Hku Inorganic Chemistry 2 Test

THE UNIVERSITY OF HONG KONG
DEPARTMENT OF CHEMISTRY
CHEM2303 Intermediate Inorganic Chemistry
CHEM3341 Inorganic Chemistry II
9:30 am - 12:30 pm
December 8, 2014 (Monday)
Only approved calculators as announced by the Exan1inations Secretary can be used in this examination. It is
candidates' responsibility to ensure that their calculator operates satisfactorily, and candidates must record the
name and type of the calculator used on the front page a/the exa111ination script.
Answer ALL questions in Section A in the YELLOW answer book.
(Total 40 marks)
Question 1 (6 marks)
Question 3 (I 0 marks)
Question 5 (I 0 marks)
Answer THREE questions in Section Bin the BLUE answer book.
(Total 60 marks)

A Periodical Table and a Tanabe-Sugano diagram are provided on the last pages of this
question paper.
Page 1of11
Section A
Answer ALL qnestions in this section in the YELLOW book. (Total 40 marks)
I.
(a)
Predict the product of reactions between Vaska's complex with 02, h and CH3l
respectively.
Vaska's Complex
(3 marks)
(b)
2.
The v(CO) of Vaska's complex is 1967 cm- 1 Predict whether the CO stretching
frequency of the three products produced in part (a) would be higher or lower
than that of the Vaska's complex. Explain briefly.
(3 marks)
Rationalize the following observations:

(a) Strained alkenes such as cyclopropene or norbornene bind unusually strong to
transition metals to form complexes.
Cyclopropene
Norbornene
(3 marks)
(b)
The v(CO) frequencies in the IR absorption spectrum of Fe(C0) 5 are higher than
that ofFe(COh(PPh3)z.
Fe(CO)s
v(CO)
2025 and 2000 cm- 1
Fe(C0)3(PPh,)z
1944, 1886 and 1881 cm-'

(3 marks)
(c)
In the substitution reaction of V(C0) 6 with phosphines, the rate of reaction

increases according to the order PMe 3 > PBu 3 > P(OMe h > PPh3.
(3 marks)
Page 2of11
3.
Suggest a plausible mechanism for each of the following reactions. You should
clearly indicate the electron count of the intermediates and the type of organometallic
reactions involved in each step in the mechanism.
co
a)
I
Co
A_
oc/ "co
PPh3
(6 marks)
~NO
I
2
b)
Rh
~NO
I
2
PPh 3
oc/ "co
oc/
Rh
+CO
'PPh 3
[Note: for reaction 3(b), your mechanism must be consistent with the following
observations: (i) using excess PPh3, the rate is first order in rhodium complex; (ii) c.st
is negative.]
(4 marks)
4.
(a)
Give the ground state Russell-Saunders term for Co2+ ion. Give also the spectral
terms in an octahedal field that would correlate with this Russell-Saunders term.
(2 marks)
(b)
Classify the following electronic configurations as T, A, or Estates:

(i)
(t2g)\eg)4 in an octahedral metal complex
(ii)
(t2g) 3 ( eg) 3 in an octahedral metal complex
(iii) (e) 4 (t2 )4 in a tetrahedral complex

(3 marks)
5.
(a)
Correlate the strength of the following ligands to the ligand field splitting (t.0 ) in
an octahedral complex. Illustrate your answer with the aid of simplified molecular
orbital diagrams.
(i) er-donor ligands
(ii)
n-acceptor ligands
(iii) n-donor ligands

(6 marks)
(b)
Give the classification of the ligand types for terminal CO, F- and H-. Based on
(a), describe how these ligands would affect the t.0 value.
(4 marks)
Page 3of11
Section B
Answer THREE questions in this section.
6.
(a)
(Total 60 marks)
The reaction between PtC'2 and carbon monoxide gas at high pressure and 200 C
yields a product with molecular weight of 322.
(i)
Identify the product of the reaction and suggest possible isomers of the
product.
(3 marks)
(ii)
Comment on the relative M-C and C=O bond lengths in these isomers.
Explain briefly.
(3 marks)
(iii) Suggest a characterization method to distinguish between these isomers.

Explain briefly on your expected results.
(2 marks)
(b)
At -44C, the 1H NMR spectrum ofFe2(C0)4 (ri 5 -C 5 H5) 2 consists of a single peak,
but at -66C it shows two signals. The IR spectrum is unchanged over this
temperature range, and contains peaks in the 2000-2100 cm- 1 and 1800-1900
cm- 1 regions. Suggest processes that account for these data, and draw all
relevant structures.
10.0 Hz
(4 marks)
(c)
Calculate the valence electron count on the following iron-sulphur cluster.

Determine if there is a bond between the two Fe atoms.
K
sx
oc~Ft~~:~~--)e~co
/'
oc bo
c\.
ot
"co
(3 marks)
Page 4of11
7.
(d)
Write a short essay on the structure and electron transfer properties of

iron-sulphur clusters and their importance in nitrogen fixation.
(5 marks)
(a)
Design two-step syntheses of cis- and trans-[PtCh(N02 )(NH3)r starting from

