CHEM 352 Binh Nguyen

Migratory Insertion Reactions in Organo Transition-Metal Chemistry

Synthesis and Characterization of Mo(II) Alkyl and Acyl Complexes

Analysis

The three dimensional structure of the starting molybdenum
material, [
5
CpMo(CO)
3
]
2
, is shown in Figure 1
1
. Assuming the
cyclopentadienyl rings are rotating very fast, this structure has C
2h
symmetry
because it has a C
2
axis coming out of the paper, a
h
reflection plane
passing through OC-Mo-Mo-CO plane and an inversion center in the middle of
the Mo-Mo bond. . Note that this assumption is reasonable, because NMR
spectra cannot distinguish the protons (in
1
H-NMR, Table XXX) and the
carbon atoms (in
13
C-NMR, table XXX) of the rings. This proposed
structure is confirmed by Infrared Spectroscopy: IR spectrum shows 3
absorptions bands in the carbonyl region (see attached spectrum). Deriving
the vibrational normal modes for CO stretches in the C2h symmetry yields
2A
g
+ B
g
+ A
u
+ A
2u
. Because A
g
and B
g
are not IR-active, we would expect 3
IR bands for CO stretches. This is exactly what we see in IR spectrum
mentioned above. Another possible structure is the cis-isomer shown in Figure 2, which has C
2v

symmetry. This isomer would exhibit 5 IR active stretching bands.
From the structure of [
5
CpMo(CO)
3
]
2
, one likely structure for
[MoMe(CO)
3
(
5
C
5
H
5
)] is shown in Figure 3, which has C
s
symmetry (it has a
reflection plane passing through OC-Mo-Mo-CO plane). By symmetry, we would
expect to see two equivalent carbonyl ligands. This observation is supported by
13C-NMR, which only shows 2 types of Mo-CO resonances (see Table XXX).
With C
s
symmetry, group theory predicts that there are three IR-active
stretching CO bands (2A + A). However, IR spectrum only shows 2 bands in
the carbonyl stretching region (see attached spectrum). It seems that we might
have an overlap between two of three expected bands (maybe between A and
A because two A bands cannot have the same energy due to the lack of degeneracy). But this
disagreement cannot be resolved without any further information.
The product of migratory insertion has two possible structures shown in Figure 4: cis and
trans isomers. The trans isomer has Cs symmetry and the cis isomer has C1 symmetry. Group
theory predicts 2 IR active Mo-CO stretching bands for both of the structures, which is exactly
what we see in the obtained spectrum (see the attached spectrum). However, these two structures
have a fundamental difference: two CO ligands are equivalent in the trans isomer but not
equivalent in the cis isomer. Therefore, we would expect to see 2 distinct Mo-CO resonances in
for the cis isomer and only 1 Mo-CO resonance for the trans isomer in
13
C-NMR. The
13
C-NMR
of the product shows only one Mo-CO resonance, so the correct structure of
[Mo(COMe)(CO)
2
(
5
C
5
H
5
)(PPh
3
)] is the trans structure in Figure 4.
Figure 1. Correct structure of
[
5
CpMo(CO)
3
]
2

Figure 2. Possible Cis-isomer
Figure 3. Structure of
[MoMe(CO)
3
(
5
C
5
H
5
)]
CHEM 352 Binh Nguyen

