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Universidade Estadual de Campinas

Instituto de Química
Departamento de Química Orgânica

QO427- Química Orgânica I


(Engenharia Química)

Profa. Dra. Denize C. Favaro


Ter: 19/21:00 IQ01 Sala: A5-105B
Sex: 21/23:00 IQ01
E-mail: denfavaro@iqm.unicamp.br

1
PROGRAMA DE DISCIPLINA

CÓDIGO: QO427
NOME: QUÍMICA ORGÂNICA I (Engenharia Química)

EMENTA
Orbitais híbridos. Hidrocarbonetos. Petróleo. Benzeno e
derivados. Haletos orgânicos. Álcoois. Éteres. Ácidos
carboxílicos e derivados. Aldeídos e cetonas. Aminas.
Compostos heterocíclicos. Polímeros. Noções de estereoquímica.

BIBLIOGRAFIA

2
Bibliografia
L. G. Wade, Jr., Organic Chemistry, Prentice Hall-International Inc., 1987.

J. McMurry, Química Orgânica, Thomson Learning Ltda., 6a. Ed., 2005.

P. Y., Bruice, Química Orgânica, Pearson Prentice Hall, S. Paulo, 4a. Ed.,
2006.

R. C. Atkins and F. A. Carey, Organic Chemistry - A Brief Course, McGraw-


Hill Public. Co., 1990.

T. W. G. Solomons, Química Orgânica, Livros Técnicos e Científicos


Editora S.A., 1983.

3
Programa
1. Estrutura e propriedade do carbono;
2. Alcanos, Alcenos e Alcinos;
3. Introdução a Estereoquímica;
4. Cicloalcanos: conformações;
5. Benzeno e Derivados;
6. Petróleo
7. Haletos de Alquila;
8. Álcoois, éteres, ácidos carboxílicos e derivados;
9. Aldeídos e cetonas
10. Aminas
11. Compostos Hetereocíclicos
12. Polímeros
4
Avaliações

Três (3) provas cuja avaliação será de 0-10 e


a nota final será dada pela media simples
das 3 notas obtidas:

M= (P1+ P2 + P3)/3

5
Calendário de Avaliações

12/09: Prova 1;
17/10: Prova 2;
28/11: Prova 3;
12/12: Exame Final.
6
Revisão

7
Origens da Química Orgânica

1780: Compostos Orgânicos: compostos que podiam Vitalismo


ser obtidos de organismos vivos;

Compostos Inorgânicos: fontes não vivas.

1828 – 1850: grande número de composto “orgânicos” foram sintetizados a partir de


fontes “inorgânicas”.
O
calor
NH4+NCO- C
1828: Friedrich Wöhler H2N NH2

Cianato de amônio Ureia

Química Orgânica: Química dos compostos de carbono.


8
Química Orgânica: Química dos
compostos de carbono

9
O que torna o C tão especial?
Diferentemente de outros elementos, o C forma ligações fortes
com outros átomos de C e uma variedade de outros elementos.

10
Estrutura das moléculas

Propriedades dos compostos são determinadas não apenas pela


composição atômica, mas também pelo arranjo espacial dos
átomos.

Loop Ω (154-174) W167/L168


Loop β5-β6
(221-230) Loop P(95-119)

SAV(V130)

STFK(S81-K84)

Ambos compostos por átomos


de C, mas as propriedades
físicas e químicas são
diferentes. 11
Ligações Químicas

12
Ligações Químicas

Ligação Iônica: Formada pela transferência de 1 ou mais


elétrons de um átomo para o outro para formar íons

Ligação Covalente: Ligação que resulta quando os átomos


compartilham elétrons

Idéia central do trabalho de Lewis: Átomos sem a


configuração eletrônica de um gás nobre geralmente
reagem para produzir tal configuração.
13
Ligações Iônicas
Ligações Iônicas: transferência de um ou mais elétrons de um
átomo para o outro (formando íons). Reação entre átomos com
eletronegatividade bem diferentes.

element H
(EN) (2.1)
Li Be B C N O F
……..………
(1.0) (1.6) (2.0) (2.5) (3.0) (3.5) (4.0)
Na Mg Si P S Cl
………………...……
(0.9) (1.2) (1.8) (2.1) (2.5) (3.0)
K Br
………………………..…………………………………
(0.8) (2.8)
Rb I
………………………………………………..…………
(0.8) (2.5)
Cs
……………………………………………………………………
(0.7)

14
Compostos iônicos – geralmente chamados de sais (altos pontos de fusão
e ebulição); conduzem eletricidade em solução aquosa, por exemplo.