[PtCl4] 2 -.
(4 marks)
(b)
Briefly explain why the c1s-1somer of [Pd(CH2CH3) 2 (PR3)2] decomposes

immediately to give butane but the trans-isomer produces a 1: 1 mixture of
ethylene and ethane.
(4 marks)
(c)
The palladium dialkyl complex A was found to react readily with CD3I at room
temperature to release 1, 1, 1-trideuterioethane (CH 3CD3) as the only gaseous
product detected by mass spectrometry. Explain briefly.
fH3
Ph2P-;d-PPh2
H3C
Complex A
(4 marks)
8.
(d)
Suggest some strategies for the design of stable transition metal alkyl complexes
and illustrate your answer with appropriate examples.
(8 marks)
(a)
A neutral first row transition metal carbonyl complex [M2 (CO)x] (X), has a
relative molecular mass 341.95 and contains 28.1 % carbon by mass. The IR
spectrum of solid X shows three strong CO absorption bands at 2071, 2042 and
1853 cm- 1 respectively. Treatment ofa hexane solution ofX with high pressure
of H2 generates a product, Y, which has IR bands at 2053 and 2030 cm- 1 and a
1
H NMR signal at -12 ppm. Based on the spectral information, what is the
metal M? Assuming both complexes obey the 18-electron rule, deduce the
chemical structures of X and Y and explain your reasoning. You should also
account for the spectral data of the two complexes.
(10 marks)
Page 5 of 11
(b)
9.
Write a short essay on innersphere electron transfer mechanism. Describe also

the experiment conducted by Taube that led to the establishment of the
mechanism.
(JO marks)
Explain the following experimental findings with reasons. Illustrate and elaborate
your answers with the aid of appropriate chemical principles, rules and mechanisms.
(a)
The structure of [Cu(bpy) 3 ] 2+ has equatorial Cu-N bonds of 2.03 A and axial
distances of2.23 and 2.45 A (bpy = 2,2'-bipyridine).
(4 marks)
(b)
Copper(II) chloride in aqueous solution is pale blue in colour whereas an intense

blue solution is obtained when it is dissolved in aqueous ammonia.
(6 marks)
(c)
The self-exchange or electron exchange reactions of copper(II) complexes are

usually slow.
(6 marks)
(d)
[Mn(OH2)6]2+ appears very pale pink to almost colourless whereas [Mn0 4 is

very intense purple in colour.
(4 marks)
- END OF PAPER-
Page 6 of 11
. The periodic table

3
10
11
12
13
14
15
-
16
.-
17
He
4.0026
Key:
1.008
Lithium
Berylllum
Element NamE!
Boron
Carbon
Nitrogen
oxygen
Fluorine
Neon
Atomic number
10
Li
Be
Ne
6.94
9.0122
12.011
18.998
20.180
Magnesium
Silicon
14,007
Phosphorus
15.999
Sodium
10.81
Aluminium
Sulfur
Chlorine
Argon
11
12
13
14
15
16
17
18
Al
Si
Cl
Ar
26.982
30.974
Arsenic
32.06
Selenium
35.45
Bromine
Krypton
33
34
35
36
Symbol
Atomic weight /mean relative mass\
Na Mg
22.990
24.305
Potassium
Calcium
19
"1
"'"'..,
(l)
'""
,...
,...
18
Helium
Hydrogen
Scandium
20
21
Ca
Sc
44.956
---Yttrium--
Titanium
22
Ti
47.867
Vanadium
23
Zirconium
50.942
Niobium
40
41
Chromium
24
Manganese
25
lroo
26
Cobalt
27
Cr Mn Fe Co
Nickel
28
Ni
Copper
29
Zlnc
Gallium
28.085
Germanium
30
31
32
45
46
47
48
Rb
Sr
85.468
87.62
88.906
91.224{2)
92.90612\
95.96{2)
f97.911
101.07(2)
102.91
106.42
107.87
112.41
114.82
118.71
121.76
caesium
Barium
Lutetium
Hafnium
Tantalum
Tungsten
Rhenlum
Osmium
Iridium
Platinum
Gold
Mercury
Thallium
Lead
Bismuth
55
56
57-70
71
72
73
74
75
76
77
78
79
80
81
82
83
Cs
Ba
Hf
Ta
137.33
Lu
132.91
174.97
178.49(2}
180.95
183.84
186.21
190.23(2\
192.22
Francium
Radium
87
88
89-102
Fr
Ra
1223.02]
[226.03]
**
*lanthanoids
Os
Ir
Lawn:mr:ium
Rutherfordium
Dubnium
Seaborgium
Bohrium
Hasslum
Me!tnerium
103
104
105
106
107
108
109
Lr
Rf
'262.11 1
'265.12)
Lanthanum
Cerium
57
58
la Ce
138.91
Actinium
89
**actinoids
w Re
140.12
Thorium
90
Ac Th
r221.031
232.04
Pt Au Hg
195.0B
196.97
Darmstadtium Roentgenium
110
111
Te
Xe
127.60(3)
126.90
131.29
Polonium
Astatine
Radon
84
85
86
51
44
Ru Rh Pd Ag Cd
54
Antimony
50
43
38
Zr Nb Mo Tc
53
Tin
49
42
37
52
Indium
65.3Br2l
Cadmium
69.723
Molybdenum
63.546(31
Silver
In
Tl
200.59
204.38
Copernicium
Ununtrium
112
113
Sn Sb
Pb
207.2
Flerovium
114
Bi
Kr
Tellurium
78.96(3}
58.693
Palladium
Br
83.798(2)
74.922
58.933
Rhodlum
40.07814\
Strontium
39.948
79.904
Iodine
72.63
55.845(2\
Ruthenium
39.098
Rubidium
39
Cu Zn Ga Ge As Se
54.938
Technetium
51.996
Po
At
Xenon
Rn
208.98
'208.981
[209.99]
[222.021
Ununpentium
Livermorium
Ununseptium
Ununoctlum
115
116
117
118
Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo

