CHAPTER

Fundamental Principles and Special Topics

One begins a study of reaction mechanisms by examining some of the basic principles. A basic understanding of these concepts helps largely in understanding of reactions and their mechanisms. Thiols undergo an oxidative coupling when treated with mild oxidizing agents to give disulphides: 2RSH + H2O2 RSRS + 2H2O. The understanding of this reaction requires a knowledge of bond dissociation energy. The bond dissociation energy of the SH bond of thiols (~ 80 kcal/mol) is much lower than the OH bond of alcohols (~ 100 kcal/mol). It is this weakness of the SH bond which allows thiols to undergo an oxidative coupling, and the alcohols do not display this reaction. On treatment with oxidizing agents, oxidation at the weaker CH bond (~ 85 kcal/mol) takes place rather than at the strong OH bond. Thus a knowledge of the nature and strength of bonds is essential for the chemical investigation of organic molecules. Similarly the properties of molecules are influenced by their structure.

1.1 STRUCTURE AND BONDING IN ORGANIC COMPOUNDS

A. Atomic Orbitals The motion of the electrons around the nucleus can be described by wave equations. The solutions to these equations are atomic orbitals, which roughly delineate regions in space where there is a high probability of finding the electron. An s orbital is spherical; a p orbital looks like two touching spheres, or a spherical figure eight (Scheme 1.1). The sign of the orbital can be positive, negative, or zero (node). These signs do not represent positive or negative charges, since both lobes of an electron cloud must be negatively charged. They refer to the signs of
y
nodal plane

y z x z
1s orbital

x z y
2px orbital

2px, 2py, and 2pz orbitals superimposed

SCHEME 1.1

Organic Reactions and their Mechanisms

the wave function . When two parts of an orbital are separated by a node, always has opposite signs on the two sides of the node. With increasing energy, there is an increasing number of nodes. Each orbital can be occupied by a maximum of two electrons of opposite spin (Pauli exclusion principle, Hunds rule). B. Molecular Orbitals and Bonding In the molecular orbital method, a bond is formed when two atomic orbitals overlap. Atomic orbitals of the same sign overlap to give a bonding molecular orbital of lower energy. Atomic orbitals of opposite sign give rise to an antibonding molecular orbital of higher energy and containing a node. The number of molecular orbitals is equal to the number of atomic orbitals from which they derive. The overlap of atomic orbitals leads to the formation of sigma and pi bonds. Bonds made by overlap along the internuclear axis are called bonds (as in H2, I; HF, II; F2, III, Scheme 1.2) and those made by overlap of p orbitals perpendicular to the internuclear axis are called bonds. (Scheme 1.2).

+
1s

+
2px s bond

2p

+
2p

1s 1s s bond

s bond

+
H2 (I)

+
d+ HF d (II)

F2

2p

2p

p bond

(III)

SCHEME 1.2

The hydrogen molecule is cylindrically symmetrical about a straight line drawn through the two nuclei and a cross-section of the molecular orbital when cut perpendicular to the bond axis is circular. This type of molecular orbital is termed orbital or bond. Similarly in the molecule of HF, the bond is again cylindrically symmetrical about a line passing through the two nuclei. The electrons in the bond of HF are however, not shared equally between the two dissimilar atoms of different electronegativities and unlike in H2 or F2 in HF, the electron distribution is highly polarized (Scheme 1.2). C. Hybrid Orbitals: Bonding in Complex Molecules Hybridization of atomic orbitals accounts for observed bond angles and molecular geometries of the molecules. (i) sp Hybrids give Linear Structures In e.g., beryllium hydride BeH2, formation, consider the following points. In its ground state the beryllium atom has 1s2 2s2 electronic configuration. Only a small amount of energy is needed to promote one electron from the 2s orbital to one of the 2p levels. In the 1s2 2s1 2p1 configuration (I, Scheme 1.3) beryllium could enter into bonding, as now two singly filled atomic orbitals are available for overlap. Energy lost in possible promotion of an electron from the 2s orbital to one of the 2p levels could be regained by bond formation. A bond formation could occur by overlap of the 2s orbital of Be with the 1s orbital of one H, on the one hand and the 2p

Fundamental Principles and Special Topics

orbital of Be with second H, on the other (Scheme 1.3). This possible arrangement would give two different bonds of unequal length and at an angle. Theory of electron repulsion, however predicts that compounds like BeH2 to have linear structure with the bonds to Be of equal length (Scheme 1.3).
2 H 1s

Be H
Not correct

2s 2p

Be

(I)

