1.

SLrucLure and 8ondlng

8ased on
McMurry's Otqoolc cbemlstty, 7
Lh
edlLlon,
ChapLer 1
Crganlc ChemlsLry
Crganlc" - unLll mld 1800's
referred Lo compounds lsolaLed
from llvlng sources
mlneral sources were lnorganlc"
Wh|er ln 1828 showed LhaL
urea, an organlc compound, could urea, an organlc compound, could
be made from a non-llvlng source:
2
Crganlc ChemlsLry
1oday, organ|c compounds are Lhose based on
carbon sLrucLures and organ|c chem|stry
sLudles Lhelr sLrucLures and reacLlons
lncludes blologlcal molecules, drugs, solvenLs, lncludes blologlcal molecules, drugs, solvenLs,
dyes, food addlLlves, pesLlcldes, and oLhers.
uoes noL lnclude meLal carbonaLe salLs and oLher
slmple lonlc compounds (lnorganlc) such as
cyanlde, cyanaLe, LhlocyanaLe.
3
Crganlc compounds
+
Crganlc ChemlsLry
5
What so special with Carbon?
How about Si?
1.1 8evlew of Lhe ALomlc SLrucLure
SLrucLure of an aLom
oslLlvely charged oocleos (very dense, proLons and neuLrons) and
small (10
-13
m)
negaLlvely charged elecLrons are ln a cloud (10
-10
m) around
nucleus nucleus
ulameLer ls abouL 2 10
-10
m (200 plcometets (pm)) [Lhe
unlL ooqsttom () ls 10
-10
m = 100 pm]
6
ALomlc number & Mass number
1he otomlc oombet (2) ls Lhe number of
proLons ln Lhe aLom's nucleus
1he moss oombet (A) ls Lhe number of
proLons plus neuLrons proLons plus neuLrons
All Lhe aLoms of a glven elemenL have Lhe
same aLomlc number
7
ALomlc number and ALomlc Mass
All Lhe aLoms of a glven elemenL have Lhe same
aLomlc number
Isotopes are aLoms of Lhe same elemenL LhaL have
dlfferenL numbers of neuLrons and Lherefore
dlfferenL mass numbers dlfferenL mass numbers
1he atom|c mass (otomlc welqbt) of an elemenL ls
Lhe welghLed average mass ln aLomlc mass unlLs
(amu) of an elemenL's naLurally occurrlng lsoLopes
8
1.2 ALomlc SLrucLure: CrblLals
uantum mechan|cs: descrlbes elecLron energles and
locaLlons by a wove epootloo
wove fooctloo ls a soluLlon of Lhe wave equaLlon
Lach Wave luncLlon descrlbes an orb|ta|,
A ploL of
2
descrlbes Lhe probabllllLy of flndlng Lhe
elecLron
1he elecLron cloud has no speclflc boundary so we show
elecLron
1he elecLron cloud has no speclflc boundary so we show
Lhe mosL probable volume.
1he boundary ls called a probabllllLy surface"
9
Shapes of ALomlc CrblLals for LlecLrons
lor Lhe exlsLlng elemenLs, Lhere are four dlfferenL
klnds of orblLals for elecLrons based on Lhose
derlved for a hydrogen aLom.
uenoLed s, p, J, and f
s and p orblLals mosL lmporLanL ln organlc
chemlsLry (carbon aLoms have no J or f orblLals)
s and p orblLals mosL lmporLanL ln organlc
chemlsLry (carbon aLoms have no J or f orblLals)
10
Shapes of ALomlc CrblLals for LlecLrons
s orblLals: spherlcal, nucleus aL cenLer
11
Shapes of ALomlc CrblLals for LlecLrons
p orblLals: dumbbell-shaped, nucleus aL mlddle
12
p-CrblLals
ln each shell Lhere are Lhree perpendlcular p orblLals, p
x
, p
y
,
and p
z
, of equal energy
Lobes of a p orblLal are separaLed by reglon of zero elecLron
denslLy, a node
13
CrblLals and Shells
CrblLals are grouped ln she||s of lncreaslng
slze and energy
As shells lncrease ln slze, Lhey conLaln larger
numbers and klnds of orblLals
Lach orblLal can be occupled by Lwo elecLrons Lach orblLal can be occupled by Lwo elecLrons
(aull Lxcluslon rlnclple)
1+
CrblLals and Shells
llrsL shell conLalns
one s orblLal, denoLed
1s, holds only Lwo
elecLrons
Second shell conLalns
one s orblLal (2s) and
Lhree p orblLals (2p):
one s orblLal (2s) and
Lhree p orblLals (2p):
elghL elecLrons
1hlrd shell conLalns an
s orblLal (3s), Lhree p
orblLals (3p), and flve
J orblLals (3J): 18
elecLrons
15
CrblLals and Shells
16
1.3 ALomlc SLrucLure: LlecLron
ConflguraLlons
Ground-state e|ectron conf|gurat|on of an aLom llsLs orblLals
occupled by lLs elecLrons.
