Inorganic Chemistry Structure and Bonding

 Learning Objectives  1.

Describe how the elements form bonds with each other by sharing electrons

 2.  3.

Derive Lewis structures for molecules or polyatomic ions. Predict when resonance structures are possible and draw the various structures

 Reference:  Inorganic Chemistry , 3rd Edition, Chapter 2, pg. 30-33.  Basic Inorganic Chemistry, 3rd Edition, Chapter 3, pg. 73-79

Bonding
 Chemical bonds may be classified into two main

categories: ionic and covalent bonds.

 Ionic bond - purely electrostatic attraction between

oppositely charged particles (ions). Electronegativity difference, (EN, between elements is relatively large.


Covalent bonding - used to describe the bonds in compounds that result from the sharing of one or more pairs of electrons. (EN, between elements is zero or relatively small. -two center (localized) vs. multicenter (delocalized) covalent bonding

The Localized Bond Approach

 3 relevant theories work simultaneously to

explain bonding and geometry of molecules and complex ions:

- Lewis electron-pair bond theory - Hybridization theory - Valence Shell Electron Pair Repulsion

(VSEPR) theory

Covalent Bonding Lewis Concepts

One covalent bond between two atoms results from the sharing of a pair of electrons between the two atoms.

This pair of electrons is called the bonding pair and is represented by a line connecting the two atoms

Covalent Bonding Lewis Concepts

Electrons that are not shared are not involved in the bond and are localized as lone-pairs (non-bonding electrons) on atoms within the molecule.
 One bonding pair one bond, three bonding pairs three bonds

(triple bond)

 These diagrams are called Lewis Diagrams

Using the concept that the electronic structure of the entire molecule is represented by the sum of all the bonding and lone pairs of electrons, Lewis diagrams can be drawn for a molecule or ion to represent the approximate arrangement of atoms and the valence electrons within the structure.

Deriving Lewis structures:

Here are nine points to take into account in deriving Lewis structures:
(i) (ii) (iii) (iv) (v) (vi) (vii) (viii) (ix) only valence electrons are used a simple (symmetrical) geometry is used to represent the shape of the molecule, or polyatomic ion metals must be the central atom, and H is peripheral. The least electronegative element is usually the central element the bond is represented by a dash or line each non hydrogen atom is given an octet (8 electrons). This is the OCTET RULE. There are exceptions to the Lewis octet rule. if any atom has less than an octet, multiple bonds may be used so that all atoms have an octet electrons not shared between atoms remain as lone pairs of electrons on the parent atom for a cation, subtract 1 electron for each +ve charge, and in the case of an anion, add 1 electron for each ve charge the entire structure of the molecule (ion) is represented by the sum of all bonding and lone pairs of electrons.

A stepwise approach to writing Lewis structures

 Step 1:

Determine the total number of valence electrons. Write the skeleton structure of the molecule. Use two valence electrons to form each bond in the skeleton structure. Try to satisfy the octets of the atoms by distributing the remaining valence electrons as nonbonding electrons (lone pairs). Use FC (formal charges) to decide which of more than 1 possible structures is correct.

 Step 2:  Step 3:

 Step 4:

Step 5:

A stepwise approach to writing Lewis structures

 Example

Derive the Lewis Structure for the chlorate ion ClO3-.

Step 1: Determine the total number of valence electrons.

 ClO3-: Cl has 7 valence electrons

= 7 e-

 Each O atom has 6 valence electrons (3 x 6) = 18 e add 1 electron for the negative charge=

Total

1e26 e-

Step 2: Write the skeleton structure of the molecule.

 a simple (symmetrical) geometry is used to represent

the shape

Cl

Step 3: Use two valence electrons to form each bond in the skeleton structure.

Cl

O
 Two electrons for each bond is 3x2 = 6 e-

This leaves 26 e (total) 6 e (bonding) = 20 nonbonding electrons

Step 4: Satisfy the octets of the atoms lone pairs

.. .... O

..
Cl

.. O .. ..

.. .... O

Molecules that Contain Too Few Electrons Multiple Bonds

 Sometimes the molecule does not have enough

valence electrons
 Cant get satisfactory Lewis structure by sharing

a single pair of electrons, then share two or even three pairs of electrons.
 Result double or triple bonds  Elements that form strong double or triple bonds

are C, N, O, P, and S

Molecules that Contain Too Few Electrons Multiple Bonds

 Example

Derive the Lewis Structure for the nitrate ion NO3-.