Por que esses íons se formam?


Teoria de Lewis-Kössel: ficar com o octeto completo
Doa 1 e- para

Na Cl
1s2 2s2 2p6 3s1 1s2 2s2 2p6 3s2 3p5
(1 e- na CV) (7 e- na CV)
Ligação Iônica

Na+ Cl–
1s2 2s2 2p6 1s2 2s2 2p6 3s2 3p6

8 8
15
Ligações Covalentes
Mesma/próxima eletronegatividades à envolve o
compartilhamento de elétrons.

16
v  Íons também podem conter ligações covalentes.

H
H+ N
N H H
H H
H H
(ammonia) (ammonium cation)
(3 bonds on N) (4 bonds on N with
a positive charge on N)

17
Estruturas de Lewis

Cada traço representa um par de elétrons compartilhado por


dois átomos.

18
Estruturas de Lewis
LIGAÇÕES MÚLTIPLAS E PAR DE ELÉTRONS NÃO LIGANTES.

19
Carga Formal: Número total de elétrons de valência do átomo

neutro livre (Z) – Número de ligações que o átomo faz na

molécula (N˚L) – Número de elétrons não compartilhados (NC);

CF = Z – N˚L - NC
A soma das cargas formais é igual à carga da molécula ou íon.

Obs: Cargas formais não representam as cargas reais sobre os

átomos.

20
Atribua a carga formal ao átomo colorido em cada
uma das seguintes estruturas:

21
Isomerismo: Importância das
fórmulas estruturais

C3H6O

D i f e r e n ç a n a
conectividade dos
átomos à Isômeros
constitucionais

C2H6O

22
Tipos de ligações Covalentes

Cl-Cl Ligação covalente não-polar

Ligação covalente polar: Ligação covalente polar:


mólecula apolar mólecula polar
23
Ressonância (Linus Pauling): Duas estruturas de Lewis “coexistem”

O O
Estruturas de Lewis corretas
O O ou O O

Apenas mudados as posições dos O


O
elétrons. Os átomos NÃO mudam O O O O

O Raio-X: Ligações mesmo comprimento


-1/2 O -1/2
O daí a teoria de ressonância

I.  Nenhuma das estruturas de ressonância é a representação correta da molécula ou

íon. Nenhuma está completamente de acordo com as propriedades físicas e

químicas da substância. Estruturas de Ressonância só existem no PAPEL;

II.  A molécula ou íon: melhor representada pelo híbrido (média) dessas

estruturas 24
Híbridos de Ressonância: Elétrons
deslocalizados

I.  Estruturas de ressonância só existem em


teoria, jamais poderiam ser isoladas

II.  A molécula real será melhor representada


por um híbrido dessas estruturas

25
III. Quanto mais estável uma estrutura – maior sua contribuição para o híbrido.

1.  Octeto completo;

2.  N˚ de ligações covalentes;

3.  Separação de cargas

26
Regras para desenhar estruturas de ressonância

a)  Somente os elétrons se movem. O núcleo dos átomos nunca se move.

b)  Os únicos elétrons que podem se mover são os elétrons π e elétrons

não compartilhados.

c)  O n˚ total de elétrons na molécula não muda.

Os elétrons podem ser movidos de acordo com uma das seguintes

formas:

a)  Mover elétrons π em direção à carga positiva – exemplo 1.

b)  Mover elétrons livres (NC) ou elétrons π em direção à ligação π –

exemplo 2.
27
Obs1. Os elétrons não se movem em direção a um carbono

hibridizado sp3 – não pode acomodar mais elétrons;

Obs2. Cada contribuinte de ressonância deve ter a mesma carga

líquida.

Obs3. Deslocalização è ganho de estabilidade è híbrido de

ressonância é mais estável que qualquer uma das estruturas de

ressonância contribuintes.

Obs4. Quanto maior o n˚ de contribuintes de ressonância

relativamente estáveis è maior é a energia de estabilização por

ressonância. 28
Resumidamente: Características que diminuem a

estabilidade das estruturas de ressonância:

a)  Octeto Incompleto* à Principal.

b) C a r g a n e g a t i v a q u e n ã o e s t á n o á t o m o m a i s

eletronegativo e carga positiva que não está no átomo

mais eletropositivo;

c)  Separação de cargas.


