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Molecular Bonding Part II

Molecular Bonding Part II

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Unit One Parts 3 & 4: molecular bonding

Unit One

Parts

3&4
Pages 34 & 46

Bond strength Bond polarisation

Resonance

Unit One

Parts

3&4
...today we continue to make our simple model more complex!

Bond strength Bond polarisation

Resonance

Pages 34 & 46

how strong are bonds?
...and we’re talking about covalent bonds...the important ones for organic chemists

bond strength
C C C C

the values aren’t important...only the concept / pattern

C C

>
C C C C
836 kJ mol–1 610 kJ mol–1

>
C C
347 kJ mol–1

Pg 40

bond strength
C C C C C C

>
C C
836 kJ mol–1

obviously, it takes C C more energy to break an alkyne apart...breaking three bonds not one

>
C C
347 kJ mol–1

610 kJ mol–1

Pg 40

bond strength
C C C C

the differences are getting smaller...nearly twice as much energy needed to break 2 bonds but much less needed to break the third

C C

>
C C C C
836 kJ mol–1 610 kJ mol–1

>
C C
347 kJ mol–1

Pg 40

but...

bond strength

C

C

C

C

a single σ bond is much stronger than a single π bond (head-tohead results in better overlap)

C

C

C

C

Pg 40

bond strength

C

C

C

C

...this is the reason alkenes are functional groups but alkanes are not!

C

C

C

C

Pg 40

are bond length and bond strength related?

what about bond lengths?

bond strength
←120→ C C ←134pm→ C C C ←154pm→ C
shorter the bond the stronger it normally is...

Pg 40

bond strength
←138→ C F ←178pm→ C Cl C ←193pm→ Br

C

F

Pg 40

C

Cl

C

Br

shorter the bond the stronger it normally is...better overlap of atoms / orbitals

how do we explain?

similar size and bond lengths but big difference in energy; why?

←134pm→ C C 610 kJ mol–1

←122pm→ C O 736 kJ mol–1

C
77 pm

O
73 pm
similar size so good orbital overlap...

so far, our picture of bonds has said electrons are shared evenly between two atoms...

bond polarisation

bond polarisation

...as always, we teach you a simple model and then say “reality is more complex!” So lets take a step back...

two kinds of bond...which one is it?

is HCl covalent or ionic?

Polar covalent bond
H Cl H+
electrons shared evenly in a covalent bond...or...

Cl–

H Cl

H

Cl

Pg 34

Polar covalent bond
H Cl
one electron lost from H and given to Cl (an ionic bond)

H+

Cl–

H Cl

H

Cl

Pg 34

Polar covalent bond
...or somewhere in the middle...

H

Cl

H Cl

δ+ δ–

H Cl

H

Cl

Pg 34

Polar covalent bond
H Cl

a covalent bond but with the electrons predominantly on one atom (ionic character)

H Cl

δ+ δ–

H Cl

H

Cl

Pg 34

H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 B 2.0 Al 1.5 C 2.5 Si 1.8 N 3.0 P 2.1 O 3.5 S 2.5 F 4.0 Cl 3.0 Br 2.8 I 2.5

electrons Bond Typerarely EN difference Examples shared evenly in a covalent bond...

Calculation 3.0(Cl) - 0.9(Na) = 2.1 3.5(O) - 2.1(H) = 1.4 3.0(Cl) - 2.1(H) = 0.9 2.5(C) - 2.1(H) = 0.4 2.1(H) - 2.1(H) = 0.0

ionic polar covalent covalent

> 1.7 0.5 – 1.7 0 – 0.4

NaCl CH3O–H H–Cl CH3–H H–H

Pg 35

H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 B 2.0 Al 1.5 C 2.5 Si 1.8 N 3.0 P 2.1 O 3.5 S 2.5 F 4.0 Cl 3.0 Br 2.8 I 2.5

Bond Type ionic

EN difference Examples > 1.7 NaCl CH3O–H H–Cl CH3–H H–H

Calculation 3.0(Cl) - 0.9(Na) = 2.1 3.5(O) - 2.1(H) = 1.4 3.0(Cl) - 2.1(H) = 0.9 2.5(C) - 2.1(H) = 0.4 2.1(H) - 2.1(H) = 0.0