1271.13]
[270"
f277.151
[276.151
[281.161
r280.161
r285.17l
[284,161
r2s9.191
r288.19i
12931
Praseodymlur
Neodymium
Promethium
Samarium
Europium
Gadolinium
Terb!um
Dysprosium
Holmium
Erbium
Thulium
Ytterbium
59
60
61
62
63
64
65
66
67
68
69
70
{268.131
Pr Nd Pm Sm Eu Gd Tb Dy Ho
140.91
Protactinium
91
Pa
231.04
Er Tm Yb
144.24
[144.911
150.36{2)
151.96
157.25{31
158.93
162.50
164.93
167.26
168.93
173.05
Uranium
Neptunium
Plutonium
Americium
Curium
Berkelium
Californium
Einsteinium
Fermium
Mendelevium
Nobelium
93
94
95
96
97
98
99
100
101
102
92
238.03
Np Pu Am Cm Bk
'237.0~
[244.06]
1243.06]
[247.on
r241.on
Cf
[251.081
Es Fm Md No
1252.081
1257.101
1258.101
[259.10]
[294]
1294"
d 2 Tanabe-Suga no diagram
d Tanabe-Sugano diagram
'T,
'T:
lT,
iT~
ffi
~/
10
20
'A,
30
10
0/8
20
AIB
Page 8of11
30
d Tanabe-Suga no diagram
'A,
70
'GI
:~r
'G:~
VA:::O)
.I
/'E(Gl
'F
:~50
'F
o,
21
A~
V/'E
o~ ~ 'm.~5'~S
~~
'A
ms4o
'E
'G
'A~,
" " - """'
'T,
30
::~~~p---A,
'H~
~~ ~ /,::
201
.......'\
.......
/ /
'E
~ I
'l /
10
20
Ml
/>
'T,
10
I
ts
30
'A
1o
2o
JlJB
Page 9of11
\JI
30
'T,
'T.
'A,
'A,
'A,
'E
I
'G
70
'E
io
60+
I
I
60
'P
'F
'T,
'F
40
'D
's
,,
IB 40
,' sr2
,,
'G
'D
.,
,,,"!,
... .
'H
20
..
,.,, '
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'T,
v._,..
,. . ~'
, ''
,,
30
'G
'F
'P [ /
'
iil
,.,.."
,,..,'
,,
,,'' ,,
, ........
,, ,
,,
20
,,' ,...,.,,..
,,,,.,,,..
'G
,..,.../'
'T,
'D
10
,,,'
. ...
'A,
'T,
'F
//
............
..........
10
....... , .. ' '

20
fllB
Page 10of11
'
,.
--:~..
40
,
'
'
,' '
.'T
' '
,,
'T,
////
10
30
''
,,'
2D
fllB
,' '
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'T,
'A,
'P
'' ,.;,*""
..,.... /,,''
10
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,,
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30
'p
'H
-,1
I
I
'F
'o
,,.._
,,.....' /
'
50
50
,,/
'
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''
4
T1
2E
30
,4T,
E
....ro
JC"
0
M
tl.O
ro
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c
ro
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tl.O
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<l

CHEM3341 Inorganic Chemistry U

9:30am~
December 21, 2013 (Saturday)
12:30 pm
Only approved calculators as announced by the Examinations Secretary can be used in this examination. It is
candidates' responsibility to ensure that their calculator operates satisjGctorily, and candidates must record the
name and type ~f the calculator used on the front page of the examination script.
Answer ALL questions in Section A in the YELLOW answer book. (Tota140 marks)
Question I (15 marks)
Answer THREE questions in Section Bin the BLUE answer book. (Total 60 marks)
Each question carries 20 marks.
A Periodic Table and a Tanabe-Sugano diagram are provided on the last page of this question
paper.
Page 1 oflO
Section A
Answer ALL questions in this section in the YELLOW answer book. (Total40 marks)
1. (a)
Arrange the ligands, F-, NH 3 and CN-, in an order of the spectrochemical series. With
the aid of simplified molecular orbital diagrams, explain the order by correlating the
strength of the ligands to the ligand field splitting (i1o) in an octahedral complex.
(7 marks)
(b)
"Metal carbonyls with octahedral geometry and d 6 electronic configuration are usually
diamagnetic."
(i)
Comment whether this statement is true or false. Justify your choice with
reasons.
(3 marks)
(ii)
Give the ground state Russell-Saunders term for d 6 electronic configuration.

6
Give also the ground state spectral terms for both weak field and strong field d
electronic configuration.
(2 marks)
(iii) Identify and assign all the possible electronic transition(s) that can occur in
octahedral d6 metal carbonyls.
(3 marks)
2.
Suggest two possible structures for the chromium complex [(11 5 -C 5H5 )Cr(C0) 3 ]2 which
obey the 18 electron rule. Indicate the spectroscopic methods by which you could
distinguish these structures. Explain briefly.
(4 marks)
3.
The v(02 ) IR stretching frequencies of the two cobalt(III) complexes, [Co(salen)(py)Oz]

(py = pyridine) and [ {Co(NH3 ) 5 }202 are at 1144 and 805 cm- 1 respectively. Discuss
the electronic structure of these two complexes and explain the difference in v(0 2 )
frequencies.
t+
Salen
(5 marks)
Page 2 of 10
4.
Soluble guanylate cyclase (sGC) is a Fe(II) hemoprotein receptor for nitric oxide. sGC is
isolated as a five-coordinate, heme protein with histidine as the axial ligand. Upon NO
coordination, the Fe-NO unit is bent with an Fe-N-0 angle of 140 and an unusually
long Fe-N bond is observed for the coordinated histidine. Write a short essay on the
structure and bonding ofheme-NO and briefly account for the long Fe-N bond observed
for the coordinated histidine.
(8 marks)
5.
Comment on the following observations:

