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    Cha 1

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    Cha 1

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    Dav Sugo
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    CHA-1 (1)

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    Cha 1

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    Dav Sugo

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    of 30

    UNIT- ONE

    Bonding, Structure and


    Reactivity
    OUTLINES
     Historical background of organic chemistry

     Energy Levels and Atomic Orbitals

     Bonding in carbon compounds:


    Valence Bond Concept
    Orbital Hybridizations

    Molecular Orbital Concept

     Factors influencing electron availability and reactivity of organic


    compounds
    Inductive effect
    Resonance effect

    Steric effect
    INTRODUCTIONS
     What is organic chemistry?
    Organic chemistry is the study of carbon compounds.
    Carbon compounds are central to the structure of living
    organisms and therefore to the existence of life on earth.
     By the eighteenth century some scholars develop vital force
    theory.
     Compounds derived from living organisms were believed to
    contain an unmeasurable vital force that is the essence of life.
     These called “organic compound.”
    Cont…
     What makes carbon so special?

     Because of:-
    Positions of the carbon atom in the periodic table
    Carbon’s electronic structure: Carbon can form four
    strong covalent bonds. Furthermore, carbon atoms can
    bond to one another, forming long chains and rings.
    1.1. Energy Levels and Atomic Orbitals

     An atom contains a negatively charged electron and a small,


    dense nucleus made of neutrons and positively charged protons.
     Each element is characterized by a unique atomic number Z,
    which is equal to the number of protons in its nucleus.
     A neutral atom has equal numbers of protons, (positively
    charged) and electrons (negatively charged).
     Atomic orbital: a mathematical expression describing the
    probability of finding an electron at various locations; usually
    represented by the region of space around the nucleus where
    there is a high probability of finding an electron.

     Atomic orbitals are grouped into different shells (energy


    levels). Each shell is identified by a principal quantum number,
    n

     These numbers are assigned the values n = 1, 2, 3, 4, and so


    forth.
    Quantum numbers

     Quantum numbers are used to differentiate between electrons


    i. In quantum theory, each electron in an atom is assigned a
    set of four quantum numbers.
    ii. Three of these give the location of the electron, and the
    fourth gives the orientation of the electron within the orbital.
    1. The principal quantum number (n)

     describes the size of the orbital.


     For example, orbitals for which n = 2 are larger than those for
    which n = 1. The principal quantum number also indirectly
    describes the energy of an orbital.
    2. The angular quantum number or azimuthal quantum
    number (l)
     describes the shape of the orbital.
     The angular quantum number (l) can be any integer between 0
    and n - 1.
     For example, If n = 3, l can be 0, 1, or 2.
    Subshell Value of l
    s l=0
    p l=1
    d l=2
    f l=3

    3. Magnetic quantum number (ml)

     describes the orientation in space of a particular orbital.


     The magnetic quantum number (ml) can be any integer
    between -l and +l. If l = 2, ml can be -2, -1, 0, +1, or +2.
     The only allowed combination of quantum numbers for :
    n = 1 is

    n l ml Subshell
    name
    1 0 0 1s

    n=2 n l ml Subshell name


    2 0 0 2s
    2 1 -1
    2 1 0 2p
    2 1 1
     There is only one orbital in the 2s subshell. But,
     there are three orbitals in the 2p subshell and etc.
    4. The spin quantum number (ms)

     An orbital can hold no more than two electrons.


     One of the electrons in an orbital is arbitrarily assigned an m s

    quantum number of +1/2; the other is assigned an ms


    quantum number of -1/2.
    1.2. Bonding in carbon compounds
    1.2.1. Valence Bond Concept

     According to valence bond theory, a covalent bond forms


    when two atoms approach each other closely and a singly
    occupied orbital on one atom overlaps a singly occupied
    orbital on the other atom.
     In the H2 molecule, for example, the H–H bond results from
    the overlap of two singly occupied hydrogen 1s orbitals:
    1s 1s

    . . H2
    H H
     How close are the two nuclei in the H2 molecule?

    • If they are too close, they will repel each other because both
    are positively charged, if they’re too far apart, they won’t
    be able to share the bonding electrons.
    • There is an optimum distance between nuclei that leads to
    maximum stability called the bond length, this distance is
    74 pm in the H2 molecule.
    1.2.2. Orbital Hybridizations

     Hybridization refers to the process of mixing of atomic orbitals.

