Reaction of ether and thioether functionalised 1-Alkenes with the cationic permethylzirconocene olefin polymerisation catalyst [(η5-C5Me5)2ZrMe]+. Molecular structure of the insertion product [(η5-C5Me5)2ZrCH 2CH(Me)CH2OEt]+

DOI: 10.1016/S0022-328X(97)00431-2

Source and publish data:

Journal of Organometallic Chemistry p. 159 - 164 (1998)

Update date:2022-08-03

Topics:

Authors:

Bijpost, Erik A.

Zuideveld, Martin A.

Meetsma, Auke

Teuben, Jan H.

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Article abstract of DOI:10.1016/S0022-328X(97)00431-2

Reaction of [(η⁵-C₅Me₅)₂ZrMe][MeB(C ₆F₅)₃] (1) with (thio)ether functionalised alkenes: 3-ethoxy-1-propene and 3-(methylthio)-1-propene gives stable insertion products [(η⁵-C₅Me₅)₂ZrCH ₂CH(Me)CH₂XR][MeB(C₆F₅)₃] (2: X=O, R=Et; 3: X=S, R=Me) in which the (thio)ether function is intramolecularly coordinated to zirconium. The molecular structure of 2 shows a regular 1-oxa-2-zirconacyclopentane in an envelope conformation. The metallacycles in 2 and 3 are stable toward further insertion of (functionalised) alkenes and cannot be activated for ethene polymerisation by pre-complexation of the (thio)ether function with strong Lewis acids (AlCl₃, MgCl₂, B(C₆F₅)₃ or [Ph₃C]⁺). The strong alkylating co-catalyst Me₃Al regenerates complex 1 by exchange of the (thio)ether function for methyl and thus initiates polymerisation of ethene.

Full text of DOI:10.1016/S0022-328X(97)00431-2

Journal of Organometallic Chemistry 551 1998 159–164

Reaction of ether and thioether functionalised 1-Alkenes with the

cationic permethylzirconocene olefin polymerisation catalyst

wž

x^q

h -C₅Me_{5 2}ZrMe . Molecular structure of the insertion product

wž

x^{q 1}

h -C₅Me_{5 2}ZrCH₂CH Me CH₂OEt

)

Erik A. Bijpost, Martin A. Zuideveld, Auke Meetsma, Jan H. Teuben

Groningen Centre for Catalytic Olefin Polymerisation, Department of Chemistry, UniÕersity of Groningen, Nijenborgh 4, Groningen, 9747 AG,

Netherlands

Received 20 May 1997; received in revised form 18 June 1997

Abstract

wŽ

. x Ž .

Reaction of h -C₅Me_{5 2}ZrMe MeB C₆F₅

1 with thio ether functionalised alkenes: 3-ethoxy-1-propene and 3- methylthio -1-

. x Ž

propene gives stable insertion products h -C₅Me_{5 2}ZrCH₂CH Me CH₂XR MeB C₆F₅2: XsO, RsEt; 3: XsS, RsMe in

which the thio ether function is intramolecularly coordinated to zirconium. The molecular structure of 2 shows a regular 1-oxa-2-

zirconacyclopentane in an envelope conformation. The metallacycles in 2 and 3 are stable toward further insertion of functionalised

alkenes and cannot be activated for ethene polymerisation by pre-complexation of the thio ether function with strong Lewis acids AlCl₃,

x^q.

MgCl₂, B C₆F₅or Ph₃C . The strong alkylating co-catalyst Me₃Al regenerates complex 1 by exchange of the thio ether function

for methyl and thus initiates polymerisation of ethene. q 1998 Elsevier Science S.A.

Keywords: Metallocene; Zirconium; Olefins; X-ray structure; Polymerisation; Catalysis

1. Introduction

Neutral group 3 hydrides h -C₅Me_{5 2}LnH and

the metal centre to give stable intermediates that subse-

quently obstruct polymerisation.

wŽ

Rapid splitting of C–X bonds Xsheteroatom by

x^q

cationic group 4 alkyls h -C₅Me_{5 2}ZrR are active

early transition metal complexes to yield stable M–X

w x

catalysts for the polymerisation of ethene 1 . An impor-

bond containing species is well-established 2,3 . Our

tant extension of the scope of catalytic potential of these

compounds is the copolymerisation of 1-alkenes with

functionalised monomers, since this may result in highly

valuable polymers, e.g., with improved adhesive proper-

ties, higher affinity for dyes and better compatibility

with other polar polymers.

