34 Chapter l Fundarnental Concepts Problerns 35

,
Il (fr\(~ /fi4Jeccf-l'w ,0, j:':-u.. 1.4 Cyclic groups are formed by taking the series of powers on a single element up
I
c);/ll.J-t i u_/):(I'f1!);,_{)r' (,j, J
t1J. to the order of the group, such that G = [X, X2, ... , Xh = E]. Taking each of the
120(J_ I -,:
I
H -
oQL'tl- following operations as the base elernent of a cyclic group, determine the series
I
1;( fr-G'>- ~l~_ i)~{~'{IfV,d.t,-.~,
'BHfl!. k Tw-L19A..,;. f--.
of all operations that constitutes the group, identify the group, and develop its
",/ --a1-:J::;- __-,_,-//
r:rJ. -ff-L.~yt~' multiplicationtable: (a) C3, (b) C6, (c) 54 Identify all the subgroups of these
cyclic groups.
H ' Figure 1.21 The structure of hydrogen per- 1.5 Develop the multiplication table for the group C2h, which consists of the opera-
tions E, C2, i, and a.; [Hinl: Determine the effects of the operations on an arbi-
oxide (point group C2).
trary point whose initial coordinates are x, y, el Is this group Abelian?
point group D3. As this illustrates, chiral molecules may have some symme- 1.6 Determine the point group of each of the following shapes:
t!t
try, In generai, the restriction is that a molecule is dissymmetric and may be J
chiral either if il is asymmetric or if has no other symmetry than proper re:

tation. The point group D3 satisfies the latter criterion, since the group con-
(a) Q (c)
*
sists of the operations E, 2C3, 3C2. In light of these restrictions, only mole-
cules belonging to certain point groups are candidates for chirality. The
possible chiral groups are Cl (asymmetric), Cn, and Dn*
(d)
(e) <l (f) >-
The traditional test of chirality is to draw or build models of the suspect
species to see if nonsuperimposable, mirror-irnage isomers exist. As a practi-
cal matter, this exercise need only be carried out if the molecule belongs to
one of the possibly chiral point groups. In most cases, molecules belonging to
any of these groups will be chiral, but in rare cases enantiomeric pairs cannot
(g) ~ (h) T
actually exist. For example, hydrogen peroxide, B202, whose structure is
(j) a Styrofoam coffee cup (no decoration)
shown in Fig. 1.21, belongs to the point group C2 but is not optically active. (k) a ceramic coffee mug with handle (no decoration)
While it is possible to build two models that are not superimposable, the dis- (I) a dumbbell (no markings)
tinction does not exist for the actual molecular structure, because relatively (m) a tennis ball, including the seams (o ne colar, no markings)
free rotation about the O-O bond continuously interconverts the two hypo- (n) an airplane propeller with four blades
thetical enantiorners. Bere, stereochemical nonrigidity precludes chir ality, (o) a soccer ball, including the seams (one color, no markings)
1.7 Determine the point group of each of the following molecules or ions, whose
shapes can be determined by use of valence-shell electron-pair repulsion
Problems (VSEPR) theory: (a) SeF s,
(b) CIFr, (c) AsF4, (d) XeF2, (e) XeF4, (f) BeF},
(g) SiFl-, (h) OCW, (i) AsCl~, (j) OSF4, (k) trans-FNNF, (1) cis-FNNF, (m)
1.1 For the following molecules, which afe shown in Fig. 1.14, sketch the locations ClSSCl (nonplanar), (n) S20~-, (o) trans-(OH)4Xe02
of all the symmetry elements, and Iist al! operations associated with each sym- 1.8 Consider the following ideaI geometries far MX" molecules (n = 3-6) and the
metry element: (a) NH3 (C3v), (b) IFs (C4v), (c) B(OH)3 (C3,,), (d) BCl3 (D3,,), distortions described far each. What are the point groups of the ideai geometry
(e) C2H6 in the staggered conformation (D)d). and the distorted geometry?
1.2 Given the set of operations (E, C4, (ThL determine the other operations that must (a) MX) trigonal planar distorted by lifting the M atom out of the plane.
be present to form a complete point group. [Hint: Consider all the products of (b) MX4 tetrahedral distorted by-slightly flattening the rnolecule along one of
the given elements with themselves and with each other.] Identify the point ~~~. .
group for the complete set of operations, What is the order of the group? (c) MX4 square planar distorted by equally elongating two trans-related M-X
1.3 Aside from the trivial group CI, the point group formed from the complete set bonds.
of operations from Problem 1.2 has six subgroups, Identify the subgroups and (d) MXs trigonal bipyramidal distorted by equally elongating or shortening the
give the order of each. two axial bonds.
(e) MX, trigonal bipyramidal distorted by elongating one of the equatorial
bonds.
*The rotational cubic groups T, O, and [ can also be added to this list, but no molecules with (f)MXs trigonal bipyramidal distorted by elongating one of the equatorial bonds
these symmetries are likely to be encountered. and shortening one of the axial bonds (or vice versa).
 36 Chapter J Fundarnental Concepts Problerns 37
Qlnl~~
(g) MX6 octahedral distorted by elongating two trans-related bonds.
(h) MX6 octahedral distorted by slightly closing the 90 angles between the three
M-X bonds in both sets of cis-related positions.
1.9 Identify the point group for each of the following FeJ+ complexes with the biden-
tate oxalate ligand (ox = C20~-). Where allowed by the point group, determine
which complexes are chiral. [Hint: Use models to help identify the point group
WC1
F F
~ F F
and to verify the existence of enantiomers.]
(q) (r) (s) (l)
(a) tris( oxalato )ferrate(III), [Fe( oxhf-
(b) lrans-dichlorobis( oxalato )ferrate(III), [FeCl2( ox)z]3-
(c) cis-dichlorobis( oxalato )ferrate(III), [FeCI2( OX)z]3-
x x
(d) cis-di bromo-trans-dichlorooxalatoferrate(III), [FeBr2Cl20x]3-
(e) cis-dibromodichlorooxalatoferrate(III), [FeBr2CI20x f-.
1.10 Identify the point group of each of the following structures.
LL F~~
Cl Cl
F~
CI F Cl
Fl(CI F (u)
X
( v) (w)
(a) (b) (c) (d)
o CI-Q
Cl
~ ~ ~
F
F~
F ClD
O OCi OCi
F F F CI F F F F F Cr _
Cr
(e) (f) (g) (h)
F F
p:j
c:::J

Cl
FPCl (x) (y) (z)
F F CI CI
(i) (j) (k) (l)
1.11 Identify the point group of each of the following cyclopentane derivati ves in the
configurations shown.
8 HA~
F
~F~
~ ~ ~
F
F F
(m) (a) (b) (c)
(n) (o) (p)
 38 Chapter 1 Fundamental Concepts Problerns 39
00 V b
F F F
~ ~ ~
(k) (l)
F (i) (j)
(d) (e) (I)
F
tb 1; ~
F (o) (p)
Cm) (n)
F
?b C2J
F
(g)
F

(h) (i)
F

~ #
CC?
(r) (s) (t)
(q)
~
F
(j) (k) (1)
1.12 Identify the point group of each of the following structures.
(a) (b) (c) (d)
(e) (f) (g) (h)