Molecules that Contain Too Few Electrons Multiple Bonds

 NO3-:N has 5 valence electrons  Each O atom has 6 valence electrons (3 x 6)  add 1 electron for the negative charge

= = =

Total

5 e18 e1e24 e-

 If we use only single bonds then the N atom would only have 6 valence

electrons ( 2 from each bond)

Lewis Structure

O N O O

Molecules that Contain Too Few Electrons Electron Deficient

 Consider BF3.  Note neither B nor F tends to form multiple bonds so B

will have only six valence electrons and the Lewis structure is written with less than an octet on B. Molecules that feature electron deficiency usually involve B, Be and sometimes Al.
What is the difference b/w an unsaturated system and an electron deficient one?

Molecules that Contain Too Many Electrons Valence Shell Expansion

 Consider SF4:  6 + 4(7) = 34 valence electrons  4 covalent bonds requires 8 e so S has its octet

 

26 nonbonding valence electrons remaining (34e 8e = 26e) Each fluorine atom needs 6e to satisfy its octet total 24 e

Molecules that Contain Too Many Electrons Valence Shell Expansion

  

But there are 26 nonbonding electrons in this molecule. We have an additional pair of valence electrons (26e 24 e = 2e) So we expand the valence shell of the sulfur atom to hold more than eight electrons.

How does sulfur hold 10 e Lewis Structure in its valence shell?

Other examples where octet rule does not apply

 Coordinate covalent bonds in coordination

compounds: -ligands as Lewis bases (electron-pair donors) -metals as Lewis acids (electron-pair acceptor) more in C10K!!!

Example of the use of FC in writing correct Lewis Structures

 Class Exercise:

Write the most favorable Lewis Formula, (Draw the most favorable Lewis Structure) for nitrosyl chloride, NOCl. (3 marks) Problems you might experience with this question: Two possible structures. Hint: which is preferable? Where do I put the double bond? Advice: Use formal charges (FC) to decide

More than 1 possible Lewis Formula?? Use Formal Charges (FC) to get correct formula
 FC is the hypothetical charge on an atom in a molecule or polyatomic

ion. Formal charges must add up to the actual charge on the species, that is 0 for molecules and the ionic charge for ions.

 The most energetically favorable Lewis Formula is the one in

which FC on each atom is 0 or as near to 0 as possible.  -structures placing negative formal charges on more electronegative elements are usually favored.

TO CALCULATE FC FC = (group number)-[(number of bonds) + (number of unshared electrons)]

 Complete Class Exercise:

Calculate the FC involved and then write the correct Lewis Formula for nitrosyl chloride, NOCl. Go to the board !

More than 1 correct Lewis Formula?? Consider Resonance

 Resonance structures have the same relative

placement of atoms but different locations of bonding and lone electron pairs. Below are the 3 resonance forms of CO32-.
O C O O
O

2-

O C O

2-

O C O O

2-

RESONANCE STRUCTURES ARE NOT REAL DEPICTIONS! For example, the diagram above implies that 2 single bonds and 1 double bond are present in the carbonate ion and the double arrow implies that the structure switches from one resonance form to the next. NOT TRUE!

Resonance - Example CO3 .

 IN FACT experimentally, it is observed that all C-O bonds are

2-

equal, and all the O-C-O bond angles are equal.  The real molecule has an electron distribution corresponding to the average of 3 contributing structures, and is said to be a resonance hybrid of the three structures.  Each individual resonance form has no real existence, but their average gives the actual structure:
O C O O 2resonance hybrid

Note this is different from the resonance forms of NOCl discussed in class. NOCl does not exist as a resonance hybrid since the atoms surrounding the central atom are different. Hence its structure is dominated by one of the resonance forms which is determined by the formal charges.

Have we achieved our objectives? CAN YOU:

 1. Describe how the elements form bonds with each other by sharing

electrons
 2. Derive Lewis structures for molecules or polyatomic ions.  3.Predict when resonance structures are possible and draw the

various structures????????? Attempt the next tutorial.

 Remember Lewis structures does not necessarily show shapes

so Next Class

Hybridization and Valence Shell Electron Pair Repulsion (VSEPR) Theory