group has shown that organolanthanide hydrides h -

C₅Me_{5 2}LnH cleave 3-alkoxy-1-propenes to form

alkoxides h -C₅Me_{5 2}LnOR and propene 2 . With

wŽ

w x

sulphur functionalised olefins, e.g., 3- methylthio -1-

propene C–X activation was not observed but the alkene

was neither oligomerised nor polymerised. Possibly,

intramolecular coordination of the sulphur atom after

insertion of the olefin into the Ln–H bond gives a stable

five-membered metallacycle, unable to undergo further

insertion.

w x

Sometimes allylic hydrogen chain transfer 2 frus-

trates polymerisation of higher olefins. More important

for olefins with polar functions is catalyst deactivation

by C–X activation Xsheteroatom . It is also possible

that insertion of the functionalised alkene leads to intra-

or intermolecular coordination of the polar function to

Kesti et al. have reported that 1-alkenes containing a

bulky polar functionality tert-butyldimethylsilyloxy, di-

wŽ

isopropylamine can be polymerised using

h -

x^q

w x

C₅Me_{5 2}ZrMe

as a catalyst 4 . Interestingly,

monomers with sterically less demanding polar sub-

stituents cannot be polymerised. Piers et al. have studied

)

Corresponding author. E-mail: teuben@chem.rug.nl.

¹Dedicated to Professor Peter M. Maitlis on the occasion of his

65th birthday.

0022-328X

(

)

160

E.A. Bijpost et al.rJournal of Organometallic Chemistry 551 1998 159–164

Scheme 1. Reaction of complex 1 with 3-functionalized-propenes.

catalytic cyclization of various functionalised dialkenes

sis of 2 and 3 shows GC-MS , in addition to C₅Me₅H

w x

with scandocene compounds 5 . They report that cy-

and C₆F₅H

, the hydrolysed alkyl ligands as

isobutylethylether from 2 and isobutylmethylsulfide

clization of diallylether is not possible and suggest that

a stable 1-oxa-2-scandacyclopentane has been formed.

from 3 as expected.

We decided to explore the potentially catalytic sys-

To determine the exact bonding of the inserted func-

tem formed by the cationic group 4 complex h -

t i o n a l i s e d

C₅Me_{5 2}ZrCH₂CH Me CH₂OEt MeB C₆F₅

a l k e n e

i n

₃x Ž . w x

₃x Ž .

2 , a

C₅Me_{5 2}ZrMe MeB C₆F₅

6 , which is isoelec-

tronic with h -C₅Me_{5 2}LnR and thio ether func-

tionalised terminal olefins to probe it for homo- and

co-polymerisation properties and to study fundamental

aspects of the interaction of the olefins with the metal

centre.

single crystal X-ray diffraction study was undertaken.

An ORTEP drawing of the molecule is depicted in Fig.

1. Selected bond lengths and bond angles are given in

Table 1.

The C₅Me₅ligands are h⁵-coordinated to zirconium

as normally is observed in bent sandwich metallocene

w x

compounds 8 . The Cp centroid –Zr–Cp centroid an-

Ž .

2. Results and discussion

gle 137.58 and Zr–C_ringdistances 2.532 9 A av are

close to those found in 1 136.68 and 2.537 A, respec-

tively 6 . The long Zr PPP Me B and Zr PPP F dis-

₃x Ž .

w x

Ž .

Reaction of h -C₅Me_{5 2}ZrMe MeB C₆F₅

with the functionalised 1-propenes, CH₂sCHCH₂XR

tances 5.114 A or longer indicate that there is no

direct interaction between cation and anion. The Zr–C23

XsO, RsEt; XsS, RsMe was investigated in

toluene with the reagents in 1:1 ratio at room tempera-

bond 2.297 12 A is longer than the corresponding

w x

ture on preparative scale. Stable products

h -

.₃x

C₅Me_{5 2}ZrCH₂CH Me XR MeB C₆F₅were iso-

Zr–C bond 2.223 A in 1 6 . The strong stabilisation

of the Zr centre by the co-ordinating oxygen atom

causes the metal centre in 2 to be less electron deficient

than in 1, resulting in a longer Zr–C bond. The dative

lated. It turned out that one single alkene insertion into

the Zr–Me bond had occurred, followed by intramolec-

Ž .

ular coordination of the heteroatom to zirconium to

Zr–O bond 2.259 6 A is longer than the ionic Zr–O

wŽ

form 1-oxa thia -2-zirconacyclopentanes

h -

bond 2.008 A in the neutral compound h -

C₅Me_{5 2}Zr CH₂CH₂CH₂CH₂O 9 , and also longer

Ž .

