CH 609, Spring 2006

Dr. Shaughnessy
Final Exam
May 10
th
, 2006
Name: answer key
1. Provide the product(s) for each stoichiometric reaction below. Where appropriate, be sure
that your answer clearly shows the stereochemistry of the metal complex and/or organic
products. For the starting complexes indicated, provide the electron count for the complex
and the oxidation state of the metal. (40 points)
Fe
OC
OC
h!
Ir
Me
3
P
CH
3
H
heat
Mn
H
3
C
OC P(OMe)
3
CO
CO
CO
CO
Ru
Oxid. State: +2
# of electrons: 16
Oxid. State: +3
# of electrons: 18
a.
b.
c.
d.
LiDBEt
3
''D

" source
Fe
OC
+ CO
Ir
Me
3
P
H
Mn
H
3
C
OC P(OMe)
3
CO
CO
O CH
3
Ru
D

2
Fe
CO
OC
OC
Oxid. State: +2
# of electrons: 18
1) PhLi
2) MeI
CH
3
Pt
Cl
Cl Cl
2
N
Oxid. State: +2
# of electrons: 16
e.
f.
Fe
OC
OC
OMe
Ph
CH
3
Pt
N
Cl Cl

2. Provide the major organic product(s) of each catalytic reaction below. Where appropriate
provide the correct relative stereochemistry for the product of the catalytic reaction. In each
case, provide the major product, if more than one is possible. (25 points)
Br O
+
Pd
2
(dba)
3
(cat)
Pt-Bu
3
(cat)
Cs
2
CO
3
Dioxane
OAc
MeO
O
OMe
O
Pd(PPh
3
)
4
(cat)
DMF
+
a.
b.
c.
OH
Pd(OAc)
2
(cat)
O
2
DMSO
CO
2
Me
O
O
CO
2
Me
MeO
2
C
CO
2
Me
+
CO
2
Me
CO
2
Me
CO
2
Me
Minor

3
N
Ts
Ru
Cy
3
P
PCy
3
Cl
Cl
Ph
CH
2
Cl
2
LRh(CO)
2
H (cat)
CO
H
2
toluene
O
PPh
2
PPh
2
L =
d.
e.
N
Ts
O
H

3. Draw a detailed catalytic cycle for two of the reactions in problem 2. Your catalytic cycle
should show full structures for each intermediate metal complex, with appropriate
stereochemistry. (30 points)
a. Pd-catalyzed aerobic oxidation. See notes, chapter 17.
b. Heck coupling. See notes, chapter 7. Note, that due to the constraints of the ring, the
conjugated enone product cannot be formed.
c. Pd-catalyzed allylation. See notes, chapter 16.
d. Enyne metathesis: See notes, chapter 15.
e. Hydroformylation: See notes, chapter 12.
4
work space
5
4. For each problem below, provide an answer and a brief explanation of the fundamental
basis (why) for your answer. (40 points)
a. Place the alkyne complexes below in order of increasing C-C-C bond angle (see indicated
angle).
Mo
C
C
CH
3
CH
3
CCC
Mo
CO
OC
OC
C
C
CH
3
CH
3
Mn
CO
OC
OC
C
C
CH
3
CH
3
1 2 3

2 < 3 < 1
The angle will increase with increasing backbonding, since the carbons will become more
sp
2
-like. Cp is a stronger electron donor than CO, which is a pi acid. The higher
oxidation state Mo
3+
will be a weaker back bonder than Mn
2+
.

b. Place the compounds below in order of increasing rate of susceptibility to nucleophilic
attack.
Cl Pd
Cl
Cl
Cl Pd
N
N
C
C
CH
3
CH
3
H
2
O Pd
Cl
Cl
1 2 3

3 < 2< 1
As the charge on Pd becomes more positive, the alkene will be more electrophilic.

