CHEMISTRY 120A Inorganic Chemistry Fall 2012

PROBLEM SET 1
Due Monday, October 22nd 2012 by 1:30 pm in Pacific Hall 4502
Guidelines (Please Read Carefully): Please include this top page in your submission to
facilitate the grading of your problem sets and the assignment of grades. Please write
clearly (especially your name, student ID and email address). Please write your
answers clearly in the spaces provided. Do not attach additional sheets. Please bring
your UCSD ID with you when you hand in the problem set. Be prepared to sign-out on
your problem set to receive credit. Thank you!

Question 1 ________/ 10

Question 9 _________/ 25

Question 2 ________/ 10

Question 10 ________/ 20

Question 3 ________/ 15

Question 11 ________/ 30

Question 4 ________/ 25

Question 12 ________/ 20

Question 5 ________/ 25

Question 13 ________/ 20

Question 6 ________/ 10

Question 14 ________/ 20

Question 7 ________/ 10

Question 15 ________/ 45

Question 8 ________/ 15

NAME: _____

Answer KEY_________________________

SECTION: _____________________________________________
PID: __________________________________________________
UCSD Email Address: ___________________________________

TOTAL

/ 300


Question 1 (10 points). In the spaces provided, sketch the radial wave function and
the radial probability function for a 5P orbital. In both your plots, label the radial nodes.







2

Question 2 (10 points). On the axes below, draw the angular component of the
indicated wavefunction.

Z

py

dyz

dz2

dxy

Question 3 (15 points). Rank order the following sets of orbitals from highest to lowest
energy:
A) N(2s) F(2px) C(2pz) O(2s) B(1s) C(2s) B(2pz) F(1s) N(2py) O(2px)
B(2pz) > C(2pz) > N(2py) > O(2px) > F(2px) > C(2s) > N(2s) > O(2s) > B(1s) > F(1s)
Ranked by from least electronegative to most and by principal quantum number.
B) Se(3pz) S(3px) Se(4py) Te(4s) Te(5s) Te(5px) O(2px) S(2pz) O(2s) Se(4s)
Te(5px) > Te(5s) > Se(4py) > Se(4s) > Te(4s) > S(3px) > Se(3pz) > S(2pz) > O(2px) >
O(2s)
Ranked by principal quantum number and effective nuclear charge.
Question 4 (25 points). Draw a qualitative molecular orbital bonding scheme between
px orbitals of the following pairs of atoms. Draw both the bonding and anti-bonding
component of the molecular orbital scheme.
A) C-N

B) C-S

C) B-O

D) N-O

x
C

x
C

E) P-B

N
C
O

Question 5 (25 points). Name the compound and draw the structure, including any
isomers.
a. K4[Ru(CN)6]
potassium hexacyanoruthenate(II)

b. [Cu(H2O)6]SO4
hexaaquacopper(II) sulfate

c. [Cu(H2O)2(NH3)4]SO4
cis/trans-tetraamminediaquacopper(II) sulfate

d. [Co(en)3]Cl3
/-tris(ethylenediamine)cobalt(III) chloride

e. W(CO)3(PPh3)3
fac/mer-tricarbonyltris(triphenylphosphine)tungsten(0)

Question 6 (10 points). Name the following compounds:

a. cis-diamminetretrachlororplatinum(IV)

b. sodium tetrachloronickelate(II)

c. fac-trichlorotripyradinerhodium(III)

d. pentaaquahydroxoiron(III) bromide

e. mer-bromotricarbonylchloroiodomolybdenum(III)

Question 7 (10 points). Name the following coordination complexes (Underlined atoms
designate connectivity):
a. [Zn(NH3)4]I2
tetraamminezinc(II) iodide
b. K2[Pt(Cl)6]
potassium hexachloroplatinate(IV)
c. K2[ReH9]
potassium nonahydridorhenate(VII)
d. [CrF4]Cl2
tertrafluorochromium(VI) chloride
e. [Co(ONO)(NH3)5]Cl2
pentaammine(nitrito-O)cobalt chloride
Question 8 (15 points). Draw the structures of the following compounds:
a. ammineaquadichloroplatinum(II)

cis/trans

b. tricarbonyltris(triphenylphosphine)molybdenum(0)

mer/fac

c. tetraammineaquapyridinecopper(II) sulfate

cis/trans
d. bis(ethylenediamine)dichlorocobalt(III) iodide

cis/trans
e. pentaaqua(thiocyanato-S)iron(III) bromide

Question 9 (25 points). Draw all possible isomers of (underlined atoms designate
connectivity):
a. Na[PtBrCl(NO2)(NH3)]

b. CoCl3(NH3)3

c. [CoCl2(NO2)2(NH3)2]-

d. [Co(ox)3]3-

e. (NH4)2[Ni(C2O4)2(H2O)2]

Question 10 (20 points). Determine the point group of the following molecules.
Cl

Cl

Cl

Hg
Cl

Cs

Co

OC

O
C

O
C

O
C

C2

OC

CO
OC

C
O

C
O

D3d

Mo

Co

C
O

Cs

D6h

C2v

O
C

CO

Co

CO

Co
CO

OC

C
O

D2d

O
O

Cl
Cl

Mo

Cl
N

Cl

Mo
Cl

Cl

Cs

C4v
NH3

F
F

H3N

NH3

Br
OC
N

Br

Rh

Rh
Br
Br

CO

C!v

Ci

OH2

Fe
H2O
OH2
H2O
OH2
!

