HOMEWORK PROBLEMS: STRUCTURE, BONDING & HYBRIDIZATION

1. The molecule shown below is Griseofulvin, an antifungal compound.

OCH3 O OCH3

O
H3CO O
Cl H3C 1
3
4 2

a. Give the hybridization of carbons 1, 2, 3 and oxygen 4.

C1: sp3 C2: sp3 C3 sp2 O4 sp3

b. What is the geometry at each of these atoms? (Ignore distortions.)

C1: tetrahedral C2: tetrahedral C3 trigonal planar O4 tetrahedral

c. Fill in all nonbonding electrons and H's on the structure below. (Assume neutral charge.)

OCH3 O OCH3
H
H
O
H3CO O
H
Cl H3C H H

2. For the molecule shown give the information corresponding to each letter as indicated below.
a. give the hybridization of these atoms.

b. give these bond angles.

sp2
sp2
120°
O
OH
120°þ Prostaglandin E2
O
109.5°
HO OH

sp3
sp3
3. Consider acetylene anion, shown below.
H C C

a. Give the hybridization of all carbon atoms.

H C C
sp sp

b. In what type of orbital does the nonbonding pair of electrons reside?

sp orbital

4. Draw reasonable skeletal (line/angle) formulas for the following condensed

formulas/structures. Next, draw good 3D structures by adding wedges and dashes to your simple
skeletal structures.

The answers include the 3D of the skeletal and an expanded idea of the 3D structure with the
hydrogens added back in (essentially hybrids of the skeletal and Lewis).

a. CH3CH2CH2CH(CH3)2
H
H H
H H
H
H H

H H H
H H H

b. CH3CH2CHBrCH2C(CH3)3
H
H H H
H H Br H
Br Br H H
H
H
H
H H H H H

c.
H3C O

H3C CH2 CH C OH
 H H O
O O
H
OH
OH OH
H H H
H H
H

d.
CH2
CH2 CH

CH2 CH
C

CH2
H H
H H
H
H
H H

H H

5. Convert the following skeletal structures to Lewis structures. Make sure to include all atoms
and lone pairs.

H H
H H
C HH
H O
H C C H H C C
H C C C C C
Cl O
C C C C C
O C C H N C C H
H H
H H H H H
H H

6. Convert the following Lewis structures to skeletal structures.

O OH OH

NH2 O

N O
H
7. In the following molecule, identify all atoms that have a trigonal planar geometry. Can you
make any correlations between obvious structural features and the geometries? Explain.
O

Cl

N OH

All the atoms here that are invovlved in double bonds have trigonal planar geometry and will be
best described as sp2-hybridized. This trend is generally true (note allenes as special cases). The
key feature overall is that large regions of the molecule are flat. Interconnected groups of trigonal
planar atoms lead to planar regions of a molecule. Moreover, as we think about the orbital
pictures, we recognize that these planar regions have electrons residing above and below them
because the p-orbitals used to make the pi bonds lie perpendicular to the plane with the sigma
bonds. Interesting chemistry will result from these electron clouds.
CHEM24 Dr. Spence

8. (a) Provide the ground stateelectron configuration and the number of valence electronsfor carbon
and silicon. Describehow thesetwo atoms are similar. (b) Which bond do you think is stronger,ger,aaC-C
C-(
bond
orsi-si?Explain'
I g"o, c on,l 5, hc,vr sc,n{ j
('t
I P oc tqltnct eletkna"i ). N
l
o
\
C-g 6'^l
-
is I'l*\
4
'* | 1_
L1
lllou.re.rtc
, \ lL
t\r*'n5' -5-'qt ;t \ " 'lt 1yL
L( r1 '1 - lo'*; 1l
lrng or)r,hl: k nr,Z"l lt',erltr
I
a,
1v
L5 : | ,r
ogp*d J" 2(o'
V'dslw)l z5 1L.
lot I
4v a"'rcr-lqa
t:1" j
ll [ (,*".*h,,r, hfie',r Is k
ocb,.lau)
s;,zzJ
l-.,iruc|s,,r,,|ur
Carbun I \ 5 ilicovr
9. (a) What hybridization do you predict for the carbonatom in CH:n, CH:-, and :CHz? (b) What do yr
predict for the H-C-H bond angle for eachof thesespecies?(b) What do you predict for the molecular
geometry?
@ I i,
rl -Z-rl rt - C-tt H * C-hl
i f

Fl rl
h1b.iJ X' s?t s('
rl
H-c- lLo' /09,5" ILA'
a,nn)w
tt\yon.o,l
' t*1onol
rroo)ec....r)*t- , b<"lt
ryom,a\ fi',o,2+: (1fan:'dal
10. Draw the Lewis/Kekule structuresfor SiH+,PHgand HzS. Provide the electronic geometryand the
moleculargeometryfor eachas predictedby VSEPR theory.