(a) Free nitrogen molecule is IRinactive but exhibits a vibrational band at 2331 cm- 1 in
the Raman spectrum. Upon coordination to a metal as a terminal ligand, this
v(N=N) band becomes IR active and shifts to about 2200-2000 cm- 1
(4 marks)
(b)
The H NMR spectrum of(CsHs)2Fe(C0) 2 shows two peaks of equal area at room
temperature but give four resonances of relative intensity of 5:2:2:1 at low
temperature.
(4 marks)
Section B
Answer THREE ont of four questions in this section in the BLUE answer book.
(Total60 marks)
6.
Cobalt(II) chloride indicator papers are prepared by soaking a piece of filter paper into an
aqueous solution of hydrated cobalt(II) chloride (CoCh6H20), followed by drying it in
an oven to give a distinct blue colour. The indicator paper can then be cut into small strips
and stored in a desiccator. Upon exposure to moisture or water, the colour of the indicator
paper will turn from the distinct blue colour to a pale pink colour. The blue colour
observed in the anhydrous state is believed to be due to the formation of a tetrahedral
complex.
(a)
Identify the blue species. Identify also the species that gives rise to the pale pink
colour when exposed to moisture or water. Rationalize the observed colour
changes.
(4 marks)
(b)
Suggest the origin of the electronic transitions that are responsible for the blue
colour and the pale pink colour and give the spectral assignments for these
electronic transitions.
(4 marks)
(c)
State the selection rules for electronic tansitions and describe two mechanisms for
the relaxation of the Laporte selection rule. Rationalize the observed differences in
both their colour and intensity and discuss them in the context ofligand field theory
and the selection rules.
(12 marks)
Page 3 of 10
7.
(a)
(b)
(i)
Describe the outersphere electron transfer mechanism. State the Marcus

Cross Relation for outersphere electron transfer reactions.
(4 marks)
(ii)
Explain why the redox reaction between [Ru(NHJ)6] 3+ and [Cr(Hz0)6] 2+ is

slower than that between [Ru(NH3)6] 3+ and [V(H2 0)6] 2+ in spite of the fact
that [Cr(H20) 6] 2+ is a stronger reducing agent than [V(H2 0)6] 2+.
(6 marks)
Cis-platin is the first generation of platinum anticancer drug. Briefly describe its
mechanism of action and explain why the trans-isomer lacks anticancer activity.
(5 marks)
(c)
A method for distinguishing between the cis- and trans- isomers of platin
complexes was developed by reacting [PtCh(NH3 ) 2] with thiourea in water. One of
the isomers would produce a deep yellow solution of [Pt(Th) 4 ] 2+ (Th = thiourea),
whereas the other isomer produces a white complex which has low solubility in
water. Explain the rationale of this chemical characterization method and propose a
structure for the white complex.
Chemical structure ofthiourea

(5 marks)
8.
(a)
Metallocyclopentanes (A) are more stable compared to their bis-alkyl analogues

(B). Explain briefly.
Hz
/C--...CH3
M
\.....-CH 3
Hz
(B)
(A)
(4 marks)
(b)
and illustrate your answer with examples.
(8 marks)
Page 4 oflO
9.
(c)
Based on the Dewar-Chatt bonding model, comment on the following C-C bond
lengths in coordinated ethene (1 pm = 0.01 A) and discuss the various factors that
would affect the representation of metal-alkene complexes as coordinated alkene or
metallo-cyclopropane.
C2H4
133.5 pm
K[PtCl3(C2H4)]
137.5 pm
[Pt(PPh3)2(C2~)]
143 pm
[Os(C0)4(C 2 ~)]
149 pm
C2H6
153.2 pm
(8 marks)
(a)
A study on CO substitution reaction by PPh3 of various (L)Rh(CO)z complexes was

carried out, where L is an aromatic ligand as shown below. The kinetic study
indicated that the mechanism of substitution was associative in nature. The relative
rates of substitution were shown below.
LRh(C0)2 + PPh3 - - LRh(CO)PPh3 + CO
Ligand
Relative rate of
substitution
(b)
Cyclopentadienyl
Indenyl
()@
3.8
Fluorenyl
10
>lOw
(i)
Write the rate equation and propose an intermediate for the ligand
substitution reaction.
(4 marks)
(ii)
Drastic increases in the relative rates of substitution were observed for the
complexes with indenyl and fluorenyl ligands. Provide an explanation to
account for the differences in reactivity.
(10 marks)
The complex trans-[Rh(bpy)2Cbt reacts with various T, giving [RhY(bpy)2Clt.

