CHAPTER 2

Intramolecular Cyclization of Titanocene(Alkenyl)Chlorides

with Lewis Acids

44

Introduction

When a-olefins are polymerized with Ziegler-Natta catalysts, a new stereocenter is produced with each monomer addition._ Three types of stereopolymers may be obtained: isotactic .!_, syndiotactic

l

and atactic 3. These are exemplified for polypropylene.

~n ^~

ⁿ

1 2 3

The stereoregularity of the polymer obtained depends on the catalyst used as well as the polymerization conditions. Isotactic polypropylene is of major practical importance because of its physico-mechanical properties.

The explanation of the stereochemistry for both mechanisms, Cossee and Green, lies on the fact that the entering monomer will orient itself as to minimize steric repulsions with the growing polymer (Scheme 1).

During the polymerization of a-olefins, there is also the possi- bility of an ~-hyd~ogen participation to control such stereochemistry.

The a-hydrogen participation is well documented for other systems. ¹ If existent, this interaction can be either of bimetallic 4 or mono-

metallic~ type. It is known that when such participation exists, there

(

/M'

···H

M-4<D

H

4 5

Scheme 1

Cossee explanation of stereochemistry

...

Green explar~tion of stereochemistry

46

Is a preference for a M···H-C interaction over a M···D-C interaction.1i If there is a structure like

i

or ~ during the polymerization, then, by having an alken-1-yl-1-d1 chain, there could be a preference for the

formation of some stereoisomers as shown in Scheme 2.

(

f' ·~ ^'

~ l~

Scheme 2

...

M

M favored

A system that brings these two concepts together was developed, along with two non-deuterated analogs, and their behaviour is described in this chapter.

Results and Discussion

The problem can be approached by designing a metal alkyl system that will insert only one olefin. A very convenient way of doing this is by having an alkyl chain containing a pendant olefin which is

appropriately situated for intramolecular insertion. This technique provides an artificially high local olefin concentration while providing only one olefin per metal alkyl. Once cyclization had occurred, if free ethylene was admitted to the system, polymerization would occur according to Eqn. 1.

(1)

Such interaction between a -iT-electron system and a metal atom has been shown to yield some stable complexes with transition metals and it has been established truit these complexes play an extremely important role in the stereochemically controlled reaction of these systems.

The intramolecular metal-~-electron interaction has been suggested in 3-butenyllithium,2 several hexenyl-metal derivatives,3 in some

alkenyl-aluminum derivatives4 and for some Grignard reagents arising from unsaturated species. 5 This type of interaction has also been postulated as the initial step in the intramolecular cyclization processes observed for the corresponding hex-5-en-1-yl derivatives.

These reactions are depicted as occurring via an internal addition across the double bond with the ease of reaction shown to be a function of chain length.6 No cyclization occurs when using 5-carbon or 8-carbon

48

and larger olefins. In fact, ring opening of cyclobutylmethylmagnesium compounds occurs5b as an intramolecular analog to the reverse of the addition step during a polymerization. Only partial cyclization is evident for the 7-carbon olefin (0.9% methylcyclohexane vs. 99.1%

n-heptane), while the 6-carbon olefin affords almost entirely cyclized product (97.6% methylcyclopentane vs. 2.4% n-hexane). The ease of cyclization of the hexenyl metal derivatives follows the order Al>Mg>Li>Zn>>Hg=0. 7

-The target molecules were prepared by similar routes (Scheme 3).

The systems were studied to determine if, in the presence of a Lewis acid, cyclization ^of~ into

I

would occur, if such cyclization was faster than free monomer insertion (polymerization) and the stereo- selectivity of such cyclization.

Preparation of 6a and 7a. ^An attempt was made to synthesize 6a by slow addition of a diethyl ether solution of hex-5-en-1-ylmagnesium chloride to titanocene dichloride suspended in dichloromethane at

0 8

-35 C. After isolating the product, though, it unexpectedly proved to be 7a instead, as shown by the absence of both, vinylic protons in the

1H-:~IR spectnun and olefinic carbons by ^{1 3}C-NMR. The hydrolysis prod- uct derived from the new compound was methylcyclopentane and not 1-hexene, as shown by GC analysis with authentic standards.