I
H - 5; -t{ H- P - H i1*?.-H
I t
r-l l-l
eo 9gorrr: -ittr'qheJr".\ I
ieTc.,heJ{" *trahcdrEI

nt_l<w dml tnqu,r,al g+nt

/-
lc /st{-uhr
9a'* ginm,J"l
 CHEM24 Dr. Spence

11. Considerthe Lewis/Kekule structurefor PH3. (a) What value do you predict for the H-p-H bond
angle? (b) Is P-H a strongerbond or weaker bond than an N-H bond in NH3? Explain. (c) Is
hybridization necessaryto explain the trivalent natureof phosphorus?Explain. If it doesundergo
hybridization, what hybridization statewould PH3have and why would it undergo hybridization?
[a ) bonJ ang)<- : lO9,5" (iyoert-
al,Eftl,n>)

(frl ?-d rJ c, weqke.rfu'"ol fhan N-d .Jre J, (oa( ouerlctfaE la{E1J.

It
? r{ a*}',t,\ (€t*- N lb,Lil),ryrthH n5 N{o.rhrb,l (Zl sre|)
tl-p'H
I
l"t (C) N1i.t){rhlbnJ'zr/ ? cc4n &rrn 3 banJs (r*a., € cwfigrrql'oo)

tQ oo hlfi,di"qion ,10" bw,J bo*Js (g,u'rero'^:wlug

(r))
" 1n*S $ uueqlst
bnnJs anJ
wl p-orbrto!/ 5"(' hlVnrlizolron lr-'r-t 51<amryr
bq,5" VanJ c;nglnst Sr,l1>F-f v1E?R theof/
lZ.Draw anorganicmoleculewhich contains^the
followingtype of bonds:
(a) a Csp'- Osp' sigmabond (c) Nsp'- C.p' sigmaand pi bond

- -Yl
' I orf
CHr ,-\'ZN
\
(b) Csp3- Crpt sigmabond (d) Nsp2- Crp' sigmabond(with no pi bondlfc* lea:t nut be1#6f.a;
\ At t^nt'lL /
/->' l *rt'O
13. Why is an sp hybridizedC-H bond strongerthan an sp'C-H bond? ,\ rr
cnrnpred
Rn 5f arb',fql ,: rrao'rtdire."t\rlo*I (l4ten.''t) Siott-'f '> 5Oy"S
fo 2{z trrqA i: wl1""%'L S". A rnort Jrtcfiooq/ orbifuI rrfr)I
ort( laf b<ilsr rrrrth H ls orbthi 7b grtL q Skooopl- bo"d,

14. Are the hydrogenatomsin the moleculeH2C=C=Q=CHzin the sameplane or in planes

perpendicularto eachother? Explain using the hybridization of eachcarbon atom.
t"
ftll ,', fcam<-plc,r{. r'rtvq)can?ir'l.ockJ')"tft 17 baalS a{L /rrrlel

H-.."0,4rffi.,o.il
ctlt l1'5 art

,,o'(4784\1 f VoacJl
t|.r p)rtn\,

V<cguodrcvlr^r'
fu ?"{
CHEM24 Dr. Spence

15. When energyis suppliedto the n bond of ethylene,one electronis promoted from a molecular
orbital of lower energyto one of higher energy. (a) Show what this excited stateMO diagram would
look like. (b) What happensto the n bond if this occurs(considerbond order before and after)? (c)
Basedon values of bond strengths,how much energyis neededfor this excitation to occur?
i l
l r l l
b'"Jin1 ()
t"-_tonh rL \(i.'11\DTv'lrfi
'''1 ,-1
--t 1
/? L'.,
'j--
7( hr 1 ".
;-
I
- . t

"'#j \ ' 1 , ' .

bon,J''nry r | . r
Y2onc'l\flc,\
,

rn0 rO)
a
I

!
1n"eul{6r*J orJe{ €rrn
slx,nyes 1- lu O ( {"6"-t
7
I h"nJ w;ll
C =C tpontl *trtn3\h = &tX F5)lmer)