The rate law for appearance of the product is Rate= (k1 + k2[T])[Rh(bpy)2Cl/].
Suggest a possible mechanism for this reaction which accounts for the rate law.
(bpy=
o-o
N
-END OF PAPER-
Page 5 oflO
)
(6 marks)
--
--
--
--
helium
He
4.0026
1.0079
bef)11l\Jm
boron
cmton
nllr<:Qen
oxygen
nuorlne
Li
Be
&.941
sodium
9.0122
magnesium
10.811
12.011
aluminium
15.999
sulfur
18.998:
s~icon
14.007
phosphorus
20.180
chlorine
argon
12
13
14
15
16
17
18
lithium
11
22.990
24.305
potassium
calcium
scandium
manlum
vanadium
chromium
mang::mese
lroo
eo ball
nickel
copper
19
20
21
22
23
24
25
26
27
28
29
Se Ti
K ea
39.098
rubidium
40.078
strontium
37
38
44.956
....
0
85.468
caesium
87.62
barium
55
56
Cs Ba
132.91
fmnclum
87
137.33
radium
88
Fr Ra
,,.
12231
57-70
*
**
89-102
~1trium
50.942
niobium
39
40
41
42
*Lanthanide series
**Actinide series
AI
Si
28.0136
zinc
gamum
aerman!Um
30.974
arsenic
32.065
selenium
35.453
bromine
krypton
30
31
32
33
34
35
36
43
58.933
58.693
63.546
sii>Jer
65.39
C::i:lmlum
69.723
pall~dlum
lndium
72.61
!in
74.922
antimony
78.96
teHurium
79.904
Iodine
xenon
44
45
46
47
48
49
50
51
52
53
54
92,906
tantok.lm
95.94
tungsten
19SI
rhenium
101.07
osmium
102.91
iridium
106.42
platinum
107,87
gold
71
72
73
74
75
76
77
79
79
180.95
dubnlum
183.84
seaborglum
186.21
bohrium
190.23
has slum
192.22
metlnerium
195.08
ununntnum
196.97
unununlum
200.59
ununblum
105
106
107
108
109
110
111
112
Re Os
lr
112.41
mercury
ao
103
Lr
Rf Db Sg Bh Hs Mt Uun Uuu Uub
tanUmnum
cerium
57
58
13!!'.91
actinium
140.12
thorium
89
90
2621
.,,
114.82
lhal!lum
11H]1
Xe
121.76
bismuth
127.60
polonium
126.90
aslotine
131.29
81
82
83
84
85
86
20S.9S
2091
2101
222
1260
12641
12691
12681
12711
12721
121n
204.38
2!.i7.2
ununquadium
114
Uuq
12891
neodymium
promethium
samarium
europium
!ladolinlum
lerb!Um
dysprosium
holmium
erbium
lhullum
ytterbium
59
60
61
62
63
64
65
66
67
68
69
70
140.91
prolnc~nium
144.24
uranium
91
92
praooodymiu
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
Ac Th Pa
2271
23-2.04
23-1.04
23-!!.03
""
93
neptunium
150.36
pltltontum
151.95
americiUm
157.25
curium
159.93
berkelium
162.50
caHornlum
164.93
einsteinium
187.26
fermium
168,93
mendelevium
173.04
nobelium
94
95
96
97
98
99
100
101
102
Np Pu Am Cm Bk Cf Es Fm Md No
12371
12441
1243
83.80
radon
Pt Au Hg Tl Pb Bi Po At Rn
104
261
39.948
rhcdium
91.224
hafnium
174.97
17SA9
lawmnclum rutherron:lium
Cl Ar
55.845
rutheniUm
Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te
Lu Hf Ta
F Ne
26.91!2
88,9(15
lutellum
12621
Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
51.996
5-1.938
molyl:ldenum technetium
47.867
;z:Trcontum
Rb Sr
""'"
10
Na Mg
~'""
"',...,
--
hydrogen
12471
247
''"'
1252
257
12581
12591
'T,
'T,
'T,
'r,
fll
10
20
/r'A,
30
10
20
~B
~B
Page 7 of!O
30
70
701
'
./
./
'A,
<~f
'F
'F
'D
50
,T,
'E(D)
V I I/::.
I
'F
'G
's
Yl
/'A,
'
f - - - - - - - - - - j '-
/'E(G)
}I
'A,
~;
:wz
,.,fa~
'~~
~11
30
'A,
~ I
:\:SZs
~~~-
~~"V~:::
~ ""1/ j/'T,
201
'E
'T
'"
,~/.'
/
10
20
:
s
30
10
20
~
Page 8 oflO
30
d6 Tanabe-Sugano diagram
:zA:z
'A,
4A:z
I
I
'G
70
60+
''Fe L - - -
50
'T,
50
'F
'D
40
'S
~ 40
'I
30
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.... , ..
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60
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30
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f!-

CHEM3341 Inorganic Chemistry II

December 12, 2015 (Saturday)
9:30 am - 12:30 pm
Only approved calculators as announced by the Examinations Secretmy can be used in this examination. It is
candidates' responsibility to ensure that their calculator operates satisfactorily. and candidates must record the
name and type of the calculator used on the front page of the examination script.
Answer ALL questions in Section A in the YELLOW answer book.
(Total 40 marks)
Answer THREE questions in Section Bin the BLUE answer book.
(Total 60 marks)

A Periodical Table a nd a Tanabe-Sugano diagram are provided on the last pages of thi s
question paper.
Page 1of11
Section A
Answer ALL questions in this section iu the YELLOW book. (Total 40 marks)
I.
The variable temperature 1H NMR spectra of (rJ6-C 6Me6 )Ru('r{C6 Me 6) from -10 C to
+42 C are shown in Figure I. At -10 C four peaks are observed at 151.92, 1.77, 1.47
and 1.27 ppm with relative intensity 2:6:2:2. At 42 C, they coalesce to a single peak.
(a)
Account for the four peaks observed in the low-temperature (-10 C) NMR
spectrum.
(4 marks)
(b)
Given that a 20-electron species is unstable and is unlikely to form, predict a