A possible source of the problem (cyclization) was believed to be light, so a second reaction was done in complete darkness. However, another (fortunate) variable was also introduced. The initiation of the Grignard reaction had been difficult, so the magnesium used for

Scheme 3 ~ _o )MCl

)~

H-fffiz)n

~!Hz

n g

=:..

Cp Ti-(Oiz n . 2 \ 1HF Cl 6

i<

CpzTiClz

rnp~

_0zln HCl

>

(OID-0!3

Et20 .

ep

2

r1

\Cl ]_

~Crnz)tiMgCl I

compmmd n -- 41 6a 7a 51 6b 7b

so

the synthesis of new hex-5-en-1-ylmagnesium chloride was activated by treatment with a small amount of ethyl bromide. The ethylmagnesium bromide formed was removed by washing the magnesium repeatedly with dry 1HF. Afterwards, 1HF was poured into the flask to cover the magnesium and the corresponding alkenyl chloride was added to prepare the Grignard reagent. (Even after this activation, sometimes the formation o£ the Grignard reagent would not start immediately and the mixture had to be refluxed for a few hours. The key to the synthesis of 6a, though, was the use of the stronger coordinating solvent THF, as described below.) The new reaction to obtain 6a was done protecting the mixture from light (which latter was shown not to be responsible for the cyclization) exactly under the same conditions as the previously described. Finally, 6a was isolated as a thick, dark red, thermally and light stable oil that had characteristic vinylic proton and olefinic carbon -signals in the

1H- and ¹³C-M4R spectra. The ¹H-NMR of 6a is shown in Fig. 1. Compound 6a does not cyclize to 7a at room temperature in toluene solution, even after several days of exposure to light. Hydrolysis with HCl of a toluene solution of 6a was analyzed by GC and showed the presence of 1-hexene while methylcyclopentane was not detected (Scheme 3).

Being readily soluble in hexane, the UV spectrum of 6a was recorded and for the first time the wavelengths for the a ~ d* and the ~ ~ d*

transitions were observed in a titanocene system (Fig. 2). Compare it with the UV spectrum of titanocene(dodecyl)chloride9

(Fig. 3). It should be noticed that both UV spectra are very similar therefore discarding the possibility of an intra~ or intermolecular metal-d0Uble bond coordination

*

--~---~--------'

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I''''

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I

8 7 6 5 6 4 (ppm) 3 2 1 0 Fig. 1. 1H-NMR spectrum of

ep

2Ti(hex-5-en-1-yl)chloride;* =solvent (C6D6).

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Fig.

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1

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'~~~1 : ~ -· 1 , - : - _ · 1 ,· · ,· · : 1

l=lo-2 cm

: · : :; , -·,~ ·: :1

!l!i 'lli'!il .!··;'Ill.';,'!.' ::• '·' . ·,

I : : . .

I~ ' I ' . ;:1 l,il 1;8litlh•rrrrrr·~-;--,,rrrrn''''''l••···--•,~·:r---.:....---· .-r7.·--"·~-~--i y--v.1·-,··1· :r-, .. --· ... · .-,~;~--,--1--.-, 1 I I I 200 300 nm 400 500 Fig. 3. UV spectrum of Cp 2Ti(dodecyl)chloride in hexane. OIFoptical density.

54

of 6a. If there had been a coordination of the double bond, a new energy level would had fanned by mixing metal d orbitals and olefin 'IT*

"bo d" b" 1 10 Thi b" d b uff" . 1 b 1 ant1 n mg or 1ta s. · s new or 1tal woul e s 1c1ent y e ow the energy level of the original metal 3d orbitals so that an electron from the metal-carbon cr-bond could easily be excited into it, i.e. the cr ^-+ d* transition should had been observed at a longer wavelength, which was not the case. The absence of such coordination is also evident from the ¹ H- and ^{1 3} C-NMR spectra were the chemical shifts of the vinylic

protons and carbons are essentially the same as those of the free olefin:

