Molecular Shapes, Symmetry and Molecular Orbital Theory

1st year Inorganic Chemistry Lecture Course 6 Lectures: Hilary Term, weeks 1-3 Synopsis 1. Initial models of inorganic molecules: Lewis structures, the valence shell electron pair repulsion (VSEPR) model. An introduction to molecular symmetry. 2. Symmetry elements and operations and the identification of molecular point groups. 3. Introduction to molecular orbital theory The electron distribution in H2. The LCAO method. The exclusion principle and antibonding orbitals. MO diagrams. Bond orders. 4. Homonuclear diatomics. p and p MOs. MO diagrams and bond orders for N2, O2 and F2. Bond energy trends. Symmetry classification of MOs. 5. Heteronuclear diatomics. MO diagrams and charge distribution. Examples of HF, BH. Hybridisation and the simultaneous use of s and p orbitals. Electronegativity difference and bond strengths. 6. Polyatomic molecules. Directed valence, hybridisation and bond angles. 3-centre molecular orbitals; simple application to electron deficient and hypervalent molecules. Bibliography Adequate accounts are given in inorganic textbooks , e.g. Shriver and Atkins Inorganic Chemistry OUP 5th edition Jack Barrett David Hayward Mark J Winter Structure and Bonding Quantum Mechanics Chemical bonding RSC Tutorial Chemistry Text, 5 RSC Tutorial Chemistry Text, 14 Oxford Chemistry Primers, 15 L. J. Smith

For Molecular Symmetry introductory chapters in Alan Vincent Molecular Symmetry and Group Theory J.S. Ogden Introduction to Molecular Symmetry Oxford Chemistry Primer 97 David Willock Molecular Symmetry For more thorough accounts of Molecular Orbital Theory McWeeny Coulsons Valence OUP, 3rd edition DeKock and Gray Chemical Structure and Bonding University Science books Murrell, Kettle and Tedder The Chemical Bond, Wiley

Lecture 1

Molecular Shapes and Symmetry

1. Initial models of inorganic molecules G. N. Lewis (1875-1946) covalent bonding described in terms of shared pairs of electrons. Octet rule In many molecules each atoms shares electrons with neighbouring atoms to achieve 8 valence electrons (an octet). Lewis structures provide a simple representation of the bonding. To draw a) identify the total number of valence electrons present in each contributing atom b) if the molecule is charged subtract or add extra electron(s) to account for the positive or negative charge respectively c) distribute electrons in the structure so that there is an electron pair forming a single bond between each pair of atoms that are bonded together. The extra electrons are then added as lone pairs or form multiple bonds until each atom has an octet. e.g. NO2

Resonance when several alternative low energy Lewis structures are available the bonding can be described in terms of resonance between the structures. Heavier elements can show octet expansion or hypervalence. e.g. ClF3

Formal charge the charge an atom would have if all covalent bonds in a molecule were broken and the electrons assigned equally to the atoms involved. Formal charge = (no. of valence electrons in neutral atom) (no. of lone pair electrons) (1/2)(no. of electrons in bonds formed). Lewis structures with low formal charges typically have the lowest energy e.g. ONC

VSEPR (Valence Shell Electron Pair Repulsion) model This simple model predicts the structure of molecules by assuming that the geometry of a molecule depends only upon electron-electron interactions. To make a VSEPR prediction: a) Write down Lewis structure for a molecule and identify the central atom b) Count the number of bonding electron pairs and lone pairs around the central atom. To achieve the lowest energy these electron pairs position themselves so they are as far apart as possible: Number of electron pairs 2 3 4 5 6 7 Arrangement Linear Trigonal planar Tetrahedral Trigonal bipyramid Octahedral Pentagonal bipyramid

From the arrangement of electron pairs, the location of the atoms and hence the shape of molecule can be identified. In a trigonal bipyramidal arrangement the lone pairs occupy equatorial sites. In an octahedral arrangement if there are two lone pairs these are positioned trans to each other. c) Refinement of the basic shape is then made by recognising i) Electron-electron repulsions decrease in the sequence: lone pair- lone pair > lone pair-bonding pair > bonding pair-bonding pair ii) When the central atom is involved in multiple bonds electron-electron repulsions decrease in the order: triple bond-single bond > double bond-single bond > single bond-single bond iii) Repulsions between bonding pairs in ABx depends on the electronegativity difference of the central (A) and terminal (B) atoms. As the terminal atoms become more electronegative the bonding electron pairs are drawn away from the central atom and the electron-electron repulsions reduce. e.g. ClF3 e.g. XeOF4 e.g. NO2

Exceptions VSEPR is a useful tool that works well for most main group compounds (but not transition metal compounds) although some exceptions are known e.g. XeF6 (6 bonding pairs and one lone pair) has a distorted octahedral structure in the gas phase. SbPh5 and InCl52- (5 bonding pairs) adopts a square pyramidal structure. SeCl62- and TeCl62- (6 bonding pairs and one lone pair) adopt regular octahedral structures.

2. Symmetry operations and symmetry elements A symmetry operation is an action that leaves a molecule apparently unchanged. For example, if we take an H2O molecule and rotate it by 180 about an axis passing through the central O atom (between the two H atoms) it will look indistinguishable.

Each symmetry operation has an associated symmetry element, which is the axis, plane, line or point with respect to which the symmetry operation is carried out. Important symmetry elements and their corresponding symmetry operations Symbol E Cn i Sn Symmetry element whole of space n-fold axis of rotation mirror plane Centre of inversion n-fold axis of improper rotation Symmetry operation Identity Rotation by 360/n Reflection Inversion Rotation by 360/n followed by reflection in plane perpendicular to the rotation axis

Mathematically the operation of doing nothing is a symmetry operation called the identity operation (E). The corresponding symmetry element is the entire molecule. Every molecule has at least this element. A molecule possesses an n-fold rotation axis if the molecule appears unchanged after rotation by 360/n about the axis (symbol Cn) C3 e.g. BF3 C4 e.g. XeF4

C5 e.g. IF7

C6 e.g. C6H6

A molecule possesses a plane of symmetry (mirror plane, symbol ) if reflection in the plane leaves the molecule looking the same. e.g. The H2O molecule contains two perpendicular mirror planes

An improper rotation consists of rotating through an angle of 360/n about an axis, followed by reflecting in a plane perpendicular to the axis. The axis is called an n-fold axis of improper rotation (symbol Sn).

The inversion operation is carried out with respect to a centre of inversion (symbol i). In this operation every atom is projected in a straight line though the centre of inversion and then an equal distance on the other side. If the centre of symmetry is defined as the origin (0, 0, 0) then inversion involves moving each point (x,y,z) to (-x,-y,-z). Molecules with a centre of inversion are termed centrosymmetric.