...electrons will closer to polar covalent be0.5 – 1.7 the more electronegative atom...given by the Pauli scale above (bigger number covalent 0 – 0.4 more electronegative)

Pg 35

H 2.1 Li 1.0 Na 0.9 K 0.8 Rb 0.8 Be 1.5 Mg 1.2 Ca 1.0 Sr 1.0 B 2.0 Al 1.5 C 2.5 Si 1.8 N 3.0 P 2.1 O 3.5 S 2.5

...difference in value indicates the nature of the F bond... 4.0 Cl 3.0 Br 2.8 I 2.5

Bond Type ionic polar covalent covalent

EN difference Examples > 1.7 0.5 – 1.7 0 – 0.4 NaCl CH3O–H H–Cl CH3–H H–H

Calculation 3.0(Cl) - 0.9(Na) = 2.1 3.5(O) - 2.1(H) = 1.4 3.0(Cl) - 2.1(H) = 0.9 2.5(C) - 2.1(H) = 0.4 2.1(H) - 2.1(H) = 0.0

Pg 35

you do not need to learn these values!

!

polarisation explains reactivity
of molecules
H3C I
δ+ δ– δ+ O δ–

δ– means more electrons or partial negative charge

H

CH3

Mg δ– Br CH3

δ+

O δ–
δ+ δ+ δ–

H3C

OMe

polarisation explains reactivity
of molecules
H3C I
δ+ δ– δ+ O δ–

δ+ means lack of electrons or partial positive charge

H

CH3

Mg δ– Br CH3

δ+

O δ–
δ+ δ+ δ–

H3C

OMe

polarisation explains reactivity
of molecules
H3C I
δ+ δ– δ+ O δ–

H

CH3

δ+ (or slightly positive) part of a molecule will be δ+ attacked by... δ– Mg

O δ–
δ+ δ+ δ–

Br

CH3

H3C

OMe

polarisation explains reactivity
of molecules
...the negative part of a Grignard reagent...in fact we can explain most chemical δ+ δ– reactions by these δ–/+ H3C I charges

δ+ O

δ–

H

CH3

Mg δ– Br CH3

δ+

O δ–
δ+ δ+ δ–

H3C

OMe

polarisation explains carbonyl

bond strength (& reactivity)

so, carbonyl stronger bond than alkene because it has ionic bond character (electronic attraction between the two atoms)

C
CC

C
OO

δ+δ+ δ– δ–

polarisation explains carbonyl

bond strength (& reactivity)

C
CC

C
OO

δ+δ+ δ– δ–

but carbonyl also more reactive because the δ+ charge attracts electrons

so far, so good...

i hope!

so let's apply what we know...

draw nitromethane CH3NO2

C + 3H + N + 2 O

here are the constituent atoms...

Pg 45

C + 3H + N + 2 O

H O H C N O H

this structure obeys the octet rule

Pg 45

C + 3H + N + 2 O

H O H C N O H

≡HC
3

O N O

doesn’t look quite right...need to sort out formal charges

Pg 45

C + 3H + N + 2 O

H O H C N O H

≡HC
3

O N O

fc = 6-4-½(4)=0
top oxygen has no formal charge

Pg 45

C + 3H + N + 2 O

H O H C N O H

≡HC
3

O N O

fc = 5-0-½(8)=+1

nitrogen has a +1 charge

Pg 45

C + 3H + N + 2 O

H O H C N O H

≡HC
3

O N O

fc = 6-6-½(2)=-1
bottom oxygen has –1 charge

Pg 45

C + 3H + N + 2 O

H O H C N O H

≡HC
3

O N O

116 pm
so structure is this?? (one N=O bond and one N–O bond)

O O
Pg 45

H3C N
130 pm

so in theory it is all very easy...

but reality is a little more complex...

O H3C N
122 pm

Pg 46

O

turns out both N–O bonds are identical

O H3C N
122 pm

Pg 46

O

...they are somewhere in between a N–O bond and a N=O bond...a structure called a...

O H3C N
122 pm

Pg 46

hybrid

resonance

O

the two extremes are resonance structures...