possible intermediate species which accounts for the single peak observed at 42
oc.
(3 marks)
OBSERVED
6 (ppm)
SIMULATED
Figure I. Variable temperature 1H NMR spectra of Cn 6 -C 6Me6 )Ru(n 4 -C 6Me6 ) from-IO C to

+42 C (* denotes an artefact in the spectrum)
Page 2of11
2.
3.
The first metal-dihydrogen complex was reported in 1984 by G. Kubas and co-workers
and had the structure W(CO)J(PCy3) 2(ri 2-H 2). (Cy=cyclohexyl)
(a)
Draw the structure of this complex.
(b)
Suggest one reason why this complex is stabilized in the dihydrogen form as
opposed to the classical dihydride structure. Suggest an experiment that you
could conduct to support your argument.
(6 marks)
(a)
For the following organometallic complexes, predict if any metal-metal bonds

should be present. You should indicate the metal-metal bond order and briefly
explain your answer.
(4 marks)
i)
.
Cl
. 'P\
f/81
'Pr--P-Ni
I\
t \
(2 marks)
/~r
Ni- P.-Pr
I\
I \
ipr = isopropyl
ii)
4.
(b)
Cobaltocene, Cp2Co, is stable at room temperature. However, the rhodium

analogue is unstable and dimerizes to give the compound with molecular formula
Rh2C20H20. Propose two possible structures for the rhodium dimer and indicate
the electron count of the two structures.
(6 marks)
(a)
Give the ground state RusseJl-Saunders terms for:

(i)
Cr3+ ion
(ii) Co3+ ion
G ive also the spectral terms in an octahedal field that would correlate with the
Russell-Saunders terms in (i) and (i i).
(3 marks)
Page 3of11
(b)
Classify the following electronic configurations as T, A, or E states:

(i)
(t2 g)\eg) 4 in an octahedral metal complex with S = I
(ii)
(t2 g)3(eg) 2 in an octahedral metal complex with S = 5/2
(iii) (t2 g) 6 (eg) 2 in an octahedral metal complex with S = 0

(iv)
(e)4(t2)2 in a tetrahedral complex with S = I

(4 marks)
5.
(a)
Compare the metal-ligand bond lengths within each of the complexes,

[Cr(OH2) 6 ] 2+, [Co(OH 2 ) 6 ] 2+ and [Co(NH3 ) 6] 3+ and justify your answers with
reasons.
(4 marks)
(b)
State the innersphere electron transfer mechanism. Predict which of the

complexes in (a) can undergo innersphere electron transfer reactions. Explain.
(4 marks)
Section B
Answer THREE questions in this section in the BLUE book.
6.
(a)
The industrial synthesis of ibuprofen is conducted through an efficient three-step

process called Boots-Hoechst-Celanese Synthesis shown in Figure 2. The key
step that transforms A to B in the presence of CO nsing the catalyst
cis-PdCh(PPh3 )2 is shown below. Propose a catalytic cycle that converts A to B.
Draw all intermediates and identify all reaction steps in the process.
c1raJA
(Total 60 marks)
cis-PdCl,(PPh,)z,
co Cl~ H,O HOkV

B
ibuprofen
figure 2. Reaction Scheme of Boots-Hoechst-Celanese Svnthesis

(12 marks)
Page 4of11
7.
(b)
The dimeric compound [('r1 5-C5Me5 )Cr(C0)2h (compound X) obeys 18-electron

rule and shows IR absorptions at around 1870 cm- 1 By reacting compound X
with excess CO at 1200-450 psi and 175 C for 10 hours, another dimeric
chromium compound Y which also obeys 18-electron rule is formed. The IR
spectrum ofY shows absorptions at around 1876 cm-1. Photolysis of compound
X with UV radiation is found to result in a 17-electron dimeric compound Z along
with the release of CO gas. The IR spectrum of Z shows a single band at 1788
1
cm- and analysis shows that it has the same metal-metal bond order as compound
X. Draw the structures of compounds X, Y and Z clearly, indicating the
metal-metal bond order and the nature of CO bonding.
(8 marks)
(a)
The following iron alkyl complex thermally decomposes to give I-butene and
2-butene. However, no alkanes are produced in this decomposition reaction.
Kinetic studies ind icated that '.lS 1 = 20 3 eu. Propose a suitable mechanism for
the decomposition reaction and account for the formation of I-butene and
2-butene.
Cp
Cp
,,"
OC'
.Fe~
OC'',.
CH3
.Fe-- H
+ 1-butene and 2-butene
PPh 3
PPh3
(10 marks)
8.
(b)
Write the rate law for the reaction.
(c)
and illustrate your answer with examples.
(8 marks)
(a)
Alkynes readily act as bridging ligands in organometallic complexes.
(2 marks)
(i) For the following reaction,
Determine the structure and electron count of the product. How many
electrons does the alkyne donate to each Co? Briefly explain your answer.
(5 marks)
(ii) What is the hybridization of the carbon of the alkyne ligand?
characterization methods that can support your answer.
Suggest two
(5 marks)
Page 5of11
(b)
The outersphere electron transfer rate constant (k 12 ) for the reaction of [Ru(NH 3) 6 ]2+
