CHEM 3013

ORGANIC CHEMISTRY I CHAPTER 1

LECTURE NOTES

1. Atomic orbitals
a. b. c. Heisenberg Uncertainty Principle The exact position of an electron cannot be specified; only the probability that it occupies a certain position of space. The electron can only exist in certain regions of space called atomic orbitals. The energy of an electron in a particular orbital has a very precise vale. i. ii. iii. Orbitals are described by two quantum numbers: The first descriptor is called the principal quantum numbers and is an interger value from one to seven. Electrons having higher numbers have higher energy. The second quantum number is called the angular(azimuthal) quantum numbers. It describes the shape of the orbital. The four letter descriptors of these shapes are s,p,d,f.

d. e.

Orbitals of higher principal quantum number have more nodes. Higher energy orbitals have the electron density located further from the nucleus.

node 1s orbital 2s orbital three 2p orbitals

Orbitals

2. Electronic Configuration a. Aufbau Rules Building the complex atoms of the periodic table.

3p 3s ENERGY 2p 2s

1s

Energy of different orbitals in a many electron atom

i. ii. iii.

Electrons are added to orbitals starting with those of lowest energy Only two orbitals per atomic orbital and these must differ in their spin quantum number (Pauli Exclusion Principal). For orbitals of equal energy, single electrons with identical spin are added untill the orbital is half-full, then the electrons of opposite spin are added (Hunds Rule).

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3p 3s ENERGY 2p 2s 2s ENERGY 2p 3s 3p

1s

1s

carbon 1s2 2s2 2p2

oxygen 1s2 2s2 2p4

Filling the orbitals of carbon and oxygen

3.

Ionic Bonding a. Inert Gas Configuration; Octet Rule. Certain elements in the periodic table are especially stable. These are the inert gases, helium, neon, argon,krypton, xenon and radon found in group 8A. The common features of these elements is that they all have a completely filled valence shell of electrons. Except for helium which has a filled shell of two electrons, all the remaining inert gases have 8 electrons in their outer shell. This special configuration can also be attained in other elements; it is the major driving force in the formation of ions (by gain or loss of electrons). Elements or ions which have a filled shell of electrons are said to obey the octet rule. b. Formation of ions. Much of chemistry can be understood in terms of the various elements' wish to gain the filled shell configuration. In the reaction of lithium with fluorine gas, both elements can satisfy the octet rule by transfer of one electron from the lithium to the fluorine. During this process the fluroine becomes a fluoride anion, the lithium a lithium cation. Both ions have the same configuration as neon.
The lithium half-reaction): Li (1s2 2s1) Elemental lithium, a source of one electron The fluorine half-reaction F (1s2 2s2 2p5) + 1 eSame electronic configuration as Ne 1 e- + Li+ (1s2) available electron Same electronic configuration as Ne F- (.....2p6)

Elemental fluorine, electron an acceptor of one needed electron Filled shell configuration by loss or gain of electrons

Elements at the left of the periodic table (like groups 1A and 2A) can most easily attain a filled shell configuration by donating electrons. Conversely, elements on the right side of the periodic table are converted to the octet configuration by accepting electrons.

c.

4.