29
Exercício

Represente as possíveis estruturas de Ressonância e o híbrido para os seguintes

íons e moléculas. Indique a carga formal quando houver

NO3-; CO32-

NH2

30
3s d block – each set of d orbitals can hold ten electrons 3p L
e
4s 3d 4p p
h

Onde um elétron estaria localizado no exemplo abaixo?


5s 4d 5p b
b
6s 5d 6p w
h
7s 6d fi
m
(H) (H) b
3
f block – each set of f orbitals can hold fourteen electrons
e
4f b
h
5f d

Física Quântica à Dualidade dos elétrons: partículas & ondas!


Graphical representations of orbitals
o elétronOne
é representado por uma função de onda (ψ)
problem with wave functions is trying to visualize them: what does a wave function look like?
Various graphs of wave functions can be plotted but they are not much help as Ψ itself has no physi-
cal meaning. However the square of the wave function, Ψ2, does have a practical interpretation; it is
proportional to the probability of finding an electron at a given point. Unfortunately, we can’t do

!
λ Th
in
→ fase positiva fu
to
el
ex
pr
pr
it
gi

λ → fase e negativa Bu
of
ph
These two waves both have the same wavelength, λ, but pr
the dashed wave is less intense than the other wave.
ph
The intensity is proportional to the amplitude squared. 31
ψ 2 = probabilidade de encontrar um ē em uma determinada região do espaço

Orbitais

§  Orbitais Atômicos (O.A.): s; p; d; f

§  Orbitais Atômicos Híbridos (O.A.H.): sp; sp2; sp3


§  Orbitais Moleculares (O.M.)

32
al plot—the contours are really spherical like thex different layers of an onion. These circles are rather
theof2sfinding
and a nodal
the plane in the
ke?likeThe
theprobability
contour linesdensity
on a map except
plot is nothat they represent
longer areas of equal probability
spherically
case of the 2p) while the 3s, 3p,
electron
pletely instead of areasorbital
different—the of equalnow
altitude.
has an orientation in and 3d orbitals each have two
Another way to represent the probability is by a density plot. Suppose we could see exactly where
hat there is a region where there is no electron density nodes (the 3s have two radial Atomic orbitals
the electron was at a given time and that we marked the spot. If we looked again a little later,
nodes, thethe3pelec-
orbitals each have
rface. This time the node is a plane in between the two
Orbitais Atômicos
tron would be xin a different place—let us mark this spot too. Eventually, if wey marked one enough
radial spots,
node and one nodal
newe representation of the 2p orbitals x
y a three-dimension-
would end up with a fuzzy picture is
like those shown for the 1s and 2s orbitals. Now theand
plane, density of orbitals each
the 3d