c. An isomer of Fe(PMe
3
)
2
(CO)
3
was found to have three CO stretching vibrations. Is this
the cis- or trans-isomer?
The trans-isomer will have only two vibration for the CO ligands which are all in the
equatorial plane. When the PMe
3
are cis, there will be three stretches (2 asymmetric, and
one symmetric).
6
d. Photolysis of Cp*Rh(PMe
3
)H
2
in a 1:1 mixture of C
6
D
6
/C
6
H
6
gave a kinetic isotope
effect of 1.05. If the same compound was photolyzed in 1,3,5-C
6
H
3
D
3
, a KIE value of
1.4 is obtained. Why do the two experiments give different values, and what does this
mean in terms of the mechanism?
Cp*
Rh
Me
3
P
H
H
h!
C
6
H
6
/C
6
D
6
Cp*
Rh
Me
3
P
C
6
H
6
H
Cp*
Rh
Me
3
P
C
6
D
6
D
1.05 : 1
Cp*
Rh
Me
3
P
H
H
h!
Cp*
Rh
Me
3
P
H
Cp*
Rh
Me
3
P
D
1.4 : 1
D
D
D D
D
D
D D

In the first case, the C-H activation occurs after the rate limiting step, which is benzene
binding. The binding of benzene does not have much if any KIE, but it determines
whether a C-H or C-D bond will break. In the second experiment, the metal still has a
choice of C-H or C-D bonds, after the rate limiting coordination has occurred. Thus the
true KIE for the C-H activation step is seen.

e. Place the compounds in order of increasing rate of oxidative addition of triethylsilane.
Ph
3
P Ir PPh
3
CO
Cl
Me
3
P Ir PMe
3
CO
Cl
(MeO)
3
P Ir P(OMe)
3
CO
Cl
1 2 3

3 < 1 < 2
Oxidative addition occurs faster at more electron-rich metal centers. PMe
3
is the best
donor and P(OMe)
3
is the weakest.
7
f. Which compound would be most likely to undergo !-hydride elimination, and which
would be least likely?
Hf
OTf
Hf
Cl
Hf
OEt
2
B(C
6
F
5
)
4
1 2 3

1 would undergo -H elimination most readily. 3 cannot, because the C-H and C-Hf
bonds can't be syn-coplanar. Complex 2 would be less prone to eliminate than 1, because
the chloride is a more strongly bound ligand than triflate. An open coordination site is
required for elimination to occur.

g. The large bite angle ligand below can coordinate in a cis or trans fashion to a square-
planar complex. Using
31
P NMR spectroscopy, how could you determine which
coordination mode actually occurs when it coordinates to Ir?
P
Me
2
Ph
2
P
Ir
CO
Cl
PPh
2
Ir
PMe
2
Cl CO

In the trans complex, you would have a very large
2
J coupling constant (2-400 Hz). It
would be much smaller in the cis-complex (< 50 Hz).

h. Which carbene compound below would be most stable in the presence of water?
Ta
t-Bu
t-Bu
3
OC Re
CO
CO
OC
CO
O
O
Me
3
P W
PMe
3
O
Cl
Cl
t-Bu
1 2 3

Complex 3 is a Fischer-type carbene that would be reasonable stable in water.
8
5. Oxidative addition of PhI to L
2
Pd(0) could occur by either Path A or Path C shown below.
These two pathways are predicted to have identical rate laws (rate = k
1
[L
2
Pd][ArI]). In order
to distinguish between the two possible mechanisms, Hartwig looked at the mechanism of the
reverse reactionreductive elimination of ArI using tri-t-butylphosphine. (21 points)
L Pd L
L Pd I
Ar
L Pd I
Ar
L
ArI
k
1
-L
k
2 Path C
L Pd (ArI)
k
1
k
2
Path A
L Pd I
Ar
xs t-Bu
3
P
L Pd L + ArI
Fe
P(t-Bu)
2
Ph
Ph Ph
Ph
Ph
L=
ArI
+ L

a. Why can reductive elimination be used to provide information about the oxidative
addition mechanism? Give the name for the concept that describes the relationship of
these two reactions, and briefly describe what it means.
Since the process is reversible, one can look at either the forward or reverse reaction
because the mechanism must be the same in each case. This is the concept of
microscopic reversibility.
9
b. Explain how you would distinguish between the reverse of Path A and Path B kinetically.
Provide the appropriate rate law expressions for each pathway and describe what kinetic
measurements you would make to definitively distinguish between the two possible
reductive elimination mechanisms. You may assume that the reductive elimination of
ArI is rate limiting in both pathways.
Path A: rate = k
2
[Pd]
Path B: rate =