C3v

CO
Br

OH2

CO

C2h

2+

CO

S4

D2h

OC

Oh

CO

CO

OC

C2

Td

Br

P
P

Pd
CO

C2h

D3h


Question 11 (30 points). Perform the operations of the D4d point group on
bis(cyclobutadienyl)cobaltate(-1), which is shown below with its 8 carbon atoms labeled
1-8. Redraw the structure for each operation, clearly showing where each carbon atom
ends up upon the application of each symmetry operation.

3

2
20

Co

6
7

20

C2'

!d

Hint:

S8 (clockwise)

E
3

20

Co

Co

20

4
20

Co

Co

C2 (z axis)

Co

Co

5
20

20

S8 (counterclockwise)

7
20

20

7
20

S83 (clockwise)

Co

20

C4 (counterclockwise)

20

20

3
20

Co
20

5
20

20

C4 (clockwise)

S8 (counterclockwise)

8
4

20

C2'
(bisects 1&8, 3&6)
6

C2'
(bisects 1&5, 3&7)
7

Co

Co

Co

Co

20

!d
(passes thru 1 & 3)
3

20

20

!d
(passes thru 2 & 4)

!d
(passes thru 6 & 8)

1
2

20

6
5

20

20

Co

Co

Co

Co

3
20

20

20

20

20

!d
(passes thru 5 & 7)

20

5
20

C2'
(bisects 2&6, 4&8)

20

20

20

C2'
(bisects 2&5, 4&7)

Question 12 (20 points). Answer the following questions for the Pt(IV) compound
below.

Y

H
H
Ph3P

Pt

PPh3

H
H

A. To what point group does this molecule belong? _____D4h__________________

B. How many C2 rotation axes are present in the molecule? _____5____________
C2'

H
Ph3P

Pt
H
H

C2''

H
PPh3

Principle rotation axis

(C4 and C2)

Pt

C2'

C2''
(view in xy plane, phosphines
omitted for clarity)

C. How many mirror planes are present in the molecule? ____5_______________

The equatorial plane of the 4 H atoms and the central Pt defines the h
plane. The 2 v and 2 d lie along the 2C2 and 2C2 axes above,
respectively, and come in and out of the plane of the paper (z dimension).
D. Using the coordinate system shown, provide the proper Mulliken symbols for
each of the atomic d orbitals on Pt.
Using the right-hand column in the D4h character table that displays the
quadratic functions corresponding to their respective irreducible
representations:
dz2 = A1g

dxz = Eg

dyz = Eg

dxy = B2g

dx2-y2 = B1g

E. Which symmetry operation(s) exchange the locations of the phosphine ligands?

2C2, 2C2, i, 2S4, h
F. Which of the operations in this group, if any, is/are equivalent to a S2 improper
rotation?
S2 = C2 x h = i
An S2 improper rotation is equivalent to an inversion operation.

Question 13 (20 points). A picture of a dx2-y2 orbital is shown below. A) In the D4h point
group, indicate the character returned for this orbital in response to each operation of
the point group (5 points). B) In the space below, draw the new orientation of the dx2-y2 in
response to each operation of the point group (15 points)

Y

x2-y2

-1

-1

-1

-1

= B1g

Question 14 (20 points total): Using the D6h character table, assign the following
SALCs to their respective irreducible representations.

A2g

B1u

A1g
a

b
a

c
f

B2g

c
c

e
e

A1g

A2u

Question 15 (45 points). Consider the ozone (O3) molecule below and complete the
following problems (this question contains parts a-d). Ozone possesses a formal bond
order of 1.5 between the central oxygen atom and the two terminal oxygen atoms (Oa
and Ob).

z
O
y

Ob

Oa

x
a) Determine the point group of O3 and, using the coordinate system above, assign the
atomic orbitals on the central oxygen atom to their respective Mulliken Symbols (5 pts)
Point Group = C2v

A1

B1

B2

A1

2s

2px

2py

2pz

b) Generate the -bonding framework for O3. Determine the irreducible representations
for the terminal oxygen orbitals in the -direction (SALCs). You can assume that each
terminal oxygen atom uses only its s-orbitals for -bonding. To receive full credit, clearly
show all your work. (10 pts)
Character summary for s-bonding SALCs (made up of flanking oxygen s-obitals).
Note change in B1 vs. B2 due to orientation.

C2v

C2

!v(xz)

!'v(yz)

"

A1

B2

-1

-1

#(A1) = 1/21/2[Oa+Ob]

#(B2) = 1/21/2[Oa-Ob]

c) Sketch a Molecular Orbital Diagram for the -framework of O3 and draw all bonding,
non-bonding and anti-bonding molecular orbitals. Also indicate the symmetry of each
molecular orbital. Be sure to draw pictures of the molecular orbitals (i.e. AOs + SALCs)
to accompany their placement in the Molecular Orbital diagram. (15 pts)
z
2b2

O
Oa

Ob

3a1

x
B1

B2

2b2
All oxygen s orbitals at
the same energy

A1

3a1
1b1

2px

2py

2pz

A1

2a1

1b1

B2

NON-BONDING
and Empty

B2
A1
2s
A1

ANTI-BONDING ()

2s

2a1

1b2

2O
(i.e. Oa & Ob)

1b2
1a1
A1
orbital
of
2pz
parentage
on
central
oxygen
atom
mixes with A1 SALC made up of
flanking oxygen s orbitals,
thereby
lowering
its
energy
a bit. This 2pz orbital is slightly bonding, but mostly non-bonding and empty.
It will engage readily in the pi-system of the O3 molecule.

1a1

BONDING ()