••Shapes
hape
the of the
dots orbital.
is an indication of2pthe
y probability of finding an electron in have
2p a given space—the two nodal
more densely planes).
packed the dots (that is, the darker
z the area), theplot
greater the2p
probability of s orbitals
z
of finding the electron in this
bital three-dimensional of the orbitals
!
The 1s orbital is spherically symmetrical and has no nodes
area. This is rather like some maps where different altitudes are indicated by different colours.
You might have noticed that each
s are similar—each has a nodal plane and the overall shape outlined in nth energy level has
ψ 2 dealso
he 3p orbital um orbital s:
has a radial node and the 4p has two
• Theorbital
radial
2ssame
nodes
the
in the
orbital
and
has one
total Atomic
number of
radial node and the 3s orbital
orbitals
nodes, 91
two radial nodes.
ital increases as the principal quantum number increases.They n – are
1. The both spherically
total number of nodes symmetrical
is the sum of the numbers of
hape of an orbital depends on the orbital angular quantum number, !.
• Shapes
rical, all
• The
nt shape.
ofx s(!
p zorbitals
The1sproblem
orbitals
= 1) are shaped like
orbital is spherically
that
y a figure
symmetrical
z eight,
and has
and
What does
radial nodes and nodal planes.
d
Thus
no take
orbitals
a both
nodes
2
Ψ the for2sa and
2p 2p
orbital
have onelook like? The probability density plot is no longer spherically
2pxthese probability density plots node a(along
radial node in the case of
symmetrical.theThis time the shape
an plane
s orbital is completely different—the orbital now has an orientation in
• The
ists need a simple easy way
2s orbital to represent
has one radial nodeorbitals.
and the The3s contour 2sradial
diagrams
orbital two
space and itcase has
and a nodes.
nodal in the
they were They are tedious.
a little both spherically symmetrical
Even simpler still is to draw just one and
Orbital
oftwo
contour
3d
the 2p)lobes.
orbitals each
s:have
Notice
while the 3s, 3p,also that there is a region where there is no electron density
two
a p orbital
90% chance of finding the electron. This meansbetween the twocan lobes—another
(theesférico
nodal surface. This time the node is a plane in between the two
it is§ 
that all s orbitals
nodes be3s have two radial
ll p orbitals
What doesby aa Ψ 2 for
pair ofalobes. lobes anddensity
2p orbital look like? The probability so nodes, known
plot the
is 3p as! a nodal
no orbitals
longer plane. One representation of the 2p orbitals is a three-dimension-
each have
spherically
x symmetrical. This timey the shape is completely
x al plot, ywhich
different—the gives
one
orbital nowanode
radial clear
has and
an idea §  semRemember
one of the
nodal
orientation
dimensional
plano
andintrue
that
that the orbitals are three-
shape
these drawingsof the orbital.
plane, andisthe
no3delectron
orbitalsadensity
each
space and it has two lobes. Notice also that there is a region where
2py two lobes—another nodal surface. 2p
between the This
z
have
time the node
there
is atwo nodal
plane
represent
in planes).
nodal
cross-section. A three-
dimensional version would look more
between the two
z
her discussion
densitytoplot
establish one fine point—the phase of andensity
of 1s orbital orbital. like a sphere for an s orbital and an old-
plot of 2s orbital
lobes and so itthree-dimensional
is known as a nodal plotplane.
of theOne
2p orbitals
representation of the 2p orbitals is a three-dimension-
fashioned hour-glass for a p orbital.
al plot, 2
which gives a clear idea of the true shape of the orbital. Actually, each lobe of a p orbital is
ψ de um orbital p:
eachThe
has2sa nodal
orbital,plane
like the and the overall
1s orbital, shape outlined
is spherical. There are in
two differences
z
betweenmuch moreorbitals.
these rounded than the usual
representation, but that! is not so
soOne
hasisathat above
radial 2sthis
the node line
orbital the
andis thephase
bigger
4p so
hasthat
twoanradial
electron in a 2sand
nodes orbital is more likely to important.
be found further
You might have noticed that each
away
s the fromofthe
principal
thenucleus
wave isthan
quantum
positive
an electron
number in a 1s orbital. The other difference between the orbitals is orbital in the nth energy level has
increases.
that, within the 2s orbital but not within the 1s orbital, there is a region where there is no electron the same total number of nodes,
bital depends on the orbital angular quantum number, !.
below
density at all. Suchthea line,
regiontheisphase
called a nodal surface. In this case there is no electron density at one set n – 1. The total number of nodes x y z
itals (! =from
1)ofare
the shaped like
wave is negative a figure eight, and d orbitals z
radius the nucleus; hence this is known as a radial node. The 2s orbital has one radial node. is the sum of the numbers of
problem is that these probability density plots take a long radial nodes and nodal planes. 2px
x y z
wave, Thus both the 2s and 2p have one
ple easyorway
musicians the towave on a vibrating
represent orbitals.string, or evendiagrams
The contour an
z ocean wave an spossess-
orbital
2px node (a radial node in the case of
mple,
tle the troughs
tedious. Even and peaks
simpler of is
still antoocean
drawwave) so too
just one do the atom’s wave
contour a pand
orbital the 2s and a nodal plane in the
ces by thinking in terms of waves. If a end stops), the second harmonic has one and the third has two so on.
rked,
each
finding node in an
thevibrates. orbital,
electron. the phase
This meansThese of the
thatare wave
allpoints function
s orbitals can changes. In the
bedoes not vibrate at all (you can even ‘select case of the 2p) while the 3s, 3p,
the string The ends
e instrument. The note we hear is
a pair ofdiagram
lobes.for the first
where the string
! Orbital p:
out’ the second harmonic on a stringed instrument if you gently press halfway and 3d orbitals each have two
nodes (the 3s have two radial
own in the along the vibrating string).
no nodes
x
1 node §  2andlóbulos
Remember that the orbitals are three-
dimensional that these drawings
2 nodes
nodes, the 3p orbitals each have
x
one radial node and one nodal y x y
higher energy A three- y
e the note its
y
§  1version
dimensional plano
would looknodal
represent a cross-section.
x
more plane, and the 3d orbitals each
2py
oto
tellestablish
the one fine point—the phase of an orbital.
2py like a sphere for an s orbital
2pz and an old- have two nodal planes). 2pz
violin playing fashioned hour-glass for a p orbital.
density plot of 2p orbital three-dimensional plot of the 2p orbitals three-dimensional plot of the 2p orbitals
harmonics are density
Actually,plot
eachof 2pof orbital
lobe a p orbital is
much more rounded than the usual 33
Plots of 3p and 4p orbitals are similar—each has a nodal plane and the overallbut
representation, shape
that isoutlined
not so in
within which there is, say, a 90% chance of finding the electron. This means that all s or
represented by a circle, and all p orbitals by a pair of lobes.