C -t b,on) r$nnrth = i5o P5l"ml

'" ener1low'l'zJ$ +cil-t
f,t> 7l bonrl = %i trSlmot

16. For the following molecule,all the atomsare in the sameplane,i.e. the plane of the paper. Is this
expected? Why or why not? If it is not expected,what doesthis tell you about this compound?
| T? 6 '; 5(3
Nct e,'.Qe.-l-s.,1 Ji- ,H
h1t'r;J,ztJ,iV'l trigo'nt'lpict..,.nitlfii
50 AJanc/ tr'u Ht not
in fcam\ glc-n{ a$ c"v^\a'n t'fun I

(Y1,tfi conriir:b( (":ooqnc€ Foot^ ( to7;t Z )

OO
po n ) Z^' fet. Forr^ rvt,tif co,.tlr,WtU s'
,X;-tr 'r{ +-> p"/=.f,.tt ( , ,t s{ h-t'br;J.rr)conolg}anc^r.
h I ttt st ^ 6a"rJ s{;n qI-
rc: Fw'{"l'mwlirrx-
fv'la;of fe5. af tX"n - (trnev/lbtr Wt CwrtftvY nai:'ft olutnl
dlrnof fts \
crntr.,Wtuc C"c#,h\rr ) ?or fes h>rtns )
17. Can boron satisfythe octet rule by forming covalentbonds? Explain why or why not'

//ot c/;rt *H &o{oro ha> *t\ 3 vqf$nrt e }t rkooE d,

fYtur< t ltilny Y;aoJS ",nJ 6 eltc{t'6"t ,?s} g'
7 co'v,;b.*1t"

qt\ dturn tbQt

;+ cr.{a So\-,>C{oehl ip if bunJ'>1a a
( u q W,f I/1 tcq;. z)
5vgfirrg bot\n t)ev\run s flfevrtrazJr> /e*,5
CHEM24 Dr. Spence

18. Given below is the molecular orbital diagram for CHa. Mathematical combination of the carbon2s
and2p orbitals with the four hydrogen 1s orbitals generatesthe eight molecular orbitals as shown (note,
recall theseorbitals and their energy levels must be determinedthrough calculationsand cannotbe
predicted). In this diagram,fill in the valenceelectronsin the atomic and molecular orbitals and label
bonding and antibondingmolecular orbitals. What doesMO theory predict for the number of bonds (or
bond order) for CH+. Is this consistentwith the way we draw the Lewis structure?

\ \
\'
1t 1 t ,
t \\1 4f 1
I
4
I
' l
t
c2p - -, /-
C2s --1
1l-."". \ a,
a/ 4XHlsorbitals

\\ \\ a t

\. '.
t t '

4r
'-!L 4t nl .,','
t
Ir" lL .'
t a I
t
)eonJ orJ+C
\
'.. z
'> 'Jo.,l
,,' 4U -fv , i [I - ' i;k ,^ \
\ t t r
"J-L"
. '
-z : L
- l ll
\ l e w n l n S t r o c l w t \- )

rt - c-H
For your information:
The MO diagramfor CH+ illustratesthat of the 8 bondingelectronsin this molecule,two'are
lower in energythan the other six. This result cannotbe predictedbasedon Lewis structuresor valence
bond theory, and the questionbecomesis this truly the case? In a technique called photoelectron
spectroscopy,the ionization potential (the energyneededto remove an electron from a molecule) of CH+
can be measured.If all electronshad the sameenergyvalue,photoelectronspectroscopywould give a
singlevalue for the ionizationpotential. This is not the case. Photoelectronspectroscopyprovidestwo
valuesfor the ionization potential of CH+ (dependingon which electronsare ejected)as predictedfrom
MO theory - sincethere are electronsat two different energylevels, they require a different amount of
energyto be removed.
MO is a more accuratetheory to describebonding, but it is very mathematicaland not as easyto
understandas valencebond theory. For this course,valencebond theory and Lewis structuresonly run
into trouble when no one single Lewis structurecan be drawn and the concept of resonanceis used.
Consider ozone,theonly difference in the two major resonancestructuresis in the location of the n bond
(or n electrons)and nonbonding electrons. The atomsare in the sameposition, and the geometryis the
samein eachcase. As a result,valencebond theory givesa good descriptionof the o bondsbut a poor
descriptionof the n bonds, where the electronsare delocalizedover the molecule. This delocalizationis
preciselywhat MO theory doesbest! During this coursewe will primarily utilize valencebond theory to
describethe electronsin o bonds (or bonds forming in a reaction) as localized betweenthe two atoms,
and in later chaptersuse MO theory to show how the n electronsof certain molecules (and reactions)are
delocalizedover the entiremolecularstructure.
@ @
-O- <-+ /o__o
o o
o o