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molecular bonding
Unit One
Parts 3&4
Bond strength
Bond polarisation Pages
Resonance 34 & 46
Unit One
Parts 3&4
...today we continue
to make our simple
model more
complex!
Bond strength
Bond polarisation Pages
Resonance 34 & 46
how strong are
bonds?
C C C C C C
> >
C C C C C C
C C C C C C
C C C C C C
> >
C C C C C C
a single σ bond is
much stronger than a
single π bond (head-to-
head results in better
overlap)
C C C C
Pg
40
bond C C
strength
C C
C C C C
Pg
40
are bond length
and bond strength
related?
←134pm→
C C
←154pm→
C C
Pg
40
bond Pg
strength 40
C F
←138→
C F
C Cl
←178pm→
C Cl
←193pm→
C Br 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→ ←122pm→
C C C O
610 kJ mol–1 736 kJ mol–1
C O
similar size so
good orbital
overlap...
77 pm 73 pm
so far, our picture of
bonds has said
electrons are shared
evenly between two
atoms...
bond polarisation
...as always, we teach
you a simple model
bond polarisation 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+ Cl–
electrons shared
evenly in a covalent
bond...or...
H Cl H Cl
Pg
34
Polar covalent bond
H Cl H+ Cl–
H Cl H Cl
Pg
34
Polar covalent bond
...or somewhere in
the middle...
H Cl
δ+ δ–
H Cl H Cl H Cl
Pg
34
Polar covalent bond
δ+ δ–
H Cl H Cl H Cl
Pg
34
H
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca Br
0.8 1.0 2.8
Rb Sr I
0.8 1.0 2.5
EN
Bond Typerarelydifference
electrons Examples Calculation
shared evenly in a
covalent bond...
ionic > 1.7 NaCl 3.0(Cl) - 0.9(Na) = 2.1
covalent 0 – 0.4
CH3–H 2.5(C) - 2.1(H) = 0.4 Pg
H–H 2.1(H) - 2.1(H) = 0.0
35
H
2.1
Li Be B C N O F
1.0 1.5 2.0 2.5 3.0 3.5 4.0
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca Br
0.8 1.0 2.8
Rb Sr I
0.8 1.0 2.5
EN
Bond Type difference Examples Calculation
Na Mg Al Si P S Cl
0.9 1.2 1.5 1.8 2.1 2.5 3.0
K Ca Br
0.8 1.0 2.8
Rb Sr I
0.8 1.0 2.5
EN
Bond Type difference Examples Calculation
covalent 0 – 0.4
CH3–H 2.5(C) - 2.1(H) = 0.4 Pg
H–H 2.1(H) - 2.1(H) = 0.0
35
you do not need
!
to learn these values!
polarisation δ– means more
explains reactivity
electrons or partial
negative charge
of molecules
δ+ δ– δ–
H3C I δ+ O CH3
H
δ+ O δ–
Mg δ– δ+ δ+
Br CH3
H3C OMe
δ–
polarisation
explains reactivity δ+ means lack of
electrons or partial
δ+ δ– δ–
H3C I δ+ O CH3
H
δ+ O δ–
Mg δ– δ+ δ+
Br CH3
H3C OMe
δ–
polarisation
explains reactivity
of molecules
δ+ δ– δ–
H3C I δ+ O CH3
H
δ+ (or slightly
positive) part of a
molecule will be
δ+
attacked by...
O δ–
Mg δ– δ+ δ+
Br CH3
H3C OMe
δ–
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– δ–
H3C I
charges
δ+ O CH3
H
δ+ O δ–
Mg δ– δ+ δ+
Br CH3
H3C OMe
δ–
polarisation
explains carbonyl
so, carbonyl
stronger bond than alkene
C C
δ+δ+ δ–δ–
CC OO
polarisation
explains carbonyl
bond strength (& reactivity)
δ+δ+ δ–δ–
CC OO
so far, so good...
i hope!
so let's apply what
we know...
draw nitromethane
CH3NO2
here are the
constituent
C + 3H + N + 2 O atoms...
Pg
45
H O this structure
obeys the octet
C + 3H + N + 2 O H C N rule
H O
Pg
45
H O O
C + 3H + N + 2 O H C N
O
≡HC
3 N
H O
doesn’t look
quite right...need
to sort out
formal charges
Pg
45
H O O
C + 3H + N + 2 O H C N
O
≡HC
3 N
H O
fc = 6-4-½(4)=0
top oxygen
has no formal
charge
Pg
45
H O O
C + 3H + N + 2 O H C N
O
≡HC 3 N
H O
fc = 5-0-½(8)=+1
nitrogen has a
+1 charge
Pg
45
H O O
C + 3H + N + 2 O H C N
O
≡HC3 N
H O
fc = 6-6-½(2)=-1
bottom
oxygen has –1
charge
Pg
45
H O O
C + 3H + N + 2 O H C N
O
≡HC
3 N
H O
116 pm O
H3C N
so structure is
this?? (one N=O
bond and one
130 pm
N–O bond)
O Pg
45
so in theory it is all
very easy...
but reality is a little
more complex...
Pg
O 46
H3C N
122 pm
O
turns out both
N–O bonds
are identical
Pg
O 46
H3C N
122 pm
O
...they are somewhere
in between a N–O bond
and a N=O bond...a
structure called a...
Pg
O 46
H3C N
122 pm
O
resonance
hybrid
the two Pg
extremes are
resonance 46
structures...