1. LowesL-energy orblLals flll flrsL: 1s 2s 2p 3s 3p
4s 3J (Aofboo (bulld-up") prlnclple)
2. LlecLron spln can have only Lwo orlenLaLlons, up and 2. LlecLron spln can have only Lwo orlenLaLlons, up and
down . Cnly Lwo elecLrons can occupy an orblLal, and Lhey
musL be of opposlLe spln (looll exclosloo ptloclple) Lo have
unlque wave equaLlons
3. lf Lwo or more empLy orblLals of equal energy are avallable,
elecLrons occupy each wlLh splns parallel unLll all orblLals have
one elecLron (nooJ's tole).
17 18
LlecLron ConflguraLlons
19
1.4 uevelopmenL of Chemlcal 8ondlng
1heory
kekule and Couper lndependenLly observed LhaL
carbon always has four bonds
1eLravalenL - lL blnds wlLh for oLher elemenLs
kekule proposed LhaL carbon
20
Friedrich August Kekule
kekule proposed LhaL carbon
aLoms bond Lo one anoLher
Lo form exLended chalns and
rlngs
1.4 uevelopmenL of Chemlcal 8ondlng
1heory
van'L Poff and Le 8el proposed LhaL Lhe four bonds of carbon
have speclflc spaLlal dlrecLlons
ALoms surround carbon as corners of a LeLrahedron
21
Note that a wedge indicates a
bond is coming forward
Note that a dashed line
indicates a bond is behind
the page
J. H. van't Hoff
1eLrahedral Carbon:
22
1.3 1he naLure of Lhe Chemlcal 8ond
ALoms form bonds because Lhe
compound LhaL resulLs ls more
sLable Lhan Lhe separaLe aLoms
lonlc bonds ln salLs form as a
resulL of elecLron Lransfers resulL of elecLron Lransfers
Crganlc compounds conLaln
covalenL bonds, from sharlng
elecLrons (C. n. Lewls, 1916)
23
1.3 1he naLure of Lhe Chemlcal 8ond
Lew|s structures show valence elecLrons of
an aLom as doLs
Pydrogen has one doL, represenLlng lLs
1s elecLron
Carbon has four doLs (2s
2
2p
2
) Carbon has four doLs (2s 2p )
A sLable molecule resulLs when Lhe
ouLermosL (valence) shell ls compleLed:
ocLeL (elghL doLs) for 2
nd
perlod maln-group
aLoms (Lwo for hydrogen)
2+
number of CovalenL 8onds Lo an ALom
ALoms wlLh one, Lwo, or Lhree valence
elecLrons form one, Lwo, or Lhree bonds
ALoms wlLh four or more valence elecLrons
form as many bonds as Lhey need elecLrons Lo
flll Lhe s and p levels of Lhelr valence shells Lo flll Lhe s and p levels of Lhelr valence shells Lo
reach a sLable ocLeL
25
Some slmple molecules:
26
number of CovalenL 8onds Lo an ALom
27
valences of Carbon
Carbon has four valence elecLrons (2s
2
2p
2
), formlng
four bonds (CP
4
)
28
valences of Cxygen
Cxygen has slx valence elecLrons (2s
2
2p
4
) buL forms
Lwo bonds (P
2
C)
29
valences of nlLrogen
nlLrogen has flve valence elecLrons (2s
2
2p
3
) buL forms only Lhree bonds (nP
3
)
30
non-bondlng elecLrons
valence elecLrons noL used ln bondlng are called nonbond|ng
e|ectrons, or |one-pa|r e|ectrons
nlLrogen aLom ln ammonla (nP
3
) shares slx valence
elecLrons ln Lhree covalenL bonds, Lhe remalnlng Lwo valence
elecLrons are a nonbondlng lone palr elecLrons are a nonbondlng lone palr
31
1.3 valence 8ond 1heory
A covalenL bond forms when Lwo aLoms
approach each oLher closely so LhaL a slngly
occupled orblLal on one aLom ovetlops a
slngly occupled orblLal on Lhe oLher aLom
32
slngly occupled orblLal on Lhe oLher aLom
1.3 valence 8ond 1heory
LlecLrons are palred ln
Lhe overlapplng orblLals
and are aLLracLed Lo
nuclel of boLh aLoms
P-P bond resulLs from P-P bond resulLs from
Lhe overlap of Lwo slngly
occupled hydrogen 1s
orblLals
P-P bond ls cylloJtlcolly
symmettlcol, s|gma ( )
bond
33
8ond Lnergy
8eacLlon 2 P P
2
re|eases 436 k!/mol
roducL has 436 k!/mol less energy Lhan Lwo aLoms: P-P
has bond strength of 436 k!/mol. (1 k! = 0.2390 kcal, 1 kcal
= 4.184 k!)
