory holds that... 

Before discussing the AIM theory, we describe in Chapters 4 and 5 two simple models, the valence shell electron pair (VSEPR) model and the ligand close-packing (LCP) model of molecular geometry. These models are based on a simple qualitative picture of the electron distribution in a molecule, particularly as it influenced by the Pauli principle. 

Molecular Geometry The Valence Shell Electron-Pair Repulsion (VSEPR) Model... 

According to VSEPR theory, the most stable arrangement of the three lone pairs of electrons would be in the equatorial position, as shown in (1), where they would be less crowded. Therefore, a linear structure is the correct molecular geometry of the molecule. 

The Lewis formula predicts 2 electron groups around the central Be atom and a linear electronic geometry. There are no lone pairs on the Cd atom, so the molecular geometry is the same as the electronic geometry linear (Section 8-5). 

The Lewis formula for the molecule (type AB4) predicts 4 electron groups around the central Sn atom and a tetrahedral electronic geometry. Since there are no lone pairs on Sn, the molecular geometry is also tetrahedral (Section 8-7). 

The Lewis formula shows 5 electron groups around the central S atom and its electronic geometry is trigonal bipyramidal. The molecular geometry is a seesaw due to the presence of 1 lone pair of electrons on the central S atom. 

The Lewis formula for the molecule (type AB2U) predicts 3 electron groups around the central N atom including 1 lone pair of electrons. The electronic geometry is trigonal planar and the molecular geometry is angular or bent (Table 8-3). 

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