~o ~ 0.15 ppm downfield from free olefin for the vinylic protons;

~o ~ 0.06 ppm downfield from free olefin for the terminal vinyl carbon and MS ~ 0. 4 ppm upfield from free olefin for the internal vinyl carbon. The chemical shift of thea-His the same as that of a titanocene(alkyl)- chloride.3b,4b,4e

Preparation-of 6b and 7b. When a 1HF solution of hept-6-en-1-yl- magnesium chloride was added to titanocene dichloride suspended in dichloromethane at -35°C and the reaction was not protected from light, the product obtained from the reaction was the anticipated 6b, as shown by ¹H- and ¹³C-NMR spectroscopy and GC of its hydrolysis products.

Compotmd 7b was prepared using a diethyl ether solution of

(cyclohexyl)methylmagnesium chloride under the same conditions as those used to prepare 6b. Analysis of 7b by NMR spectroscopy and GC of its hydrolysis products verified its authenticity. 6b does not cyclize to

7b in toluene solution at room temperature even upon exposure to light for a few days (~cheme 3).

Preparation of 6b-~. M. attempt was made to synthesize 6b-~

before knowing the importance of the coordinating power of the solvent used in the reaction. A diethyl ether solution of hex-5-en-1-yl-1-d1- magneshun chloride was used first, but the product obtained resulted in a mixture of 6b-~/7b-~

=

1/1. Note that cyclization in this case was not complete, versus 100% cyclization of 6a to 7a under the same reaction conditions.

D

6b-d - - 1

/Cl

Cp 2 ^T~

D

7b-d - - 1

Comparison with previous experiments showed that the coordination ability of the ether used for the Grignard solutions was playing a very important role in the reaction. Repeating the reaction, but using a THF solution of the Grignard reagent, afforded pure 6b-~.

It was evident that the cyclization of the titanocene(alkenyl)- chlorides was effected by one or both of the Grignard reagent and the magnesium chloride formed during the reaction. These magnesium compounds may behave as Ziegler-Natta cocatalysts because of their slight Lewis acidity.11 Depending on the coordination ability of the ether present during the reaction, the Lewis acid sites will be more or less accessible to the titanocene derivative for the formation of an active species for cyclization (vide infra). A relatively poor coordination solvent like diethyl ether leaves those sites readily available for the formation of

56

such species. However, when TiiF is used; the Lewis acidity is suppressed b ecause o f ¹ . t s s ronger coor 1nat1ng an so vat1ng power. t d. . d 1 . 4b

Reaction of 6a with EtAlC12• A toluene solution of 6a (0°C) was treated with EtAlC12 and the mixture was kept at 0°C, and protected from light. It was hydrolyzed with HCl after 20 sec of reaction and the products were analyzed by GC. Three peaks were observed: ethane, methylcyclopentane and an rmidentified peak (probably CpH, as it also appears with the same retention time when 6a itself is hydrolyzed with HCl) • This rmknown had a different. retention time than 1-hexene, which was not detected. The reaction was very clean otherwise, and as will be discussed later, the cyclization occurs with the alkenyl ligand within the coordination sphere of the titanium atom.

Reaction of 6b with EtAlC12• Upon treatment of a

o

⁰

c

toluene solu- tion of 6b with EtA1Cl2, cyclization of the heptenyl ligand is not complete after 20 sec of reaction (0°C). The hydrolysis products from the reaction were analyzed by GC and the ratio of methylcyclohexane to 1-heptene was ca. 4/1, showing that the cyclization of 6b is slower than that of 6a. This behaviour was further analyzed by polymerizing ethylene with 6a or 6b using EtAlC12 as cocatalyst.

Polymerization of ethylene using 6a and EtAlC12• A qualitative comparison was made between the rates of cyclization and polymerization of 6a and 6b. Cyclization of 6a was shown to be complete in 20 sec or less at 0°C. It is well known that the active species for this type of polymerization systems (titanocene(alkyl)halide + EtA1Cl2) is formed extremely fast12 and the time for one ethylene insertion to the Ti-C

bond of the system titanocene(hexyl)chloride ⁺ EtA1Cl2 is only 95 msec

f . . h 13 Th . "f 1" .

a ter rnax1ng t e reactants. e quest1on was 1 ^eye 1zat1on was faster than ethylene insertion.