with [Ru(phen hJ3+ is several orders of magnitude greater than that of [Ru(NH 3) 6] 2+
with [Co(NH3) 6]
under similar conditions (phen
1, 10-phenanthroline).
Rationalize the observation.

(10 marks)
9.
The electronic absorption spectra of [Ni(OH2) 6 ]2+ and [Ni(NH 3) 6 ] 2+ show weak
absorption bands and the UV-vis absorption spectral data are listed below.
fNi(OH2lo:t:
Weak bands
8,500 cm- 1
10,750 cm- 1
13,800 cm- 1
17,500 cm- 1
25,300 cm- 1
28,200 cm- 1
Very weak bands

V4
15,400 cm- 1
15,400 cm- 1
Vs
18,400 cm- 1
18,400 cm-1
(a)
With the aid of the Tanabe-Sugano diagram, assign the transitions and determine
the values of 6 0 and B for the complexes.
(8 marks)
(b)
Rationalize the observed differences in 6 0 and illustrate your answer with the aid
of simplified molecular orbital diagrams. Rationalize also the observed
differences in B.
(5 marks)
(c)
Explain the intensity of these bands based on selection rules.
(d)
Explain why v4 and Vs show the same transition energy for both [Ni(OH2) 6] 2+ and
2
[Ni(NH3 ) 6] + with the aid of orbital diagrams showing the electronic transitions
involved for v4 and vs.
(4 marks)
- END OF PAPER-
Page 6of11
(3 marks)
The periodic table

2
11
10
12
-
13
.-
14
15
16
17
He
4.0026
Key:
l.005
lithil,.1m
Be(l,i!ium
Atomic number
Li
Be
Symbol
Sodium
Mzgnesium
AhrmintJm
12.011
Slllr.on
Pho.sphe>n.a
15.999
Sulrur
11
12
13
14
15
16
18
Al
Si
17
Cl
Ar
K')'l>too
on
Ei~tner\1
N:une
19
24...'.305
C""cium
Sca~ dium
20
21
Sc
K Ca
"'<D
OQ
.....
-........
0
39098
Rt1Dfdiur:i
40.078'i.!J
4'1.P~6
S!.tont~um
Yt!rium
37
38
39
Rb Sr
BSA Ga
C3eskJm
87.62
B:uium
55
56
Cs Ba
132.91
FrarlCIUm
87
Fr
rna.ozi
137.33
88.906
Lutetium
22
Ti
4 "f.867
Zirconium
40
Vanadium
23
50.s.t.2
NrOOium
41
92 .906{:?1
ll:dnhJm
Ti'lnl01lum
71
72
73
Lu
Hf
Ta
88
89-102
Ra
**
1anthanoids
Nitrog!!n
Oxygen
Flu::irm~
10
Ne
18.998
20.180
Chlorine
Aq;on
24
Manc:;anese
25
Iron
26
5 1.996
42
54.93!!
TcchnetfJm
43
55.8..:5(21
Ruthenium
44
05,96!21
Tung:. ten
74
197.911
Rhonlutn
101.07(21
Osm'um
75
76
Re Os
1"4,007
26.982
28.08 5
J0.97.4
32.06
J5,(5
Nickel
Copper
Zirv.:
G<!!lum
G~rmc.n!um
Ars~n ic
Seleniuin
Brcmine
27
28
29
30
31
32
33
34
35
36
Br
Kr
5e,,g;33
Rho1"rJn1
45
Cu Zn Ga Ge As Se
Ni
58.G93
PaOaef1Um
46
GJ.546131
Silver
47
65.38(7.)
Cadmium
48
102.!n
k icfum
77
Ir
1 0G . 4~
107.B7
Pl.1finum
G:i!d
112 .4 1
Men:ury
78
79
80
Pt Au Hg
196.97
69.72J
Indium
49
In
11'1.82
f hal11l.fm
74 .922
Antimony
7't9Sr.' )
T<illurhlrn
79,904
Iodine
83.7!18121
Con
50
51
52
53
54
Xe
Sn Sb Te
1 18.71
Le-ad
U!1.76
6lsrnuth
81
82
83
Tl
Pb
Bi
127.60(3\
i 26.90
Astatine
131 .29
Ha.don
84
85
86
Po At Rn
204 ,38
Ununlrium
207.2
Florovium
208.98
Un>Jnpcnllum
Llvorm::irium
1209.901
Ununsc;:il ium
Unuooc1ium
112
113
11 4
115
116
117
118
1208.981
160.95
Dul:mivm
186.21
Botuium
190.2 J{21
Seab orgi~m
Has.slum
192.22
Mc!toeri\Jm
104
105
106
107
108
109
110
r2s2.:11
l255.t21
126B.13l
1211.131
12701
1277.151
1276.151
1281.161
1280.161
1285.17]
[284 18}
"-89. 191
1266,1 9l
12931
Lant11anu!ll
Cerium
Pr.asaodymlun
Ne>OdJ'lll:lJm
Pro~rn!!lhium
S:irn01t!Unl
Eutoulum
Gad'J!;nium
Terb11.1m
Dy:;pro::ium
Holmium
:=rb1um
n1 u~Ufn
Yllt!1b1um
57
58
59
60
61
62.
63
64
65
66
67
68
69
70
138.91
l\:::Hnlum
~ -4 0,12
~ .. o.91
Pt0t<1Gti1,luf1"
14-4.24
1144.0 11
Nf!p:unlum
15i.%
Amt"ricium
157.25{3)
C!Jrium
B-et'i<elluri
162 5 0
C"'..ali!Ol!l!um
f.ins:clnium
167.26
Ft::rmTum
17JOS
Uranium
t S0.3&!2l
Plul omum
168.93
Thorium
Mendel~vium
Mobelrum
90
91
92
93
94
95
96
97
98
99
100
101
102
2 38.03
12 3 7.051
124-<.0lil
1243.061
11<17.0 l'I
'2:l7.0l'l
12:51.031
Lr
111
Rf Db Sg Bh Hs Mt Os Rg Cn Uut Fl Uup Lv Uus Uuo
La Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb
Ac Th Pa
f227.C31
f222.0?l
2{;0.59
Co~rnicium
17.B.'.9(2)
Rt.1th~rlordium
1!15.06
Xenon
Po!onkim
103
Darrnsla:mum Ro,ntgenium
39.9~8
72.63
174.97
183.81
Neon
CobiJll
Cr Mn Fe Co
Mo!ybdcnUI'~
Lawrencium
89
actinoids
Chromium
Zr Nb Mo Tc Ru Rh Pd Ag Cd
S1.22412}
57-70
Radlum
(226 031
Ti:arlllJm
Carbon
10.81
Ala1nl:; weluhl {me.a.'l rl?i ottvc mas~\
0.0122
Boron
Na Mg
22.990
Pol tu.shim
"O
18
Helium
Hyd1og~f'I
?.J2.0J
231.0.;
'589J
164.93
u Np Pu Am Cm Bk Cf Es Fm Md No
rzsz.os1
1251. 10 1
risa. 101
125~ .I OI
12941
129<1
'r.
'T;
ir,
'r,
"'
iil
7'A,
10
10
20
30
10
hJB
20
hJB
Page 8 of 11
30
70
~~ /
GI
./ 'A,
/
~~
m~ ~~
v /::,
~1
'G
::.
E
'E(D)
50
~:r
'A,
v ;:%.~~'
ro
'G
""""
'T,
30
' A'
20
'E
"I /~ ,
'o
10
20
llJB
30
"
~.
''S
Page 9of11
10
20
llJB
30
'A,
'T1
'G
70
''
' 'E
60
'o
I
I
60
_.-
,,,,
40
'D
'S
11
3~
JF
Jp
JH
20
@ 2F
,..
_...,,.....