Pg 46
O

O H3C N O H3C N

O H3C N O

O

resonance structures

reality is a resonance hybrid

Pg 46
O H3C N O

O H3C N O H3C N

O O

resonance structures

O H3C N O

we can convert the extremes by pushing electrons (not atoms)

Pg 46
O

H3C N O

O H3C N O

resonance structures

Pg 46
O H3C N O H3C N O O

O H3C N O

resonance structures
lets try and explain the relationship between resonance structures and resonance hybrids...

imagine you took one man...lets call him Peter...as one of your resonance structures

resonance structures

resonance structures

...and one spider as the other resonance structure...and now you combine them...

the resulting cross is no longer either a man or a spider...

resonance structures

...and it certainly isn’t something that flicks back and forth between the two...no instead you have a hybrid or...

resonance structures

© Marvel Comics

resonance hybrid

H C H C H

H C H H

H C C H

H C H

resonance structures

DO NOT EXIST

but are useful

H C H C H

H C H H

H C C H

H C H

resonance structures

DO NOT EXIST ier as &e

but are useful

raw od t

H C H C H

H C H H

H C C H

H C H

resonance structures

DO NOT EXIST ier as &e

but are useful

they are Lewis structures so obey octet rule so we can draw them...

raw od t

resonance hybrid
H C H C H H C H

E X I Simpossible TS Lewis structure

resonance hybrid
H C H C H H C H
...the Lewis structure no longer obeys octet rule (how many electrons on central C?)

E X I Simpossible TS Lewis structure

resonance hybrid
H
...the circle you draw in the centre of benzene is a resonance hybrid but the double bonds I draw make its chemistry easier to predict...

E X I Simpossible TS Lewis structure
H C C H H C H

only electrons move
only electrons move between resonance structures (and in reactions)

all atoms are stationary
...the atoms remain stationary

this is used to represent the movement of two electrons...

curly arrow

curly arrow

it is possibly the most important ‘scribble’ an organic chemist ever learns...

with this you can bin most text books and just predict reactions instead of learning them...

curly arrow

curly arrow

words cannot describe how wonderful I think this little doodle is!

how do we draw resonance structures?

so now we know what a resonance structure is...we need to be able to spot them and draw them...

...first part is relatively easy (or at least covered in earlier material!)

O H3C C O

1

Lewis structure

Pg 46

lone pairs π bonds

N ,C

C C

2

electrons .’ ‘
..pushable

now we need to identify which electrons can be moved or pushed (for some reason we always talk about pushing ‘curly arrows’

Pg 48

lone pairs of electrons are often ‘pushable’

lone pairs π bonds

N ,C

C C

2

electrons .’ ‘
..pushable

Pg 48

lone pairs π bonds

as are double (or triple) bonds...

N ,C

C C

2

electrons .’ ‘
..pushable

Pg 48

positive charges electronegative atoms atoms with ‘pushable’ electrons

C

C O C

3

the next step is to find a target for the electrons...somewhere they want to go...

receptors

Pg 48

positive charges electronegative atoms atoms with ‘pushable’ electrons
all of the above will happily accept electrons so are good receptors

C

C O C

3

receptors

Pg 48

positive charges
this is only a receptor because it can also loss electrons (remember we do not want more than eight 8 electrons around an atom)

C

electronegative atoms

C O C

3

atoms with ‘pushable’ electrons

receptors

Pg 48

positive charges electronegative atoms atoms with ‘pushable’ electrons

C

C O C

3

NOTE: the donor and acceptor must be one bond apart (no more no less)

receptors

Pg 48

O H3C C O H3C C

O H3C C O

O O

4

resonance

forms

finally, move the electrons and form a new, valid Lewis structure

Pg 48

O H3C C O H3C C

O H3C C O

O O

4

resonance

forms

here are three resonance structures for the molecule in steps one (the ethanoate anion)

Pg 48

O H3C C O H3C C

O H3C C O

O O

4

resonance

forms

remember the resonance hybrid will be somewhere in between all these as shown on the next slide...