    • Combination of 2 or more atomic orbitals on the same atom to


    form a new set of “Hybrid Atomic Orbitals” used in bonding.
     sp3 Hybridization

    • In ground state, an isolated atom of carbon has the electron


    arrangement 1s2 2s2 2p2.
    • The 2s orbital is mixed with all three of the 2p orbitals to give a
    set of four sp3 hybrid orbitals.
    Energy

    2p2 2p3
    Promotion Hybridization

    2s2 2s1 Four sp3 hybrid orbitals

    1s2

    2s and one 2p AO One sp3 hybrid AO


    The four sp3 hybrid AOs point to the
    corners of a tetrahedron.
     When each of the four identical sp3 hybrid orbitals of a carbon
    atom overlaps with the 1s orbital of a hydrogen atom, four
    identical C–H bonds are formed and methane results

    C H
    H
    H
    ii. sp2 Hybridization

     one s orbital mixed with two p orbitals to make three equivalent


    sp2 orbitals, leaving one p orbital untouched.
     When a compound has a double bond, one of the two bonds is
    always a sigma bond.
     In ethene, each carbon forms three sigma bonds, one to each of
    the two hydrogens and one to the other carbon.
    Energy

    2p2 2p3
    Promotion Unhybridized 2p orbital
    Hybridization

    2s2 2s1 Three sp2 hybrid


    orbitals
    1s2

    • The three equivalent sp2 orbitals will arrange themselves in a


    trigonal planar configuration with bond angle 120.
    The CH bond results from
    overlap of a C sp2 AO with
    an H 1s AO

    This bond results from overlap This new type of overlap of a 2p


    of an sp2 AO on one C with an AO on each C results in a new
    type of bond, a pi bond
    sp2 AO on the other C
    iii. sp Hybridization

     A simple compound with a triple bond is ethyne (acetylene),


    HC≡CH.
     It is a linear molecule. One of the CC bonds is a sigma bond.
    The other two are pi bonds.

     The 2s orbital and one 2p orbital of carbon are hybridized to form


    two sp hybridized orbitals. The remaining two 2p orbitals are not
    hybridized.
    there are two 2p AOs, perpendicular to the sp hybrid
    AOs, remaining on each carbon.
    Energy

    2p2 2p3
    Promotion Hybridization Unhybridized
    2p orbitals
    2s2 2s1 Three sp hybrid
    orbitals

    1s2
    1.3. Factors influencing electron availability and reactivity of
    organic compounds

    1.3.1. Inductive effect


     An inductive effect results from the ability of an atom or group of atoms
    to withdraw or donate electrons through  bonds.

    Types of Inductive effect:


    i. Negative Inductive Effect (- I effect, Electron withdrawing effect):
    When an electronegative atom or group is attached, the electrons are
    displaced in the direction of the attached atom or group.
    -NO2 > -CN > -COOH > F > Cl > Br > I > OH > C6H5 > H
    ii. Positive Inductive effect (+I effect, Electron releasing effect):
    When an electro positive atom or group is attached, the electrons are
    displaced away from the attached atom or group.
    (CH3)3C- > (CH3)2CH- > -C2H5 > - CH3
    Example: Applications of Inductive effect
    Inductive effect is useful in explaining the strength of some organic acids
    and bases.

    HCOOH > CH3COOH > (CH3)2CHCOOH

    Reason: Acidic strength decreases as +I effect of the alkyl group


    increases.
     O2NCH2COOH > FCH2COOH >ClCH2COOH > BrCH2COOH>
    ICH2COOH > CH3COOH

    Reason: Acidic strength decreases as -I effect of the group or halogen


    decreases.

     Cl3CCOOH > Cl2CHCOOH> ClCH2COOH >CH3COOH

    Reason: Acidic strength decreases as the number of halogen atoms


    decreases.

     CH3CHClCOOH > CH2ClCH2COOH

    Reason: Acidic strength decreases as the distance of the halogen from


    carboxylic group increases.
    1.3.2. Resonance effect

     The representation of a molecule with two or more Lewis structures


    that differ only in the placement of their electrons is called resonance.

    Acetate ion

     A resonance effect reflects the ability of an atom or group of atoms to


    withdraw or donate electrons through π bonds. This is also sometimes
    referred to as a mesomeric effect
    Types of resonance effects

    i. Negative resonance effect (-R effect): When the electron displacement


    is towards the group. Example: -NO2 , -CHO
    O O

    CH2CHCH CH2CHCH

    ii. Positive resonance effect (+R effect): When the electron displacement
    is away from the group. Example: -OH , -OR, -Cl

    CH2CHOH CH2CHOH
     


    Applications of Resonance effect reading assignment.
    1.3.3. Steric effect
     The presence of bulky or crowded substituents around the reactive site
    of a molecule can affect the reactivity of that molecule.
     Large atoms or groups influence the manner in which molecules
    collide, often deflecting the reactants away from the angle or depth of
    collision necessary for the reaction to occur.
     For instance, CH3CH2Br is less crowded at the carbon bearing the Br

    atom than (CH3)3CBr, and hence, a difference in reactivity between


    these compounds is expected.

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