Isoelectronic Chemical Species have the same electronic configuration. Thus the ions of O-2,F -, Ne, Li+ and Mg+2 are isoelectronic, having the numbers of protons which makes them distinct chemical entities. d. Electrostatic Attraction The simple attraction of oppositely charged particles which holds the ions together in an ionic solid. Covalent Bonding. a. Not all compounds are comprised of ions. In particular, many carbon compounds are not ionic. The reason for this difference can be found in the electronic configuration of carbon (1s2,2s 2,2p x1,2p y1). To gain a filled shell configuration, carbon would have to either gain or lose four electrons. This represents an energetically unfavorable situation. The solution to the bonding problem posed by carbon is to share electrons in a covalent bond. This type of bonding was proposed by G. N. Lewis in 1916. The formalism depicts bonding resulting from havinga pair of nuclei being shared between two nuclei. The models resulting from this formalism are called Lewis Structures. This model is the cornerstone of understanding organic reaction mechanisms and is exceptionally useful for electronic bookkeeping. b. Writing Lewis Structures i. ii. iii. iv. v. vi. Start with a central atom (usually the heaviest, but make it carbon if carbon is present). Place all the outer shell electrons on four imaginary sides. Don't pair electrons unless more than four are in the outer shell of an atom. Bring the other atoms of the molecule in to the central atom so that single electrons on the central atom can be paired with single electrons on the other atoms. If, after all atoms have been added, two adjacent atoms have unshared electrons, they share the unshared electrons to make multiple bonds. If the species is an ion, then add or subtract the appropriate number of electrons in order to obtain the charge of the ion. The final Lewis-dot structure should have eight electrons around all atoms except hydrogen,which has two. (There are a few exceptions to the octet rule but these usually don't involve compounds containing carbon.)
Covalent Bonding in methane C + 4H

Note that the hydrogen of methane have a helium closed shell and the carbon has a neon closed shell LEWIS STRUCTURES FOR COVALENT MOLECULES

H H C H or H C H H H
H

c. Unshared pairs. Not all electrons in a covalent compound are necessarliy involved in bonding; some structures have orbitals that contain unshared pairs of electrons. While these electrons are not used in determining the primary bonding arrangement of the covalent compound, they are of basic importance in determining how the compoundwill react in later reactions. In drawing Lewis Structures, the lone pairs are often not shown, but we shall draw them explicitly at this stage of the course. Lewis Structures are also useful in understanding the bonding of covalent compounds containing multiple bonds (double and triple).

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H H C H O H C H H C H O H

H3C H3C

CH3

dimethyl ether

unshared pairs

C O H3C

formaldehyde

Lewis structures with unshared pairs and/or multiple bonds

5.

VSEPR Theory a. The shape of a molecule can be predicted by allowing all the bonded and nonbonded electron pairs to move as far apart as possible. b. For the given number of different bonds and nonbonded pairs of electrons, the expected shapes would be as shown below.
Tetrahedral. WXYZ can be bonds or non-bonding electrons

Z W X A Y H H O H H N H H H

H C H

HOH = 104.5 bent

HNH = 107.3 pyramidal

HCH = 109.5 tetrahedral

Trigonal. XYZ can be bonds or non-bondingelectrons. X A Z Y

FBF = 120 planar

F F

Digonal (Linear). YZ can bebonds or non-bonding electrons X A Y

H

Bonds and geometry

6. Molecular Orbitals a. Quantum Mechanics tells us that combining two atomic orbitals leadsto two molecular orbitals. The positive combination is a bonding molecular orbital and the negative combination is an antibonding molecular orbital. The formation of a bond between two hydrogen atoms is a very favorable (104 Kcal/mole) process. This is because we put two electrons in a bonding MO downhill in energy. The combination of two atomic orbitals with spherical symmetry (e.g. 1s) generates a

MO with cylindrical symmetry (symmetric about the internuclear axis). This called a sigma () bond. b. An orbital is described as a probability function that defines the distribution of electron density in space, the overlap region of a MO, between the two nuclei has a considerably higher electron density. The covalent bond arises from the electrostatic attraction between the positive nuclei and the region of increased electron density.
Antibonding Combination Region of decreased electron density. E N E R G Y

Anti-bonding MO

Energy of isolated H atoms

sigma bond
+

Bonding Combination

Bonding MO

Overlap region of increased electron density

Molecular orbitals for the hydrogen molecule

7.