2 and

.x w x

C₅Me_{5 2}ZrCH₂CH Me CH₂OEt MeB C F₅

h -C₅Me_{5 2}ZrCH₂CH Me CH₂SMe MeB C₆F₅

xw^{6 3}Ž

.₃x

wŽ

than the dative Zr–O bond 2.122 A in h -

Ž . Ž

Scheme 1 . Remarkably, neither C–X activation

x w

C₅H_{5 2}ZrMe THF BPh₄10,11 . The atoms C21,

C23, O and Zr are located in a plane. Atom C22 is bent

nor allylic C–H activation was observed, even when

heating the reaction mixtures for prolonged times at

1008C.

away from that plane, giving the metallacycle a stable

envelope conformation 12 .

The metallacycles are stable at y208C in dieth-

Complexes 2 and 3 are inactive toward ethene,

propene, 1-hexene and 3-functionalised-1-propenes ex-

ylether and pentane under nitrogen for months. They

slowly decompose in dichloromethane-d₂room tem-

Ž .

2 and

cess of olefin, gases at 1 atm, CD₂Cl₂or C₆D₅Br,

perature with release of isobutylethylether

isobutylmethylsulfide 3 , respectively 7 . Methanoly-

25–1008C . Neither oligomerisation nor polymerisation

Ž .

w x

of the olefins was observed. This indicates that in

experiments to homo- or co- polymerise 3-functiona-

²Although formally not correct, we propose here to call the cyclic

products, containing an alkyl fragment with an M–C bond and

simultaneously intramolecularly coordinated through a dative M–X

⁴C₅Me₅H and C₆F₅H are formed during hydrolysis of h -

wŽ

bond, metallacycles.

x^q

. x^y

Ž .

Isobutylethylether 2a and isobutylmethylsulfide 3a have been

formed by hydrogen abstraction from a methyl substituent of a

cyclopentadienyl ligand by a Zr–C bond.

C₅Me_{5 2}ZrR and MeB C₆F₅

, respectively.

⁵The stability of analogous organic compounds has been well-

documented.

(

)

E.A. Bijpost et al.rJournal of Organometallic Chemistry 551 1998 159–164

161

Table 1

S e l e c t e d

lised-1-propenes using 1 as catalyst, the formation of a

w Ž

s t r u c t u r e

d a t a

f o r

1-oxa thia -2-zirconacyclopentane will be the main de-

activation pathway. This has been confirmed under

catalytic conditions in reactions between 1 and 3-

. x Ž .

C₅Me_{5 2}ZrCH₂CH Me CH₂OEt MeB C₆F₅

( )

Bonds A :

Ž .

2.259 6

2.297 12 C 22 –C 23

thio ether functionalised 1-propenes 1:200 ratio, in

Zr–O

C 21 –C 22

1.501 15

Zr–C 22

1.510 17

benzene, bromobenzene or toluene, 25–1008C, 5 days .

After quenching the reaction mixtures with methanol

the only products found were, in addition to the catalyst

residues C₅Me₅H and C₆F₅H ², unreacted alkene and

isobutylethylether with 2 and isobutylmethylsulfide

O–C 21

1.430 11 C 22 –C 26

1.537 16

Ž .

O–C 24

1.447 10

( )

Angles 8

Ž .

Ž . Ž .

Zr–C 23 –C 22

Ž .

108.5 7

Zr–O–C 21

119.9 5

with 3 . The latter in about 0.5% of the initial amount

Ž .

O–C 21 –C 23

108.8 8

C 21 –C 22 –C 26 110.6 9

of olefin used, i.e., as expected for only one insertion

Ž .

C 21 –C 22 –C 23 113.5 10 C 23 –C 22 –C 26 113.1 9

Ž .

73.5 3

Ž .

Zr–OC– 24

Ž .

O–Zr–C 23

124.3 5

per metal centre and formation of metallacycle 2 3 .

A possibility to activate the dative Zr–X XsO, S

bond in 2 and 3 is addition of a Lewis acid to compete

tion. For all four Lewis acid reactions the regular slow

release of isobutylethylether and isobutylmethylsulfide

with zirconium for the thio ether function of the in-

serted alkene and thus induce decomplexation. In this

way, a free coordination site on the metal can be

created, which should allow coordination and insertion

of a 1-alkene into the Zr–C bond of 2 and 3 and thus

w x

from the zirconacyclopentanes 2, 3 was observed 7 .

Successful activation of 2 and 3 appeared to be

possible with Me₃Al. When treated with one equivalent

of Me₃Al, ethene polymerisation started immediately.