The phase of an orbital


nó daneed
The wave diagrams função de onda
further discussion to establish one fine point—the phase of an
probabilidade de encontrar um ē = zero! (ψ = 0, e logo ψ2 = 0)
after the node, the phase 1 node
of the wave changes
acima
above desta
this line linha a fase
the phase
of the
da wave isde
função positive
onda é positiva
4 . Structure of molecules abaixo desta linha a fase
below the line, the phase
daof função
the wave isde onda é
negativa
negative

2p orbital, for example, one lobe is one phase; the other lobe is another phase with th
Just as an electromagnetic wave, or the wave on a vibrating string, or even an ocean w
between. In the standing wave above the different phases are labelled positive an
es different ‘phases’ (for example, the troughs and peaks of an ocean wave) so too do the
phases of a p orbital could be labelled in the same way (and you may sometimes see
Nos orbitais p oschemists
2 lóbulos
functions—the possuem
orbitals. Afterand
use positive eachfases
negative opostas
node in (geralmente
an orbital,
signs to mean the representadas
phasecharges,
specific of the wave function
this could ch
get con
porhalf
one sinais dep orbital
of the “+” e “–” ou por
is usually cores
shaded diferentes:
to show that it has a different phase from

here the different


+ here the different
phases of the p
orbital are labelled phases of the p
orbital are shown
plano nodal
positive and negative –
by shading one half
this can be confusing
and so is best avoided and not the other

34
The magnetic quantum number, m!
Energia dos Orbitais Atômicos (OA)

Em um mesmo período da tabela periódica:

energia OA ”p” > energia OA “s”!

OA 2p x do C

OA 2s do C

“quanto maior o número de planos nodais, maior a energia do orbital (sistema)”


35
Molecular
Molecular orbitals—homonuclear
orbitals—homonuclear diatomics
diatomics
So the
As ligações químicas
So far far the
dediscussion
has has
moléculas
discussion concernedonlyonly
são formadas
concerned the the shapes
pela
shapes and energies
combinação
and energies of atomic
Linear
of atomic orbitals
de(A
orbitals
Orbitais chemists
chemists
Atômicos really
really needneed
(OA) to look
to look at the
at the
produzindo orbitals
orbitals for whole
for whole
Orbitais molecules.
molecules.
Moleculares OneOneway way to construs
to construct
(OM)!
lar orbitals
lar orbitals (MOs) (MOs)
is toiscombine
to combine
the the atomic
atomic orbitals
orbitals of the
of the atoms
atoms thatthat
makemake up th
up the m
§  Combinação
approach
approach is known
is known Linear
as the
as the Linear
Linear de Funções
Combination
Combination ofde
of Atomic Onda
Atomic Orbitals
Orbitals (LCAO).
(LCAO).
Atomic
Atomic orbitals
orbitals are are
wavewave functions
functions andand
the the different
different wave wave functions
functions can can be com
be combi
rather
rather in the
in the wayway waves
waves combine.
combine. YouYou
maymay be already
be already familiar
familiar withwith
the the ideas
ideas of com
of combin
Existem
theythey
can can
addduas
add possibilidades
together
together de(in-phase)
constructively
constructively combinarmos
(in-phase) ondas:
or destructively
or destructively (out-of-phase).
(out-of-phase).

combinação
combine
combine
emin-phase
in-phasefase

constructive
constructive overlap
overlap
interação
construtiva

combinação
combine
combine
fora out-of-phase
de fase
out-of-phase
destructive
destructive overlap
overlap
interação
destrutiva
the ways
the two two ways of combining
of combining a simple
a simple wavewave – in-phase
– in-phase and and out-of-phase
out-of-phase 36
Estrutura de Lewis do metano (CH4):

Ligações C–H:

§  ângulo = 109,5°
§  comprimento = 1.09 Å
§  força = 104 kJ/mol

Considerando as diferenças de forma e de energia dos OA do C não seria


possível conceber a molécula de metano como um tetraedro regular!