Pg 48

delocalisation
H3C C
all bond lengths are the same...showing that the compound never has a single C–O bond or a double C=O bond

O O

O or H3C C O

1/ –

2

1/ –

2

C–O 130 pm

delocalisation
O H3C C O
the electrons are said to be delocalised over the three atoms (O–C–O)

O or H3C C O

1/ –

2

1/ –

2

C–O 130 pm

delocalisation
O H3C C O
electrons are happy when they are delocalised as they are spread over a larger area...so are further apart

O or H3C C O

1/ –

2

1/ –

2

C–O 130 pm

examples...
Ph H3C N C C H CH3

X

Ph H3C

N C C H CH3
why is this wrong? ...because it has 10 electrons in valence shell of C, which is never allowed!

examples...
Ph H3C N C C H CH3

the correct way involves pushing the lone pair of the nitrogen anion down one bond to make a double C=N bond and then pushing the electrons off the carbon (so that it doesn’t have 10 valence electrons) and...

examples...
Ph H3C N C C H CH3 Ph H3C N C C H
...moving them to the carbon at the end of the double bond (we can’t move them two bonds) and forming this new anion

CH3

examples...
Ph H3C N C C H CH3 Ph H3C N C C H CH3 Ph

N

δ–

C δ– CH3 H3C C H

the resonance hybrid shares (delocalises) the electrons over two bonds or three atoms...

examples...
we cannot move this double bond as there is no electron acceptor (and we can’t have 5 bonds or 10 valence electrons on C)

Ph H3C

N C C CH3

H H

X

Ph H3C

N C C CH3

H H

example...
the bonds in ethanoic acid are not what we would predict compared to other simple molecules...(C=O longer & C–O shorter)...why?

124pm

O

H3C C

129pm

O H ethanoic acid

H2 146pm H3C C O H ethanol

122pm

O

H3C C CH3 propanone

example...
O H3C C O H H3C
...reason is that lone pair of Oelectrons are pushable and O δ– the C=O is a good C receptor... H3C C

O H

O H

δ+

124pm

O

H3C C

129pm

O H ethanoic acid

H2 146pm H3C C O H ethanol

122pm

O

H3C C CH3 propanone

example...
O H3C C O H H3C C O H O

O δ– H3C C O H
δ+

124pm

O

H3C C

129pm

O H ethanoic acid

...which allows a new 122pm O H2 resonance structure that can contribute to the 146pm H3C C resonance hybrid and gives C H3C O the C–OH bond double H CH3 bond character so causes it ethanol to shrink... propanone

example...
H H H C C C C H C C H H H H C C H C C H C C H H H

H H

C C

C C H

C C

H H

why is phenol acidic?

or why is phenol a separate functional group and not an alcohol?

why is phenol acidic?

for a group to be acidic it must be able to give away H+ (a proton)

delocalisation...
O H H C C C C H C C H H
...if phenol losses H+ then we are left with O–...is this stable (will it readily form)?

delocalisation...
O H H C C C C H C C H H

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

...we can move the lone pair to form C=O as we can push the electrons of C=C...we have spread the electrons over three atoms so they are happy...

delocalisation...
O H H C C C C H C C H H

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

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

O C C H C C H H

Oδ– H δ– C δ– H C C H C C H C
δ–

H

turns out we can form many other resonance structures so the electrons are delocalised over 7 atoms...they are really jolly. So anion stable so loss of H+ easy so phenol is acidic

H3C CH3

CH3

CH3

H3C

CH3

CH3

CH3

H3C CH3

H3C CH3

CH3

CH3

H3C

CH3

CH3

CH3

conjugation

any double bonds separated by a one single bond can delocalise

H3C CH3

H3C CH3

CH3

CH3

H3C

CH3

CH3

CH3

H3C CH3

H3C CH3

CH3

CH3

H3C

CH3

conjugation

such double bonds are said to be conjugated

CH3

CH3

H3C CH3

H3C CH3

CH3

CH3

H3C

CH3

CH3

CH3

H3C CH3

H3C CH3

CH3

CH3

H3C

CH3

CH3

H3C CH CH3 conjugation 3
leads to coloured compounds...this is carotene from (you guessed it) carrots

conjugation

what have ....we learnt?

•e l e c t r o n s

Image created by Cary Sandvig of SGI

where they are •b o n d s & their strength • re s o n a n c e

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