Hybrid Orbitals a. As a carbon atom begins to form bonds with up to four other atoms, the ground state electronic configuration of 1s2 2s2 2p2 is purturbed and begins to change. An electron in a 2s orbital is promoted into a 2p orbital and the new electronic configuration is 1s2 2s2 2px1 2py1 2pz1. Two-electron bonds are like small magnets, the bonds tend to repel each other. Forming four covalent bonds to carbon by using three p orbitals and one s orbital is not the best energetic situation. This situation would place the sigma bond formed using the s orbital quite close to the bonds formed from the three p orbitals. By undergoing hybridization, nature creates four new orbitals of lower energy called sp3 hybrid orbitals which now have a tetrahedral structure.
E N E R G Y

b.

2p 2s 1s 2s 1s

2p

2sp3

1s

Elemental carbon

Electron promoted to 2p orbital

Completely hybridized carbon in organic compounds

Hybridization in carbon

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8. Examples of sp 3 Compounds The value of this bonding model is that it gives the chemist the ability to predict the geometry of chemical structures. This can be seen in the case of water. The oxygen in water has a ground state electronic configuration of 1s2, 2s2, 2p x2, 2p y1, 2p x1.This would suggest that oxygen would form covalent bonds with hydrogens using the half-filled 1s orbitals of each hydrogen and the half-filled 2py and 2pz orbitals of oxygen. Thus, only two sigma bonds from oxygen to hydrogen, which would seem to suggest that water has a bent structure, with a HOH bond angle of 90 degrees (the angle of the 2py and 2pz orbitals with respect to each other). But does water have a 90 degree bent structure? NO! Hybridization results in the formation of four sp3 orbitals, two filled and two half-filled. The orientation of the four new orbitals is tetrahedral (109 degrees). When hydrogen covalently bonds to the two half-filled sp3 orbitals, the HOH bond angle is 109 degrees.
E N E R G Y

2p 2s 1s

mix 2s and all three 2p

1s

2sp

new hybrid orbitals

Elemental oxygen

Completely hybridized oxygen in water

H
Hybrid Orbitals of Oxygen in Water

9.

Other Hybridizations Other hybridization states exist for the carbon atom (and others) when the number of 2p orbitals mixed in with the 2s is less than three. Hybrid orbitals of sp2 are formed when only two of the three available 2p orbitals are mixed in. This now results in the formation of three "new" sp2 orbitals, which are oriented in a trigonal planar orientation ( they look like a three-bladed propeller). There is one un-hybridized 2p orbital left over, which is oriented perpendicular to the plane of the propeller.

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E N E R G Y

2p 2s 1s 2s 1s

2p

2p

mix 2s and two 2p orbitals 1s

sp2 hybridized carbon

new 2sp2 hybrid orbitals

Elemental carbon

Electron promoted to 2p orbital

2p sp2 sp2
sp2 Hybridization in carbon

sp2

Two carbon atoms of sp2 hybridization will combine to form a (sigma) and (pi) bond. It should be noted that a double bond is comprised of two two-electron bonds ( and ); this is why double bonds are shorter and stronger than single bonds. The bond is formed by end-on overlap of the carbon sp2 orbitals. It has cylindrical symmetry about the carbon-carbon bond axis. The bond is formed by sideways overlap of the two 2p orbitals. It is not cylindrically symmetric. A bond is about 1/2 as strong as a bond.
2 C(sp2) + 4 H(1s) ======> H2C=CH2 bond (two p orbitals)
H

+
H H

bond (two sp2 orbitals from the two carbons). Bonding

in sp2 Hybridized Carbons

Hybrid orbitals of sp hybridization are formed when one 2s and one 2p orbital are mixed together. A carbon atom which has sp hybridization has two sp orbitals (oriented at 180 from each other) and two orthogonal 2p orbitals.

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E N E R G Y

2p 2s 1s 2s 1s

2p

2p sp 1s
sp hybridized carbon

mix 2s and one 2p orbital

new hybrid orbitals

Elemental carbon

Electron promoted to 2p orbital

2p orbitals sp hybrid orbital

sp hybrid orbital

sp Hybridization in Carbon