Hibridação de Orbitais Atômicos:

“o conceito de hibridação de OA confere direcionalidade às ligações químicas”

Diferentes combinações entre OA s e OA p resultam em arranjos eletrônicos


distintos!

37
orbital, which adds to one lobe bu
emistry, it is helpful to consider the molecule as being made up of atoms held tracts from the other.
isting of a pair of electrons. When working out the MOs for methane, we used The four sp3 orbitals on one c
hree of the 2p orbitals to combine with the hydrogen 1s orbitals. Each orbital
atom point to the corners of a tetrah
hydrogen orbitals equally. Another way to consider the bonding would be to
Arranjo eletrônico tetraédricoand methane can be formed by ov
and 2p orbitals first to make four new orbitals. Each of these orbitals would
ping the large lobe of each sp3 orbita
be composed of one-quarter of the 2s orbital and three-quarters of one of the
itals are called sp3 hybrid orbitals to show the proportions of the AOs in each.
is called hybridization.
mic orbitals on the add four
me total number of H atoms
+ + +
of these has one- C
d three-quarters p
2s 2px 2py 2pz
bital has a planar H
atomic orbitals all on the same atom
eus like a p orbital four sp3 hybrid orbitals
er than the other
4 orbitais atômicos híbridos (OAH) sp3form a tetrahedron
ntribution of the 2s
one lobe but sub- four sp3 hybrid orbitals

2s
§  orientação nothis
espaço à tetraédrica (109º)
one is from
als on one carbon 2s + 2py

ers of a tetrahedron §  os quatro OAH sp3 são degenerados


ormed by overlap- 2py
§  25% caráter “s” e 75% caráter “p”
ach sp3 orbital with

add four combine H


H atoms sp3 and 1s

H 38
H
quarter s character and three-quarters p
2s 2px 2py 2pz
character. The sp3 orbital has a planar
atomic orbitals all on the same atom
node through the nucleus like a p orbital
but one lobe is larger than the other
because of the extra contribution of the 2s
orbital, which adds to one lobe but sub-
molécula de metano: four sp3 hybrid orbitals
tracts from the other. this one is from
2s
ligações
The four σ:sp3 sobreposição
orbitals on one carbon frontal dos 4 OAH sp3 do2sC + 2py
com os 4 OA s do H
atom point to the corners of a tetrahedron
and methane can be formed by overlap- 2py
3
ping the large lobe of each sp orbital with

combine H
add four
H atoms
sobreposição
sp3 and 1s
C
frontal H
H
H H
H
four sp3 hybrid orbitals H each MO orbital is the same
form a tetrahedron and has σ symmetry

Exemplos de hibridação sp3:


H2O; NH3; NH4+; BF4–...