Figure 4. Two possible structure for [Mo(COMe)(CO)
2
(
5
C
5
H
5
)(PPh
3
)]
Experimental Section
All the syntheses in this experiment were done under an inert-atmosphere of Nitrogen gas
inside an MBraun Unilab 2000 glove box. The starting materials, including methyl iodide,
triphenylphosphine, the 1M solution of Super-Hydride (LiEt3BH) and anhydrous solvents, were
purchased from Sigma-Aldrich or Strem and used as received. The starting molybdenum
material [
5
CpMo(CO)
3
]
2
was purchased from Strem and used as received. The neutral alumina
was purchased from Sigma-Aldrich and dried at 150
o
C under vacuum for 12 hours before use.
NMR solvent, Chloroform-d, was purchased from Cambridge Isotope Laboratories and filtered
through neutral alumina before use. Infrared spectra were taken with a solution IR cell in
dichloromethane by a Mattson Model 4020 Galaxy Series FTIR Spectrometer. NMR spectra
were obtained with a Varian Unity-Plus 400 MHz FT Nuclear Magnetic Resonance Spectrometer
at 399.95 MHz for
1
H-NMR, 100.58 MHz for
13
C-NMR and 161.90 MHz for
31
P-NMR. Both
13
C and
31
P spectra were acquired with proton decoupling. The chemical shifts for
1
H and
13
C
were referenced against CDCl
3
the residual proton at 7.24ppm and the
13
C at 77 ppm. For
31
P,
the chemical shifts were referenced to concentrated phosphoric acid, which comes at 0ppm.
The synthesis of [MoMe(CO)
3
(
5
C
5
H
5
)] was performed in an inert-atmosphere glove
box. 214.9 mg (0.4386 mmol) of [
5
CpMo(CO)
3
]
2
was dissolved in 10mL anhydrous THF in a
20mL scintillation vial with a flea-sized magnetic stir bar. 2 equivalent of Super-Hydride (1.1
mL of a 1.0 M solution in THF, 1.1 mmol) was slowly added into the vial by syringe. The
mixture was stirred for 20 minutes and 88.5 L (1.39 mmol) of methyl iodide (CH
3
I) was then
added by a calibrated pipet. The reaction mixture was stirred for 2 hours. The volatiles in the
mixture were removed in vacuo and the crude product was stored in a freezer at -35
o
C over the
course of a week. The crude product was extracted into solution by 15 mL pentane and filtered
through 1.5 cm of neutral alumina in a 30mL frit. The solution was pulled through the frit by
vacuum and the frit was washed with extra pentane until the eluent was colorless. The pentane
solvent was then removed in vacuo. The yellow solid products mass was 56.6 mg,
corresponding to a yield of 24.8%.
The migratory insertion to synthesize [Mo(COMe)(CO)
2
(
5
C
5
H
5
)(PPh
3
)] was also done
in an inert-atmosphere glove box. 87.3 mg (0.333 mmol) of PPh
3
was dissolved in 5mL
acetonitrile and the resulting solution was then transferred into a 20mL scintillation vial
containing 55.2 mg (0.217 mmol) of [MoMe(CO)
3
(
5
C
5
H
5
)] and a flea-sized magnetic stir bar.
The mixture was stirred overnight and stored until next lab period. The yellow solid product was
CHEM 352 Binh Nguyen
collected by a 30 mL frit and washed with 10mL pentane and then dried under vacuum. The
yellow product was scratched off the frit and transfer to a clean scintillation vial. 80.0 mg of
product was collected, corresponding to a yield of 71.2%.

Spectral Assignments
1. [
5
CpMo(CO)
3
]
2

2. [MoMe(CO)
3
(
5
C
5
H
5
)]












Figure XXX: Numbering scheme for
[MoMe(CO)
3
(
5
C
5
H
5
)]









3. [Mo(COMe)(CO)
2
(
5
C
5
H
5
)(PPh
3
)]
IR

Frequency (cm
-1
) Type Reference
2018.12 CO Piper
1925.46 CO Piper
Carbon
a

Chemical
Shift (ppm)
b

Pattern Notes on Assignment
1 92.4 s
2 226.5 s
3 239.8 s
This peak was assigned by comparison with 13C-NMR of
[Mo(COMe)(CO)
2
(
5
C
5
H
5
)(PPh
3
)]. Chemical shifts of C3
carbons should remain relatively unchanged.
4 -22.3 s
Proton
a

Chemical Shift
(ppm)
b

Pattern
(Rel Int)
Reference
a 5.28-5.29 m (5H) Piper
b 0.35 s (3H) Piper
CHEM 352 Binh Nguyen









Figure XXX: Numbering scheme for Figure XXX: Numbering scheme for PPh
3
.
[Mo(COMe)(CO)
2
(
5
C
5
H
5
)(PPh
3
)] Note that H atoms are not specified due to
inability to distinguish them in the obtained
1
H-NMR. This symmetry is not the same as
the symmetry of PPh
3
bounded in the
complex.

IR
Frequency (cm-1) Type Reference
1938.13 CO Barnett
1858.1 CO Barnett
1613.43 Acetyl Barnett


Carbon
a

Chemical
Shift (ppm)
b

Pattern Notes on Assignment
1 96.7 s
2 266.1 s
3 238.3 d
This peak was assigned by comparison with 13C-NMR of
[Mo(COMe)(CO)2(5C5H5)(PPh3)]. Chemical shifts of C3
carbons should remain relatively unchanged.
J = 24 Hz
4 51.4 s
5 135.47 d J
PC
= 44 Hz
6 128.5 d J
PC
= 10 Hz
7 133 d J
PC
= 10.7 Hz
8 130.35 s

Proton
a

Chemical
Shift (ppm)
b

Pattern
(Rel. Int.)
Reference
a 4.99 s (5H) Barnett
b 2.59 s (3H) Barnett
phenyl protons 7.4 m(15H) Barnett
CHEM 352 Binh Nguyen
Reference
1. Wong, R.; Ooi, M.; Tan, G.; Ng, S. Inorganica Chimica Acta, 2007, 360 (9), 3113-
3118.
2.