The reaction of the system 6a + EtA1Cl2 with ethylene gave mostly cyclopentyl-capped oligomers (97%), with only a minor amount of oligomers derived from alkyl exchange (3%), but there were no a-olefins present derived directly from 6a (Fig. 4). The presence of the cyclopentyl group on the oligomers was confirmed by GC/MS and by coinjection with a solution of oligomers resulting from ethylene polymerization by 7a.

Oligomers derived from alkyl exchange (even number n-alkanes) were confirmed with authentic standards.

The only way to justify the absence of a-olefins is by having a cyclization of 6a to 7a faster than the first ethylene insertion, i.e.

occurring in less than 95 msec. Alkyl exchange is also a relatively fast process, and could be seen to take place between titanocene(hexyl)- chloride and EtA1Cl2 at

o

⁰

c

in 0.29 sec.¹³a In the present case, the polymerization rate is faster than the alkyl exchange rate, and there-

fore the principal constituents of the reaction mixture are cyclopentyl- capped oligomers (Scheme 4) • The direct alkyl exchange between 6a and EtA1Cl2 is hindered because kc >> ka' and the cyclization reaction for this system is irreversible.¹⁴ When an authentic sample of 7a was used to polymerize ethylene, alkyl exchange occurred only in small amotmts, showing again that kp > ka''

Scheme 4 Cp 2Ti(Et)Cl

CpzT\~

'> Cp

r:-0

< Cp 2Ti(Et)Cl <: z, ;>' +Et.A1Cl 2 Cl (EtAlC1 2) Cl +EtA1C1 2 ka' kc k a k 11

'~

V1

-

k,

-

k

-

k II OJ p

- - -

p p p

M N.

k » k ( e::k 1) e::k 11 > k e:: k 1 c p p p a a

~

. '

,

....

I llsolvent

I

, ... ~· A Fig. 4. Hydrolysis products from 6a + EtA1Cl 2 + ethylene. ~~jor peaks are odd number cyclopentyl-capped alkanes, A=even number n-alkanes(alkyl exchange).

60

Polymerization of ethylene using 6b and Et.Al.Cl2. The polymerization of ethylene by 6b and EtA1Cl2 gave a completely different result. There were all three types of oligomers expected: n-alkanes derived from alkyl exchange, cyclohexyl-capped oligomers formed from the newly generated 7b and ~-olefin oligomers formed from the original 6b in a ratio of ca. 1/Z/3, respectively (Fig. 5). All of these were confirmed by capillary GC using authentic standards.

For this system, the cyclization rate is slightly slower or equal to the polymerization rate, while the alkyl exchange rate is definitely slower as can be seen from the smaller amounts of n-alkanes formed during the reaction (Scheme 5). We can then derive the relative order

kp ~ kc > ka, but it seems that kp would not be more than an order of

magnitude larger than k • _a

Reaction of ^6b-~ with EtAlC12. A Lewis acid is necessary to promote the cyclization of the alkenyl ligand in 6a and 6b. To determine if there was an ~-hydrogen participation during said cyclization, ^6b-~ was treated with EtA1Cl2 exactly tmder the same conditions as 6b (no ethylene present), except that the mixture was allowed to react for 60 sec to insure complete cyclization of the alkenyl ligand. After hydrolysis of the final mixture, a GC trace

showed that cyclization had been complete, as no 1-heptene was detected.

The product was separated from the solvent and an tmidentified compotmd by preparative GC. The ratio of methylcyclohexane-d₁(tm.known ::; 4/1.

It was not possible to collect enough of the unknown cornpotmd to allow possible identification by NMR spectroscopy. A ^{1 3}C-NMR spectrum of the

(

·-:::· ~ . ·.,~

0 0 0 0 0 10 0 0 I

c c c c

I

c c I I

⁰

A I I

~ c I

I

c

A

I I

A I A II n A I I A I I A H A II II "A II. A II Fig.

s.