39
at advantage of this method is that it can be used to build up structures of much larger
quickly and without having to imagine that the molecule is made up from isolated atoms.
y to work out the structure of ethene (ethylene) the simplest alkene. Ethene is a planar
Arranjo
ith bond angles close to 120°. Our approach willeletrônico trigonal
be to hybridize all the orbitalsplanar
needed for
amework and see what is left over. In this case we need three bonds from each carbon
o make a C–C bond and two to make C–H bonds).
re we need to combine the 2s
each carbon atom with two p
make the three bonds. We + + +
ridize the 2s, 2px , and 2py
at is, all the AOs in the plane) 2px 2py 2pz
2s
ree equal sp2 hybrid atomic
leaving the 2pz orbital
These sp2 hybrid orbitals will
hird s character and only two- 3 × sp2 AOs
in the plane
OA p “puro”
aracter.
e sp2 hybrid atomic orbitals on unchanged 2pz
n atom can overlap with three
als (two hydrogen 1s AOs and one sp2 AO from the other 3 OAH sp2to form three σ MOs.
carbon)
the two 2pz orbitals, one on each carbon, which combine to form the π MO. The skeleton
§  trigonal planar (120º)
ecule has five σ bonds (one C–C and four C–H) in the plane and the central π bond is
wo 2pz orbitals above and below the plane. §  3 OAH degenerados e 1 p “puro”
π bond
§  33% caráter “s” e 66% caráter “p”
H
H H
C + C C C
H H
H
σ bonds σ bonds
40
π bond
orbitals (that is, all the AOs in the plane) 2px 2py 2pz
2 2s
to form three equal sp hybrid atomic
orbitals, leaving the 2pz orbital
unchanged. These sp2 hybrid orbitals will
molécula de eteno:
have one-third s character and only two- 3 × sp2 AOs
thirds p character. in the plane
The three sp2 hybrid atomic orbitals on unchanged 2p
each carbon
ligaçãoatomσcan overlap
C–C: with three
sobreposição frontal dos OAH sp2 dos C;
2
other orbitals (two hydrogen 1s AOs and one sp AO from the other carbon) to form three σ MOs.
This leaves the two 2pz orbitals, one on each carbon, which combine to form the π MO. The skeleton
ligação π C–C: sobreposição lateral dos OA p dos C;
of the molecule has five σ bonds (one C–C and four C–H) in the plane and the central π bond is
formed by two 2pz orbitals above and below the plane.
lig. π
OA p π bond

H OAH sp2 H
H H
C + C C C lig. σ
H H
H H
σ bonds σ bonds

π bond
ligação σ é mais forte do que ligação π : sobreposição orbitalar mais
Ethyne (acetylene) has a C–C triple bond. Each carbon bonds to only two other atoms to form a
eficiente!
linear CH skeleton. Only the carbon 2s and 2p have the right symmetry to bind to only two atoms at
x
once so we can hybridize these to form two sp hybrids on each carbon atom leaving the 2py and 2pz
to form π MOs with the 2p orbitals on the other carbon atom. These sp hybrids have 50% each s and
p characterExemplos
and form ade
linear carbon skeleton.
hibridação sp2: H CCH ; H CO; OOO (O )...
2 2 2 3

41
to form
linear CHπ MOs withOnly
skeleton. the 2p
theorbitals
carbonon2s the
andother carbon
2px have the atom. These sp hyb
right symmetry to
p character
once andhybridize
so we can form a linear
thesecarbon skeleton.
to form two sp hybrids on each carbon atom
to form π MOs with the 2p orbitals on the other carbon atom. These sp hyb
Arranjo
p character andeletrônico linearskeleton.
form a linear carbon
+ + +

+ 2px + 2py + 2pz


2s

2s 2px 2py 2pz

+ +

2 × sp AOs
+ 2py
+ 2pz
2 OAH sp 2 OA p
two p orbitals are“puro”
unchanged
2 ×(180º)
§  linear sp AOs 2py 2pz
two p orbitals are unchanged
§  2 OAH degenerados e 2 p “puro”
§  50% caráter “s” e 50% caráter “p”

Exemplos de hibridação sp: HCCH; N2; CO, CO2...

42
43
Consequências da Hibridização

1.  Comprimentos de ligação:

2. Caráter s e p dos orbitais

sp3: 25% caráter s e 75% de caráter p;

sp2: 33,3% caráter s e 66,7% de caráter p;

sp: 50 % caráter s e 50 % de caráter p.

3. Acidez dos hidrogênios ligados ao C:


H H
H H > > H3C CH3
44
H H
Energia de Orbitais Atômicos (OA) e Orbitais Atômicos Híbridos (OAH)

Orbitais do átomo de C:
E
OA p

OAH sp3 (75% caráter p)

OAH sp 2 (66% caráter p)

OAH sp (50% caráter p)

OA s

45
RPECV: Repulsão dos pares de elétrons da
camada de valência

ü  Devemos considerar todos os


pares de elétrons de valência do Tetraédrica
átomo central: Ligantes e Não-
ligantes
Pirâmide
Triangular

ü  Tendência a ficar o mais


afastados possível devido a
Angular
repulsão entre os pares de
elétrons : Previsão da Geometria.
46
HIBRIDIZAÇÃO

EXERCICIOS

47
FÓRMULAS ESTRUTURAIS

48
Fórmulas Tridimensionais

49
FIM

•  denfavaro@iqm.unicamp.br

50