Preparation and Study of a
Monomethyl Indenyl Titanium Compound
by
James D. Modglin
Honors College Thesis
Research Advisor: Dr. Robert Morris
~..j ~
J~~03
Date: May 2, 2003
Chemistry Department
-
Ball State University
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A Note:
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. til Gd
At tht: time that this thesis was written, my research with Dr. Morris was not
complete. B.:cause I will be returning as a graduate student in the fall, my research will
be finished in the first summer term following the completion of my undergraduate
degree. As sllch, this paper is not complete in the sense that it is in a complete form fit
for submission to a scientific journal. Even so, I believe that the experiences I have had
during my year of research have given me a new look not only at my chosen career, but
also into my own abilities as well. In light of this, I proudly submit this paper as a
capstone to my undergraduate experience as well as the first stone in my continued path
into the future.
-
-
Acknowledgements:
Although this is not a standard piece of a scientific paper, I feel it is both
necessary and important to give credit to those who have allowed me to experience this
opportunity. I want to thank the Ball State Chemistry Department and especially Dr. Bob
Morris. It goes without saying that this has been one of the most difficult, frustrating,
and rewarding projects I have ever had the pleasure of working on, and through it all Dr.
Morris has been there to provide guidance, an ear to complain in, and a push in the right
direction when needed. Although I will probably not get the chance to work for him
again as a researcher, I am sure that his help will be indispensable in my future studies
and possibly into my career.
Abstract:
A series of indenyl titanium complexes were synthesized and then studied using
IH
and l3 C nuclear magnetic resonance spectroscopy techniques to determine the effects
on these compounds by aqueous environments and olefins. After study, it was found that
the target monomethyl titanium complex most likely forms a dimer when in an
environment containing water. The synthesis of this dimer created a solid that was
insoluble in many common solvents and slightly soluble in chloroform-d. The
interactions between the target compound and the olefin styrene have yet to be probed,
but the loss of the methyl group from the metal complex is quite possibly indicative of a
potential polymerization activity around the metal center.
-
-
-
Introduction:
The synthesis of useful compounds has always been a goal for chemists, but with
the foundation of plastic syntheses this goal has become more complicated. As most
people know, plastics are everywhere from the packaging of our foods to inside our very
bodies. These materials are often polymers of more simple compounds, and the
processes that allow for their production are a great area of study. An area of intense
interest is the: polymerization catalysts that are the backbone of the production of many of
these plastic~,.
The area in particular that this research deals with is the polymerization abilities
of a series of indenyl titanium compounds. These compounds are interesting because of
their basic composition. The metal center's connection to the indenyl ring has the ability
-
to "slip," as shown in figure 1.
M
Figure I: Indenyl Slippage
This is of intt:rest because the "slip" changes the electron count around the metal center,
lowering it by two. This lowering of the electron count opens the coordination site on the
metal center, allowing for increased reactivity with electron rich sites, such as olefins.
This creates the possibility of a polymerization action through the use of this compound.
The overall goal of this study is to determine the reactivity of the indenyl
compounds produced as well as to determine whether there is the possibility that one or
-
more of these compounds act as polymerization catalysts when introduced to olefin
containing compounds (e.g. styrene). The mechanism we believe is the backbone of this
polymerization is shown in figure 2.
Q
OW>
\
b enzen e-d.
Cl-..._~-Ti
\
Cl-----"1 i -CH
H
Cl
3
Cl
Q
b enzen e-d.
\
Cl-
-
H
-Ti
-
Cl
1----1--- C H 3
Figure 2: Proposed Mechanism ofIndenyl Compound Polymerization
The theory behind this mechanism is as follows. When the indenyl ring "slips" from the
'15 to the '13 position, the electron count around the titanium atom is lowered by two. This
creates a coordination site on the titanium atom that is attracted to the pi electrons present
in the olefin of the styrene molecule. This creates an insertion reaction that adds the
methyl group already attached to the titanium to one side of the olefin while the opposite
end associates itself with the titanium. This process is then repeatable so long as there
are reactive olefin-containing compounds remaining.
H
H
Type IV Catalysts
The interest in the particular catalyst we study lies in the examination of other
type IV polymerization catalysts. Some ofthese catalyst types are shown in figure 3.