Hydrolysis products from 6b + EtA1Cl 2 + ethylene. O=odd number a-olefins, C=odd number cyclohexyl-capped n-alkanes, A=even number n-alkanes (alkyl exchange).

Scheme 5

rO

Cp 2Ti(Et)Cl ...._ ep

2

T~~ .,. Cp

2

T~ ,... 7 Cp 2Ti(Et)Cl +EtAl.Cl Cl (EtAl.Cl ) Cl ka' kp"

H

n

2 2 kc kp' kp

oN:

k ~k,~k">;.k >k ~k, p p p c a a

+EtA1C1 2 ka kp"

q

0\ N

eluted product showed that methylcyclohexane was the major component in the mixture. ^By capillary GC it proved to be 70% methylcyclohexane plus two unidentified peaks close to it (12% and 18%).

A ²H-NMR (13.76 MHz) spectrum of the labeled methylcyclohexane15 (in toluene-d0, ·benzene-d

6 as internal reference) showed two singlets at 80.83 and 1.6, with an area ratio of 1.7 to 1.0, respectively. They were assigned to cis-methylcyclohexane-2-d

1 (2 ax.) ^~ and trans-methyl- cyclohexane-2-d1 (2 eq.) 2_, respectively. Upon close inspection of the spectrum, it was noticed that the upfield signal was somewhat broad, so the sample was analyzed by ²H-NMR (77 MHz). This time the upfield signal was split into two singlets at

oO.

80 from 2_ and

oO.

87 from an

unidentified compound 10. Their integr-ated areas· ·were about 1:1. No vinylic or allylic deuteriums were present.

It was noticed on the preparative GC trace that there was a shoulder trailing the methylcyclohexane peak. To insure that the signal observed on the ² H-NMR spectrum at 6 0. 8 7 was derived from the first peak com- pound (s) and not from the shoulder compound, the sample was passed again through the preparative GC column and the products were collected as leading (major peak) and trailing (shoulder) halves. The ²H-NMR spectra of these fractions were essentially identical, so the shoulder compound was not the cause of the unidentified signal. It was possible that the presence of such signal was due to the presence of (.methyl-d1)cyclo- hexane ·in the product. An authentic sample of this hydrocarbon was prepared by hydrolysis of ti tanocene (methyl (cyclohexane) )chloride with DCl. Surprisingly, the deuterium signal of the standard grew up at

64

60.84 in between the other peakS (fig. 6). The nature of 10 remains rmcertain and is still rmder investigation. There was no cycloheptane

formed (¹H-NMR 61.52), nor cis- or trans-2-heptene (GC).

The ratio ~I ~

=

1.01 shows that there is no a-hydrogen participa- tion during the cyclization step. The analogous compm.md 6a-~ reacts with EtA1Cl2 to give a mixture of cis- and trans-methylcyclopentane-2-d1

in a ratio cis/trans = 1. 0 , 16 and strenghtens the above observation.

Polymerization of ethylene using 6b-d

1 and EtA1Cl

2. It was

possible that the presence of the unknown compm.md 10 generated during the reaction of 6b-~ and EtA1Cl

2 was caused by the relatively long contact time between the reactants (60 sec). If fonnation of 10 was slow compared to ethylene insertion, it would be possible to avoid it by polymerizing ethylene with this system, tlrus removing the heptenyl ligand from the active center after a very short time (95 msec, 1

3b vide supra).

It was lmown that not all of the heptenyl ligands would have time to cyclize and because of that, some 7-~-a-olefins were going to be formed in about SO% excess over the cyclohexyl-capped oligamers (see Fig. 5). The chemical shift of the deuterated methylene rmit derived from such olefins would be at about 61.2-1.3. Therefore, if formation of 10 was slow, it was expected that the ²H-NMR spectrum of the oligomer mixture would have three peaks at about <Sl. 6 (oligamers from ~, ca. 1. 25 8 ( · from 9), with (oligamers derived directly from 6b-9:.t_) and 0. pl:~,gomers

ratios of about 1:3:1.

The ²H-NMR spectrum of the actual mixture (_in toluene-d0, benzene-d6