!
k
1
[Pd][L]
k
"1
+ k
2

Path A would be zero order in [L], while path B would be first order in [L]. You would
want to measure the dependence on [L].
10
6. Abstraction of chloride from the Pt complex below gives a cationic alkyl Pt olefin complex.
At high temperature, an equilibrium mixture of 1 and 2 can be generated. Provide a plausible
mechanism for the interconversion of complexes 1 and 2 in the equilibrium shown below.
Show each step of the reaction, including the full structure of the organometallic species. (20
points)
Me
2
P
Pt
Cl P
Me
2
CH
3
CH
3
D
D
AgBF
4
Me
2
P
Pt
P
Me
2
CH
3
CH
3
D
D
125 C
P
Me
2
Pt
Me
2
P
CH
3
CH
3
D
D
1 2
Me
2
P
Pt
P
Me
2
CH
3
CH
3
D
D
Me
2
P
Pt
P
Me
2
CH
3
CH
3
D
D
Me
2
P
Pt
P
Me
2
CH
3
CH
3
D
D Me
2
P
Pt
P
Me
2
CH
3
CH
3
D
D

11
7. Alkyl halides can be reduced to alkanes using [HW(CO)
5
]

has a hydride source. Two

or
an electron transfer pathway. Below are listed several potential experiments that could be
performed in order to distinguish between these mechanistic possibilities. (24 points)
R X + [HW(CO)
5
]

R H + [XW(CO)
5
]

R X + [HW(CO)
5
]

R H + [XW(CO)
5
]

R X + [HW(CO)
5
]

R +
X
W(CO)
5
H
R H + [XW(CO)
5
]

S
N
2-like
Radical

Propose three distinct experiments that could be performed in order to distinguish between
these mechanistic possibilities in this particular case. You can assume that you have access
to any necessary chemicals or equipment. For each experiment, briefly describe what
observations would be expected for each mechanism, and how the outcomes would be
different. You should choose experiments that would be definitive in distinguishing between
the two mechanisms.
Stereochemistry: S
N
2 will give inversion with a chiral halide, while radical will give
racemization.
RX structure: S
N
2 will go fastest with primary RX, while radical will be faster with more
substituted RX.
X identity: S
N
2 will give fast rates with tosylate or similar leaving group, while the radical
will give very slow reactions with oxygen leaving groups.
Radical initiator/inhibitor: The S
N
2 pathway would be unaffected by radical traps or
initiators, while the radical mechanism may be accelerated/inhibited assuming a radical chain
pathway
Radical clocks: The presence of a radical intermediate could be probed with something like
5-hexenyl bromide. The radical reaction would give rearrangement if the radical has any
lifetime.
Solvent effects: The S
N
2 should be more sensitive to solvent polarity than the radical
pathway.
12















Bonus: We have discussed the work of two groups of scientists who earned Nobel prizes in the
past 5 years this semester (2001 and 2005). In total, 6 scientists were recognized in this
period. Provide their names and the specific contributions for which they are most
recognized. (12 points)
2001: William Knowles (Development of the first commercial enantioselective
hydrogenation (DIPAMP promoted reduction of L-Dopa precursor); Ryori Noyori
(development of BINAP ligand and enantioselective hydrogenation of carbonyls); K.
Barry Sharpless (asymmetric epoxidation and dihydroxylation)
2005: Yves Chauvin (proposal of the mechanism of olefin metathesis); Robert Grubbs
(development of effective Ru-based olefin metathesis catalyst); Richard Schrock
(development of carbene chemistry and the Mo-based metathesis catalyst)