Hybridization

Back lobe 2 H Front lobe

180 HBeH
Correct

Be 180

sp

sp

Hybridization in beryllium to create two sp hybrids

SCHEME 1.3

A way to explain the geometry of BeH2 and other molecules is the approach called orbital hybridization. Like mixing of atomic orbitals on different atoms to give molecular orbitals, the mixing of atomic orbitals on the same atom gives new hybrid orbital. In beryllium, mixing the 2s and one of the 2p wave functions gives two new hybrids, called sp orbitals, made up of 50% s and 50% p character. This process rearranges the orbital lobes in space (Scheme 1.3). The major parts of the orbitals (front lobes) point away from each other at an angle of 180. There are two additional minor back lobes (one for each sp hybrid) with opposite sign. The remaining two p orbitals are unchanged and overlap with the two hydrogen 1s orbitals gives linear BeH2. Thus a 2s and a 2p orbital mix in a sp hybridization to give two linear sp hybrids and the remaining two p orbitals remain unchanged. This bonding is found both in alkynes and nitriles. The nitrogen and carbon atom of a nitrile group (C N) are both sp hybridized. (ii) sp2 Hybrids give rise to Trigonal Structures Structure of Borane (BH3) has a triangular (trigonal planar) shape with the equivalent boronhydrogen bonds. In its ground state boron has the electronic configuration 1s2 2s2 2p1. Promotion of a 2s electron to one of the 2p levels gives three singly filled atomic orbitals (one 2s two 2p) necessary for the formation of three bonds (Scheme 1.4). Mixing these three orbitals gives three equivalent hybrid orbitals which are sp2. These have one part the character of an s orbital and two parts the character of p orbital. These orbitals are pointed toward the corners of an equilateral triangle with angles of 120 between their axes. The formation of borane is via the overlap of each of these three sp2 orbitals with s orbitals of three hydrogen atoms. The sp2 hybridization also offers a satisfactory model for carbon atoms which form double bonds.

4
2py 2s

Organic Reactions and their Mechanisms

H 120 B
2px Hybridization . 3 H

: H

Three sp hybrid orbitals

H
Triangular structure of BH3

1s 2 s 2 p x

5B 2

SCHEME 1.4

Trigonal boranes BH3 and BF3 have an empty 2p orbital. There is no positive charge on these compounds, but both are Lewis acids and react like cations (Scheme 1.4a).
Empty 2p orbital

: :

:F :

: :: :

Empty 2p orbital

+ BH3 H BH2

The p bond is electron rich and borane electron poor. In hydroboration the p bond of alkene acts as nucleophile and reacts with the strong Lewis acid BH3.

SCHEME 1.4a

(iii) sp3 Hybridization gives Tetrahedral Shape In the case of carbon the promotion of one electron from 2s to 2p leads to four singly filled orbitals for bonding (Scheme 1.4b). The shape of the four CH bonds of methane in space with minimum electron repulsion is tetrahedral. For this geometry the 2s orbital on carbon is hybridized with all three 2p orbitals to give four equivalent sp3 orbitals with a tetrahedral arrangement (symmetrical arrangement) and each occupied by one electron. The overlap with e.g., four hydrogen 1s orbitals gives methane.

H H H C H

: :

:F

: F:

: :

: :

H:

:F

F: F:

: F: B

F:

Fundamental Principles and Special Topics

2py

H 4
Hybridization

109.5 C H H

4(H) H
2px
6C 2 2 1 1

2pz Carbon atom with an electron promoted from the 2s orbital to the 2pz orbital (1s )2s , 2px, 2py, 2pz 1s Four sp 3 hybrid atomic orbitals
2 1
1 1 1

1 s 2 s 2 px 2 py

1s 2(sp )2(sp )2(sp )2(sp )

1s

2s

2p
3

Structure of methane, CH4 showing four equivalent s bonds (ssp molecular bond orbitals) and tetrahedral structure
SCHEME 1.4b

A Double Bond (trigonal) hybridized carbon in e.g., a carbon-carbon double bond in Consider the ethene which is a flat molecule with bond angles close to 120. Hybridization of the 2s orbital and two of the 2p orbitals leads to three equivalent sp2 hybrid orbitals and one unhybridized 2p orbital (Scheme 1.4c) on each carbon. In ethene the CC bond is an sp2sp2 molecular bond while the CH bonds are ssp2 molecular bonds. The bond results from the parallel overlap through space of the p orbitals.
p 1s 2s2px2py2pz
2 1 1 1 1

sp2

or
1s 2s 2p

hybridize 2s and 2p orbitals

sp

C sp2
2

sp2

Carbon atom with an electron promoted from the 2s orbital to the 2pz orbital
2 2 2

An sp hybridized carbon

1s 2(sp )2(sp )2(sp )2p or

p-bond sp 2 1s 2p Three sp . hybrid orbitals 2H 1s (orbital)
2

p H C H

p H C sp2 H

H C H

s bond

H C H

Ethene

SCHEME 1.4c