~
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"
d
+
+
M--R
Figure 3: Examples of Type IV Ionic and Non-Ionic Polymerization Catalysts
Some problems arise with specific types of catalysts, particularly the ionic catalysts.
Since cations cannot exist without balancing anions, there is by necessity an additional
component necessary to allow the catalyst to exist. Methlyaluminoxane (MAO) is added
to these solutions, not only those that contain ionic catalysts for charge balance, and is an
integral part of the initiation of the catalysis. MAO aids in the formation ofa methyl
starter group associated with the metal, leading to polymerization. Unfortunately, the
amounts neCt:ssary to allow the catalysts to function properly are exorbitant, often one
thousand parts MAO to one part catalyst. For industry, this is too costly to be accepted
unless there is no other option for the desired result.
The ability to produce known plastics more efficiently and without additional
costs from non-reactive species is a sought after property in the new polymerization
catalysts being produced today. The goal of this study is to produce and observe a
catalyst that not only works in the polymerizing of olefins, but to produce one that will
hopefully outperform those existing in the current industry.
-
-
Procedure:
The procedures that were utilized in the synthesis of the molecules under study
are outlined in the following sections.
Synthesis ofIndenyl Titanium Trichloride [(r{C 9H7)TiChJ
+00 CH2CI~
II
TiCl4
Si(<:II3)3
T. I h,.
2
~
~
<:1~~i_<:1
~l
These procedures were performed in an atmosphere of argon under standard
Schlenk manipulations or in the confines of an inert dry box.
A solution composed of 1-(trimethylsilyl) indene (25.0 grams/0.l33 moles) in
fifty milliliters of dichloromethane is added to a solution of titanium (IV) chloride (17.5
mi1liliters/0.16 moles) in one hundred fifty milliliters of dichloromethane in a two
hundred fifty milliliter round bottom flask. The solution in the reaction flask
immediately turns a dark red. The reaction mixture is then stirred overnight. The
mixture is th'm filtered using a cannula equipped with a filter stick with the liquid
component being transferred into a Schlenk flask. The Schlenk flask is then cooled at
-20C overnight yielding dark red crystals of the desired product [(115-C9H7)TiCi)).
Filtering the solution again yields a second crop of crystals when treated in the same
manner. The filtration procedure should be repeated until no further crystals are
obtained. Yidd: 15.7 g (43.9 %)
-
Synthesis ofIndenyl Titanium Methyl Dichloride [(1{C 9H 7)TiCH3Ch]1
Q
C
~
+ AlMe3
---,p:.:;en::.:ta=n:::.:e,..:.:R::,.:.T:.:...::..3h::.:r::..s_.
I
Cl--~i-........Cl
~l
These: procedures were performed in an atmosphere of argon under standard
Schlenk manipulations or in the confines of an inert dry box.
A solution oftrimethyl aluminum [AI(CHJhl (2.54 milliliters of a 2.0 molar
solutionlO.00504 moles) in hexane (75 milliliters) was added to a solution of (11 5 _
C9H7)TiCb (1.354 grams/0.00503 moles) in hexane (75 milliliters) at room temperature
through the use of a pressure equalized dropping funnel. The rate of addition was
controlled to produce a flow of one drop per second. As the solution is added, the
reaction mixture lightens from its original red color. After the addition is complete, the
solution is allowed to stir at room temperature for an additional three hours. The result is
a clear orange liquid with a white solid precipitate. The solution is filtered using a
cannula equipped with a filter stick, with the liquid being transferred into a Schlenk flask.
The Schlenk flask is then cooled overnight at -20C to yield red crystals of the desired
5
product (11 -C9H7)TiCH3CIz. The solution should be filtered again and cooled as
described above to yield further crops of crystals. Yield: .5655 grams (45.14%)
These procedures were performed in an atmosphere of argon under standard
-
Schlenk manipulations or in the confines of an inert dry box.
In a single addition, 0.1 milliliters of distilled water was added to a solution of
(115-C9H7)TiCH3Ch (.25 grams/.OOI moles) in hexane in a round bottom flask. The
indenyl compound should be completely dissolved before the water is added. The
solution is allowed to stir overnight. As the reaction progresses, bubble like structures
fall out of solution and coat the walls of the flask. After the solution has stirred, the
liquid is removed and the solid pumped dry using a vacuum. Because of the inability to
find an adequate solvent for purification of the compound, no yield data is at this time
available.