O O O
H3C N
O
H3C N ≡ H3C N
O O
resonance
structures
reality is a Pg
resonance
hybrid 46
O O O
H3C N
O
H3C N ≡ H3C N
O O
resonance
structures
we can convert
Pg
the extremes by
pushing electrons
46
(not atoms)
O O O
H3C N
O
H3C N ≡ H3C N
O O
resonance
structures
Pg
46
O O O
H3C N
O
H3C N ≡ H3C N
O 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
...and one spider as
the other resonance
resonance
structure...and now
you combine them...
structures
the resulting cross is
resonance
no longer either a
man or a spider...
structures
...and it certainly
isn’t something that
resonance
flicks back and forth
between the two...no
instead you have a
structures
hybrid or...
resonance
© Marvel Comics
hybrid
H H H H
C C C C
H C H H C H
H H
resonance structures
DO NOT EXIST
but are useful
H H H H
C C C C
H C H H C H
H H
resonance structures
DO NOT EXIST
&e a s ie r
but are useful to dr a w
H H H H
C C C C
H C H H C H
H H
resonance structures
DO NOT EXIST
&e a s ie r
they are Lewis
structures so obey
dr a
draw them...
to
resonance hybrid
E X I S T S
Lewis structure impossible
H H
C C
H C H
H
resonance hybrid
E X I S T S
Lewis structure impossible
H H
C C
...the Lewis structure
H C H no longer obeys
octet rule (how many
electrons on central
H C?)
resonance hybrid
E X I S T S
Lewis structure impossible
H H
...the circle you draw in C C
the centre of benzene is a
resonance hybrid but the
H C H
double bonds I draw make
its chemistry easier to
predict...
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
it is possibly the
most important
curly
‘scribble’ an
organic chemist
ever learns...
arrow
with this you can bin
most text books and
just predict reactions
instead of learning
them...
curly
arrow
words cannot
describe how
curly
wonderful I think
this little doodle
is!
arrow
how do we draw
resonance structures?
O
H3C C
1
O
Lewis Pg
structure 46
lone pairs N ,C
π bonds C C
2
now we need to identify
which electrons can be
moved or pushed (for
‘electrons .’
..pushable
some reason we always
talk about pushing Pg
48
‘curly arrows’
lone pairs of
electrons are often
‘pushable’
lone pairs N ,C
π bonds C C
2
‘electrons .’
..pushable Pg
48
as are double (or
triple) bonds...
lone pairs N ,C
π bonds C C
2
‘electrons .’
..pushable Pg
48
positive charges C
electronegative C O
atoms
atoms with C
‘pushable’ electrons
3
the next step is to find
a target for the
electrons...somewhere
they want to go...
Pg
receptors 48
positive charges C
electronegative C O
atoms
atoms with C
‘pushable’ electrons
3
all of the above will
happily accept
electrons so are good
receptors
Pg
receptors 48
positive charges C
this is only a receptor
because it can also loss
electronegative
electrons (remember we do
C O
atoms
not want more than eight 8
electrons around an atom)
atoms with C
‘pushable’ electrons
3 receptors
Pg
48
positive charges C
electronegative C O
atoms
atoms with C
‘pushable’ electrons
3
NOTE: the donor and
acceptor must be
one bond apart (no
more no less)
Pg
receptors 48
O O O
H3C C H3C C H3C C
O O O
4
finally, move the
electrons and form a
new, valid Lewis
resonancestructure
Pg
forms 48
O O O
H3C C H3C C H3C C
O O O
4
here are three
resonance structures
for the molecule in
resonance
steps one (the
ethanoate anion) Pg
forms 48
O O O
H3C C H3C C H3C C
O O O
4
remember the
resonance hybrid will
be somewhere in
between all these as
resonance
shown on the next
Pg
forms
slide...
48
delocalisation
all bond lengths are
the same...showing
that the compound
1
O
never has a single C–O
bond or a double C=O
O – / 2
bond
H3C C or H3C C
1
O O – / 2
C–O 130 pm
delocalisation
1
O O – / 2
H3C C or H3C C
1
O O – / 2
C–O 130 pm
the electrons are said
to be delocalised
over the three atoms
(O–C–O)
delocalisation
1
O O – / 2
H3C C or H3C C
1
O O – / 2
C–O 130 pm
electrons are happy
when they are
delocalised as they are
spread over a larger
area...so are further
apart
examples...
Ph Ph
X
N N
C CH3 C CH3
H3C C H3C C
H H
why is this wrong?
...because it has 10
electrons in valence
shell of C, which is
never allowed!
examples... 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
Ph 10 valence electrons)
N and...
C CH3
H3C C
H
examples...
Ph Ph
N N
C CH3 C CH3
H3C C H3C C
H H
H3C
C
C
CH3
H3C
C
C
CH3 ≡ H3C
C δ– CH3
C
H H H
Ph Ph
X
N N
C CH3 C CH3
H3C C H3C C
H H 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 122pm
O H2 O
129pm H3C C 146pm H3C C
H3C C
O H O H CH3
ethanoic acid ethanol propanone
example...
...reason is that lone pair of
O Oelectrons are pushable and O δ–
H3C C H3C C
O H
≡
the C=O is a good
receptor... H3C C
δ+
O H O H
124pm 122pm
O H2 O
129pm H3C C 146pm H3C C
H3C C
O H O H CH3
ethanoic acid ethanol propanone
example...
O O O δ–
H3C C H3C C
O H
≡ H3C C
δ+
O H O H
H3C
H3C CH3 CH3 CH3
conjugation
delocalise
H3C
H3C CH3 CH3 CH3
H3C
H3C CH3 CH3 CH3
conjugation
H3C
H3C CH3 CH3 CH3
H3C
H3C CH3 CH3 CH3
conjugation
(you guessed it)
carrots
what have
....we learnt?
•e l e c t r o n s
where they are
•b o n d s
& their strength
Image created by Cary Sandvig of SGI
• re s o n a n c e