Chemistry 3820 Lecture Notes

Dr.R.T.Boer

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Lewis dot diagrams and VSEPR structures

Review Lewis structures and VSEPR from General Chemistry texts, and consult S-A-L: 3.1-3.3 One of the basic distinctions you must learn to make is between ionic and covalent compounds. You will do much better in this course, as well as in all other chemistry courses, if you know instinctively whether the material being discussed is one or the other. So how can you learn this? Short of sheer memory work for millions of compounds, it is very possible to learn this intuitive knowledge simply by developing the habit of asking yourself: Is this compound covalent (i.e. a molecule) or ionic (i.e. composed of two or more ions)? Even if the answer is not obvious, it can usually be deduced from the information given. Often it becomes very obvious if you stop and think about it. We start by considering simple binary compounds , for which this distinction is simple. A compound AB is generally considered ionic if the difference in electronegativity between A and B is 2 units. Thus for H-F, = (3.9 2.2) = 1.7, and HF is considered to be a (polar) covalent molecule. But LiF, 6c = (3.9 1.0) = 2.9, and thus LiF is ionic. Note however that the ionic character of LiF is predominantly observed in the bulk solid - gaseous LiF (at very high temperature) will contain some Li-F molecules. We now focus on the structure and symmetry of the common covalent molecules, including common covalent or molecular ions (also known as complex ions), for which there are chemical bonds within the ionic unit. An example of the latter is an ion such as the sulfate ion, SO42-, which has covalent S-O bonds.

2.1

Valence and Lewis diagrams

In Chem. 1000 you learned how to write Lewis structures. The number of valence You were wondering electrons is taken directly off the periodic table, and can be had from the group numbers Why can we ignore previous directly. (Using the new numbering sequence, for p -block elements, subtract 10.) The shells when counting the number of valence electrons includes all s electrons since the last noble gas configuration number of valence electrons? plus the electrons of the block in which the element finds itself. Completely filled orbitals (except s orbitals) sink to much lower energy, becoming unavailable for bonding to elements in the subsequent block. Although Lewis diagrams are not 100% reliable, they have the advantage of organizing thousands of varied chemical compounds into a fast, easily understood diagrams which give a lot of useful information about the structure and reactivity of the compound. The essential postulate of this theory, first postulated in 1916 and still used today, is that bonds between atoms are due to shared electron pairs. Unshared electrons form lone pairs. Multiple bonds form between elements short of electrons. Double bonds have four shared electrons, triple bonds six. To write Lewis structures, follow the step-by-step guidelines given in the text (S-A-L) on p. 51-52. 1. Decide how many electrons are to be included in the diagram by adding together all the valence electrons provided by the atoms. Adjust for the ionic charge, if any. 2. Write the chemical symbols with the right connectivity (this cannot be deduced from the Lewis theory). 3. Distribute the electrons in pairs so that there is one pair of electrons between each pair of bonded atoms, and then supply electron pairs (to form multiple bonds or lone pairs) until each atom has an octet. 4. The formal charge gives some indication of the electron distribution in the molecule, where this is not even. For each atom, count the sum of the number of lone pair electrons and one from each bond-pair. The difference between this count and the valence of the atom is its formal charge. 5. Resonance is invoked whenever there is more than one way to distribute the electrons according to the above rules. The true structure is said to be a blend or hybrid of the various resonance isomers. 6. Finally, there are some elements for which exceptions to the octet rule occur. These include Be (4), B and Al (6 in some cases), as well as the "heavy" elements of period three and beyond, which may have 10 or 12 valence electrons about them. My rule of thumb in all such cases is to start from the outside and provide octets for the ligands first. If there are deficient or excess electrons at the central atom, verify that the atom is one of the ones mentioned here, and leave the diagram as produced.. Let's do some examples: CO2, NO3-, SO32-, NSF3, XeF4, IF5, PF5, SF6.