Preparation of Dry NMR Solvents
The solvents used in NMR spectroscopy during this experiment were dried using
the following methods under standard Schlenk procedures.
Benzene-d6 was dried using fine shavings of sodium metal in the presence of
benzophenone. The solution was allowed to stir at room temperature until the solution's
color turned a vivid blue-green to indicate the absence of water associated with the
phenone. Chloroforrn-d was dried using small pieces of calcium hydride. Both of the
solutions were vacuum distilled using a short path apparatus into separate Schlenk flasks
super-cooled with liquid nitrogen. The NMR spectra of the solvents were taken to assure
that their water content was within an acceptable range «1 ppm). If the spectra were not
sufficiently water free, the drying processes were run again until the solvents were
acceptable.
-
Instrumentation:
The IH nuclear magnetic resonance data was collected using a JOEL 400
spectrometer at 400 MHz in either chloroform-d (CDCb) or benzene-d6 (C6D6) as noted
on each spectrum. The J3 C nuclear magnetic resonance data was collected using a JOEL
400 spectrometer using either chloroform-d (CDCh) or benzene-d6 (C6D6) as noted on
each spectrwn.
-
-
Discussion:
The compound under study proved both interesting and troublesome when
attempts were made to observe its reactive properties. In the first series oftests, the
compound was placed into an NMR tube and a spectrum was taken of the unreacted
indenyl titanium complex (Indenyl Titanium Methyl Dichloride in Benzene-d6). Once
the data showed that there were no anomalies in the expected spectrum of the compound,
the tube was removed from the instrument and one to two drops of distilled water were
added through a syringe. The tube was then returned to the instrument and the sample's
spectrum tak,en as quickly as possible. Spectra were taken as quickly as possible and
continually processed until the reaction had run to completion, approximately 30 minutes
(Indenyl Titanium Methyl Dichloride + H20 in Benzene-d6, 0-32 minutes after addition).
The disappearance of the methyl peak associated with the titanium complex leads to the
belief that it is the methyl group that is lost during the reaction process, as the peak is the
strongest sample peak in the first spectrum yet completely disappears as the reaction
progresses. To aid in observing the structure of the compound, the NMR tube was
pumped dry to remove the excess water and resolvated using chloroform-d. This
produced an extremely clean spectrum that could be easily evaluated.
The actual structure of the compound is still under some question, as the
compound formed is highly insoluble in hexane, diethyl ether, and toluene. Fortunately,
the product is at least slightly soluble in chloroform-d, so a clean spectrum could again be
obtained when the reaction was run on a larger scale. The production of the product in
both methods produced NMR spectra that were almost identical, showing that the
reaction ran approximately the same on both scales.
When examining the NMR spectrum from the flask-based reaction of the
monomethyl complex with water, we see peak splitting that is characteristic of an
AA 'BB' system of splitting. When examining an indene ring, we might expect to see
only two
typl~S
of equivalent hydrogens present on the six-member ring. Examination
shows, however, that the splitting is not consistent with an AB splitting system. The
chemically identical hydrogens in the ring are not magnetically identical, which produces
indene's AA'BB' splitting. When examining the spectrum from the reaction, the only
hydrogens that are present are from the indene ring(s) in the compound. As was first
assumed, the methyl group found on the original complex has been replaced.
Unfortunately, when a
l3e NMR was attempted, the concentration of the sample was not
strong enough to produce a usable signal to noise ratio. A method must be devised to
dissolve enough of the seemingly insoluble compound to aid in the determination of the
overall structure of the new complex.
The loss of the methyl group is encouraging, however, as this is the site of what is
hoped to be the polymerization activity of the overall complex. If the methyl is the group
that is forced away by the addition of the lone electrons on the oxygen, then it is indeed
possible for the same to occur when the pi electrons of the olefin are introduced into the
system. With the next step of this project, it will be determined whether this activity
occurs solely in the presence of water, or if other areas of high-density electrons (such as
olefins) will achieve similar goals. This research is scheduled to be completed by July
2003.
Results:
All NMR spectra can be found in Appendix A. All time values are after addition
of the second reactant (H20).