3+
8ond LengLh
ulsLance beLween
nuclel LhaL leads Lo
maxlmum sLablllLy
lf Loo close, Lhey
repel because boLh repel because boLh
are poslLlvely
charged
lf Loo far aparL,
bondlng ls weak
1he energy dlagram
on Lhe rlghL ls called
a Morse ulagram
35
WhaL ls a 8ond? An Lnergy M|n|mum
36
1.6 PybrldlzaLlon: sp
J
CrblLals and Lhe
SLrucLure of MeLhane
Carbon has 4 valence elecLrons (2s
2
2p
2
)
ln CP
4
, all C-P bonds are ldenLlcal
(LeLrahedral)
37
sp
3
PybrldlzaLlon
38

3
hybr|d orb|ta|s: s orblLal and Lhree p orblLals
comblne Lo form four equlvalenL, unsymmeLrlcal,
LeLrahedral orblLals (sppp = sp
3
), aullng (1931)
1eLrahedral SLrucLure of MeLhane
sp
3
orblLals on C overlap wlLh 1s orblLals on 4 P
aLom Lo form four ldenLlcal C-P bonds
Lach C-P bond has a sLrengLh of 438 k!/mol
and lengLh of 110 pm
8ond ang|e: each P-C-P ls 109.3, Lhe
tettobeJtol ooqle.
8ond ang|e: each P-C-P ls 109.3, Lhe
tettobeJtol ooqle.
39
1eLrahedral SLrucLure of MeLhane
+0
1.7 PybrldlzaLlon: sp
J
CrblLals
and Lhe SLrucLure of LLhane
1wo C's bond Lo each oLher by overlap of an sp
3
orblLal from each
1hree sp
3
orblLals on each C overlap wlLh P 1s orblLals
Lo form slx C-P bonds
+1
1.7 PybrldlzaLlon: sp
J
CrblLals and Lhe
SLrucLure of LLhane
C-P bond sLrengLh ln eLhane 420 k!/mol
C-C bond ls 134 pm long and sLrengLh ls 376 k!/mol
All bond angles of eLhane are LeLrahedral
+2
1.8 PybrldlzaLlon: sp
2
CrblLals and Lhe
SLrucLure of LLhylene
+3
1.8 PybrldlzaLlon: sp
2
CrblLals and Lhe
SLrucLure of LLhylene

2
hybr|d orb|ta|s: 2s orblLal comblnes wlLh two 2p orblLals,
glvlng 3 orblLals (spp = sp
2
)
sp
2
orblLals are ln a plane wlLh120 angles
8emalnlng p orblLal ls perpendlcular Lo Lhe plane
++
8onds lrom sp
2
Pybrld CrblLals
1wo sp
2
-hybrldlzed orblLals overlap Lo form a bond
p orblLals overlap slJe-to-slJe Lo formaLlon a p| ( )
bond
sp
2
-sp
2
bond and 2p-2p bond resulL ln sharlng sp
2
-sp
2
bond and 2p-2p bond resulL ln sharlng
four elecLrons and formaLlon of C-C double bond
LlecLrons ln Lhe bond are cenLered beLween nuclel
LlecLrons ln Lhe bond occupy reglons are on elLher
slde of a llne beLween nuclel
+5
8onds lrom sp
2
Pybrld CrblLals
+6
SLrucLure of LLhylene
P aLoms form bonds wlLh four sp
2
orblLals
P-C-P and P-C-C bond angles of abouL 120
C-C double bond ln eLhylene shorLer and sLronger Lhan
slngle bond ln eLhane slngle bond ln eLhane
LLhylene C=C bond lengLh 133 pm (C-C 134 pm)
+7
1.9 PybrldlzaLlon: spCrblLals and
Lhe SLrucLure of AceLylene
C-C a ttlple bond sharlng slx elecLrons
+8
1.9 PybrldlzaLlon: spCrblLals and Lhe
SLrucLure of AceLylene
Carbon 2s orblLal hybrldlzes wlLh a slngle p orblLal glvlng
Lwo sp hybrlds (Lwo p orblLals remaln unchanged)
sp orblLals are llnear, 180 aparL on x-axls
1wo p orblLals are perpendlcular on Lhe y-axls and Lhe z- 1wo p orblLals are perpendlcular on Lhe y-axls and Lhe z-
axls
+9
CrblLals of AceLylene
1wo sp hybrld orblLals from each C form sp-sp bond
p
z
orblLals from each C form a p
z
-p
z
bond by sldeways
overlap and p
y
orblLals overlap slmllarly
50
8ondlng ln AceLylene
Sharlng of slx elecLrons forms C C
1wo sp orblLals form bonds wlLh hydrogens
51
Comparlson of C-C & C-P bonds:
52
Comparlson of C-P bonds:
Molecule Bond Energy {kcal) Length {pm)
C -H 100 110
Ethane
C
sp3
-H 100 110
Ethylene
C
sp2
-H 106 108
Acetylene
C
sp
-H 132 106
53
Comparlson of C-C bonds:
Molecule Bond Energy {kcal) Length {pm)
C -C 90 15+
Ethane
C
sp3
-C
sp3
90 15+
Ethylene
C
sp2
-C
sp2
1+6 133
Acetylene
C
sp
-C
sp
200 120
5+