Chemistry 3820 Lecture Notes

Dr.R.T.Boer

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2.2

VSEPR theory

Just as Lewis structures give us a fast road to mapping the electrons of molecules, the Valence Shell Electron Pair Repulsion theory gives us a quick approach to determining molecular structure for many common main-group compounds. It is not much use for transition metal complexes, except those of the metals in their highest possible oxidation states. This concept, which is especially due to Prof. Ronald Gillespie of McMaster University (along with Prof. Nyholm of the U.K.), considers the electron pairs in molecules to be bound regions of negative charge, which naturally repel each other. The basic arrangements which minimize electron pair repulsions are: # of pairs basic shape hybridization of the central atom 2 linear sp 3 trigonal planar sp 2 4 tetrahedral sp 3 5 trigonal bipyramidal dsp 3 6 octahedral d 2sp 3 But since the central atom may have lone pairs, which do not contribute to the description of the shape of the molecule, there are several derivatives of the above. Within the derivatives, the choice of structure is such as to minimize 90 interactions in the order: LP/LP repulsions stronger than LB/BP repulsions, than BP/BP repulsions. The logic behind this is that LP are less constrained than BP, therefore are larger. This also accounts for deviations in bond angle in structures such as water and ammonia. Hybridization can also be used to re-configure the atomic orbitals of the atoms in the molecule according to the observed geometry. Note that when angles deviate from the ideal values, the extent of hybridization also changes. thus while CH4 has four sp3 hybrid orbitals on carbon, the two orbitals bonding to H in OH2 are not exactly sp3. They have marginally more "p" character, and less "s". The associated lone pair orbitals have correspondingly more "s" character. Quantum chemistry texts have formulae which express hybridization functions for given values of angles. These ideas on molecular structure are at best imprecise. A much more exact and extremely powerful approach to describing molecular shape exists, using symmetry and point group labels. We start by considering symmetry operations and elements. The following table summarizes the VSEPR structure method, and includes some common examples of the different structures that are encountered. The precise names of the structures are problematic, and indeed we need a better system. This can be done much more systematically using symmetry labels, and that will be the next topic we turn to. # of electron pairs at central atom* 2 2 3 shape family hybridization of the central atom sp sp sp 2 # of bond pairs 2 1 3 0 1 0 linear linear (e.g. BeH+ ) # of lone pairs actual molecule shape

linear linear triangular-planar

triangular-planar 3 3 4 triangular-planar triangular-planar tetrahedral sp 2 sp 2 sp 3 2 1 4 1 2 0 angular linear (e.g. AlCl2+ )

tetrahedral 4 tetrahedral sp 3 3 1

triangular-pyramidal

Chemistry 3820 Lecture Notes 4 tetrahedral sp 3

Dr.R.T.Boer 2 2

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4 5

tetrahedral triangular-bipyramidal

sp 3 dsp 3

1 5

3 0

angular linear (e.g. HCl)

triangular-bipyramidal 5 triangular-bipyramidal dsp 3 4 1

seesaw 5 triangular-bipyramidal dsp 3 3 2

T-shaped 5 triangular-bipyramidal dsp 3 2 3

linear 6 octahedral d 2sp 3 6 0

octahedral 6 octahedral d 2sp 3 5 1

square-pyramidal 6 octahedral d sp
2 3

square-planar * using any resonance isomer; double and triple bonds count as a single pair!

Chemistry 3820 Lecture Notes

Dr.R.T.Boer

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3 3.1

Molecular symmetry Symmetry operations and elements

Symmetry operation:

The movement of a molecule relative to some symmetry element which generates an orientation of the molecule indistinguishable from the original. Symmetry element: A line, point or plane, with respect to which one or more symmetry operations may be performed. We designate the symmetry elements by their Schnflies symbols. The following symmetry elements are found in molecules:

a)

Identity

Symbol: E

This means do nothing. It represents the lowest order of symmetry. All molecules posses the identity symmetry element. The inclusion of this element may seem silly, but it is vital to the correct mathematical description of symmetry by group theory. Note that the C1 rotation axis, i.e. rotation by 360, is the same as the identity, so C1 is never used.

b)

Proper rotation axes

Symbol:

Cn (n = 2, 3, 4, 5, 6, 7, )

An axis about which the molecule may be rotated 2/n radians. A two-fold rotation axis means rotation by radians, or 180. A three-fold axis means rotation by 120, etc. A molecule may have more than one order of axis; that axis with the largest value of n (highest order) is called the principal rotation axis . The graphics show a molecule possessing a C2 axis at right, and a C3 axis below. To discover if a molecule has a given symmetry element, we perform the corresponding operation. If the new orientation is indistinguishable from the original, then the molecule is said to posses that symmetry operation.

c)
v h d

Mirror planes

Symbol: , v , h, d

A non-specific mirror plane (possible only if this is the only symmetry element the molecule possesses. Vertical mirror plane is a plane of reflection containing the principle rotation axis. Horizontal mirror plane is a plane of reflection normal to the principle rotation axis. Dihedral mirror plane is a plane of reflection containing the principle rotation axis which also bisects two adjacent C2 axes perpendicular to the principle rotation axis.

d)

Centre of symmetry

Symbol: i

Also called an inversion, it means simply that: invert the position of all the atoms with respect to the centre of symmetry of the molecule. In coordinate language, this means converting x, y, z to -x, -y, -z.