::~~~<. . . . .~
" '....:::.. _.......

......
-...
'
......
............................
/''
......,";' , ...,,,.,....
....,' ,, ,,,,
, . ''
,' ,...,.."
,'
, ....
_,,....
10
'A,
10
,/" 3T:
,''
,,,
....... ,,'
., ,'
20
---
,'
'
'
'
'
''
,'
,,
'T,
'T,
......,,..-"
'o
'P
,.,.... 3T1
'H
20
,,,'
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p
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30
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40
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10
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20
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Page 10of11
1"T2
30
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,.,
""'',
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50
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40
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30
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Page 11of11

Hku Inorganic Chemistry 2 Test

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THE UNIVERSITY OF HONG KONG

December 8, 2014 (Monday)

Answer ALL questions in Section A in the YELLOW answer book.

Answer THREE questions in Section Bin the BLUE answer book.

Question 6 (20 marks)

Rationalize the following observations:

1944, 1886 and 1881 cm-'

In the substitution reaction of V(C0) 6 with phosphines, the rate of reaction

Classify the following electronic configurations as T, A, or Estates:

(t2g)\eg)4 in an octahedral metal complex

(t2g) 3 ( eg) 3 in an octahedral metal complex

(iii) (e) 4 (t2 )4 in a tetrahedral complex

(iii) n-donor ligands

(iii) Suggest a characterization method to distinguish between these isomers.

Calculate the valence electron count on the following iron-sulphur cluster.

Write a short essay on the structure and electron transfer properties of

Design two-step syntheses of cis- and trans-[PtCh(N02 )(NH3)r starting from

Briefly explain why the c1s-1somer of [Pd(CH2CH3) 2 (PR3)2] decomposes

Write a short essay on innersphere electron transfer mechanism. Describe also

Copper(II) chloride in aqueous solution is pale blue in colour whereas an intense

The self-exchange or electron exchange reactions of copper(II) complexes are

[Mn(OH2)6]2+ appears very pale pink to almost colourless whereas [Mn0 4 is

. The periodic table

Db Sg Bh Hs Mt Ds Rg Cn Uut Fl Uup Lv Uus Uuo

" " - """'

....... , .. ' '

THE UNIVERSITY OF HONG KONG

CHEM3341 Inorganic Chemistry U

December 21, 2013 (Saturday)

Give the ground state Russell-Saunders term for d 6 electronic configuration.

The v(02 ) IR stretching frequencies of the two cobalt(III) complexes, [Co(salen)(py)Oz]

Comment on the following observations:

Describe the outersphere electron transfer mechanism. State the Marcus

Explain why the redox reaction between [Ru(NHJ)6] 3+ and [Cr(Hz0)6] 2+ is

Chemical structure ofthiourea

Metallocyclopentanes (A) are more stable compared to their bis-alkyl analogues

A study on CO substitution reaction by PPh3 of various (L)Rh(CO)z complexes was

The complex trans-[Rh(bpy)2Cbt reacts with various T, giving [RhY(bpy)2Clt.

Rf Db Sg Bh Hs Mt Uun Uuu Uub

THE UNIVERSITY OF HONG KONG

CHEM3341 Inorganic Chemistry II

Answer ALL questions in Section A in the YELLOW answer book.

Answer THREE questions in Section Bin the BLUE answer book.

Question 6 (20 marks)

Given that a 20-electron species is unstable and is unlikely to form, predict a

Figure I. Variable temperature 1H NMR spectra of Cn 6 -C 6Me6 )Ru(n 4 -C 6Me6 ) from-IO C to

Draw the structure of this complex.

For the following organometallic complexes, predict if any metal-metal bonds

Cobaltocene, Cp2Co, is stable at room temperature. However, the rhodium

Give the ground state RusseJl-Saunders terms for:

Classify the following electronic configurations as T, A, or E states:

(t2 g)\eg) 4 in an octahedral metal complex with S = I

(t2 g)3(eg) 2 in an octahedral metal complex with S = 5/2

(iii) (t2 g) 6 (eg) 2 in an octahedral metal complex with S = 0

(e)4(t2)2 in a tetrahedral complex with S = I

Compare the metal-ligand bond lengths within each of the complexes,

State the innersphere electron transfer mechanism. Predict which of the

The industrial synthesis of ibuprofen is conducted through an efficient three-step

co Cl~ H,O HOkV

figure 2. Reaction Scheme of Boots-Hoechst-Celanese Svnthesis

The dimeric compound [('r1 5-C5Me5 )Cr(C0)2h (compound X) obeys 18-electron

+ 1-butene and 2-butene

Write the rate law for the reaction.