The new compound formed through the reaction of water with the monomethyl
complex is still under study. With the inability to find a proper solvent for removal from
the reaction matrix and recrystalization, it may be some time before the structure and
activity of this compound is fully understood. In addition, the formation of the proposed
dimer is an additional problem, as it is not known if this compound forms a crystalline
cage structur,e or if it is a two molecule dimer without further interactions between unit
cells. Further study into the mechanism and interactions of this compound are necessary
before any solid determination can be made .
.
-
Conclusions:
The monomethyl metal complex synthesized and observed in this study seems to
have properties that may signify its ability to act as a polymerization catalyst. The nonionic nature of the synthesized catalyst holds several benefits, including the ability to
function without any additional molecules such as MAO. In addition, the appeal to
industry of a catalyst that is able to work on its own will most likely be significant if it
can replace current catalysts dependent on costly anions to balance them.
There: do appear to be drawbacks to this catalyst as well. As the first section of
this study has shown, this monomethyl complex is very reactive in the presence of water.
Although there may be some way to resurrect the original catalyst or to use the new
product in a useful way, the inability to use this complex in the presence of an aqueous
environment can be detrimental to its overall use.
-
References:
1. Morris, R. J. et ai, "Monoindenyl Titanium Alkyl Halides. The Synthesis and
Molecular Structures of (r,s-C9H7)TiBr3, (I(C9H7)Ti(CH3)Br2, and (r,sC9H 7)Ti(CH3)Ch." Inorganica Chemica Acta, 1999, 292,220-224.
2. Morris, R. J. et ai, "Monoindenyltrichloride Complexes of Titanium (IV), Zirconium
(IV), Hafnium (IV)." Inorganic Syntheses, Marcetta Y. Darensbourg, Editor.
1998,. Volume 32, 215-221.
-
Appendix A
-
T
Indenyl Titanium Trichloride in Benzene-d6
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Of
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CI
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lU
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parts per Million
U
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L _____....
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r
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(Millions)
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Indenyl Titanium Methyl Dichloride + H20 in Chloroform-d (from reaction flask)
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dEDLdt
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g
File Name
Author
Sampl. ID
Cr_tion Date
g
~
Spec Bit.
• Eclip... foOO
Spec Type
.. DELTA_IIDIR
Data Format
.. 1D COMPLEX
Dimension.
Dim Title
Dia s1 ••
Dia ODit.
AcCLulay
Changer_sample
~
• X
.. 13C
.. 32768
·
[ .....1
.. 39.G[us]
•
•
Kxper1ment
.. aingle-pul ••_dac
Field_strength
In-gO
Irr90_hi
Irr90_1o
.. 9.389766{'l']
rrr_doaaain
on
rrr....,pwidth
Lock_atatus
~
Scan.
Solvent
RAovr_gain
.. IO.1[ue)
.. 16 [us]
-.. '0,.
[us]
.. 40 [us]
.. :rDLE
• 2.
RelaxatioD_delay. l(a]
.. 196
.. CIILOROPOIUI-D
Spio...,get
.. 1f, (Rz)
Spin_lock_tO
Spin_lock_attn
Spin_set
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Spin_atat.
Spin_.tatu.
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'l'-.p_.tat.
'l'eDp_.tatu.
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X..P\ll••
X_r••olutioD
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~
~
.~
'-APR-200l 12;53;08
'-APR-200l 12:53:16
Revision Date
...
;;;
.. April_'_-_Water_R••ctt
Content
...
!
.. April_4_-_Water_Reacti
...
x.......p
.. O.1[_J
.. 20 (dB]
.. 15 (Rz]
.. SPIR OW
.. SPIN OR
.. 25.5[dC)
.. 25 [dC)
.. 'l'EIIP 01'T
.. 'l'EIIP 01'T
..
..
..
..
12.5[u.]
12 [ua]
38 Cua)
1.3008896[.J
.. llC
.
.. 100.52530333[KBzJ
.. 100 [ppm]
.. 32768
-
.. '.16666667[u.]
.. 0.76870'7'[az]
.. 25.18891688(kRz]
6
.
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T
T
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T ' ; , ' T'
"I'
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190.0 180.0 170.0 160.0 150.0 140.0 130.0 120.0 110.0 100.0 90.0
J,
{
~ ..
parts per Million: 13C
-
-
_ _ _ _ _ _ _ _ _ _ T_
. , , I '
80.0
70.0
(
60.0
50.0
40.0
• , I ' '
30.0
20.0
10.0
0
(