Chemistry 3820 Lecture Notes

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e)

Improper rotation axes

Symbol: S n (n = 3, 4, 5, 6, 7 )

Also called rotation-reflection axes , which accurately describes this type of element. One rotates by 2/n radians, then reflects through h to get the new representation. The lower orders of Sn are redundant. Thus S1 = mirror plane, while S2 = centre of symmetry, so that these are never used. Also, when a molecule possesses a proper axis and h, it is also considered to contain the corresponding improper axis. The first graphic shows the presence of an S4 axis in a true tetrahedral molecule, which lies along the line of the C2 axis (there are 3 of each in a tetrahedral molecule).

The second figure depicts the redundancy and hence non-use of S1 and S2.

3.2

Point Groups

Point groups is short for point symmetry groups. They are collections of symmetry elements which isolated real objects may possess. Clearly only certain symmetry elements will coexist in the same object. The names of the point groups are related to the names of the symmetry operations, and in some cases the same symbol does for both. Be careful to distinguish the two! With some practice, it is easy to assign the point groups of all but the most difficult cases. The flowchart shown at the right will help you is assigning the point groups. Be sure to know how to correctly interpret each question along the path to the correct assignment. Note that the questions often prompt you to look for symmetry that you may have missed. Therefore whenever a question is asked that you have not yet considered, always go back to your picture or model and try to see if the indicated symmetry element may be present.

3.3

Polarity
In order to have a permanent dipole moment, a molecule must not belong to a D group of any kind, nor Td, Oh or Ih.

3.4

Chirality

In order to be chiral, a molecule must not posses an Sn axis, nor a mirror plane, nor an inversion axis. (The latter two are equivalent to S1 and S2).

Chemistry 3820 Lecture Notes

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3.5

Examples of point groups

C?v D?h Td Oh Ih C1 Cs Ci Cn Cnv Cnh Dn Dnd Dnh H-Cl O=C=O GeH4 SF6 [B12H12]2CHFClBr NHF2 no examples H2O2, S2Cl2 H2O, SF4, NH3, XeOF4, BrF5 B(OH)3 [Cr(en)3]3+ Mn 2(CO)10, Cp 2Fe staggered BF3, XeF4 Linear, unsymmetrical Linear, symmetrical Tetrahedral (but not CH3F!) Octahedral (but not SF5Cl) Icosahedral (rare) No symmetry elements except E Only a plane Only an inversion centre Only an n fold rotation axis

Shortened Flowchart to Determine Point Group

Cv , Dh , Td , Oh , or I h ?
No No

i?

No Yes

C1

Cn ? n = principal axis
Yes

No

?
Yes

Ci Cs

nC2 Cn ?

No

h ?

No

nv ?

No

Cn

Yes Yes No

nv ?

No

Yes

Dn

Cnh

Cnv

h ?
Yes

Yes

Dnh

Dnd

Chemistry 3820 Lecture Notes

Dr.R.T.Boer

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Extended Flowchart To Determine Point Group Symmetry

Linear?
No

i?

No

C v
Dv
Yes

Yes No

I
No Yes

Unique Cn ? n = principal axis

6C5 ?
No

i?

Ih

No Yes Yes Yes

4C3 ? S 2n
No No

3C4 ?
No

i?
Yes

Oh

3S 4 ?
Yes

No

i?
Yes

No

S 2n || Cn?

Yes

n d ?
Yes

Th Td

No

Dnd
No

3C2 ?

?
Yes

No

i?
Yes

No

C1

Yes

Ci Cs
No

nC2 Cn ?
No

Yes

h ?

No

2 d ?
Yes

Dn

Yes

D2d Dnh

h ?
Yes

No

n v ?

No Yes

Cn

Cnh

Cnv