After quenching the reaction mixture with methanol, the

soluble fraction contained exclusively isobutylethylether

start polymerisation. The problem is that the Zr IV

centre is highly electrophilic, which results in a strong

dative Zr§X bond and in addition also the chelate

effect will stabilise this complexation. Therefore, it is

reasonable to assume that cleavage of the Zr–X bond

can only be accomplished by a strong Lewis acid, such

Ž .

2 or isobutylmethylsulfide 3 . The insoluble fraction

appeared to be polyethene IR . The yields of

isobutylethylether and isobutylmethylsulfide were deter-

mined and correspond with the amount of zirconacy-

clopentane 2 3 started with. This strongly indicates

that no functional groups have been incorporated in

polyethene.

To find out about the nature of the catalyst activa-

tion, an experiment was performed with Me₃Al and 2 in

a 1:1 ratio at room temperature in dichloromethane-d₂.

After 3 h the characteristic resonances of notable

amounts of h -C₅Me_{5 2}ZrMe MeB C₆F₅

as MgCl₂, AlCl₃, B C₆F₅or Ph₃C^q.

Ž .

To test this hypothesis, 2 and 3 was dissolved in

dichloromethane-d₂, treated with one equivalent of the

Lewis acid of choice and brought under ethene 1 atm,

258C . The reactions were monitored by H NMR spec-

troscopy at regular intervals for 24 h. For B C₆F₅or

MgCl₂, no ethene consumption was observed. AlCl₃

and the extremely strong Lewis acid Ph₃C^qadded as

wŽ

x w

₃x Ž .

1 and

xw .₄x.

Ph₃C B C₆F₅also did not give the expected activa-

broadening of the functionalised alkyl resonances were

observed in the H NMR-spectrum. From this, it can be

suggested that initiation takes place by transmetallation,

i.e., the alkyl thio ether fragment is transferred from

zirconium to aluminium,

yielding Me₂Al–

wŽ

alkyl thio ether and the classical cationic h -

x^q

C₅Me_{5 2}ZrMe complex, the well-known catalyst for

the polymerisation of ethene.

Intentional chain transfer of an alkyl ligand from

zirconium to aluminium has been utilized by Shaunessy

⁶Instead the Lewis acids reacted with the Me–B bond of the

. x^y

counter anion MeB C₆F₅

. These reactions have not been investi-

gated further and the identity of the products formed remains to be

. x^y

established. To avoid reaction of Lewis acids with MeB C₆F₅

less reactive counter anion, B C₆F₅

, a

w Ž

. x^y

, was used. When AlCl₃was

w Ž

a d d e d

t o

s o l u t i o n

o f

made from

and 3-methoxy-1-propene in

xw Ž

. x

wŽ

C₅Me_{5 2}ZrCH₂CH Me CH₂OEt B C₆F₅

C ₅Me_{5 2}ZrMe B C ₆F₅

dichloromethane-d₂and the mixture was brought under ethene

atm, 258C . No ethene was consumed, but also no reaction with the

h -

.₄x

Fig. 1. Perspective ORTEP drawing of the molecular structure of

complex 2 shown at the 50% probability level. Counter anion

. x^y

MeB C₆F₅

,hydrogen atoms and non-coordinating diethylether

complex anion was observed.

have been omitted for clarity.

See for example 13 .

(

)

162

E.A. Bijpost et al.rJournal of Organometallic Chemistry 551 1998 159–164

and Waymouth for cycloalkylation of a,v-dienes with

partment of the University of Groningen. The determi-

nations are the average of at least two

x^q

w x

Me₃Al with and h -C₅Me_{5 2}ZrMe as catalyst 13 .

2.1. Concluding remarks

[ (

3 . 2 .

S y n t h e s i s

o f

)

(

)

][

(

) ] ( )

C₅Me_{5 2}ZrCH₂CH Me CH₂OEt MeB C₆F₅2

This investigation has shown that oligomerisation

and polymerisation of 3-oxygen- and 3-sulphur-

₃x Ž . Ž

0.60 g, 0.66

h -C₅Me_{5 2}ZrMe MeB C₆F₅

f u n c tio n a lis e d - 1 - p r o p e n e s

b y

mmol was dissolved in 30 ml of toluene. 3-Ethoxy-1-

xw ₃x Ž .

C₅Me_{5 2}ZrMe MeB C₆F₅1 after a smooth initial

propene m100 L, 0.83 mmol was added at once,

resulting in an orange oil. After 15 min, the volatiles

were removed in vacuo. The orange residue was stripped

three times with pentane. The orange solid was dis-

solved in 30 ml diethylether. The solution was filtered,

concentrated and slowly cooled to y208C to yield 0.49

insertion is prevented by the formation of stable zir-

conacyclopentanes. The systems appear to be insensi-

tive to typical catalyst deactivation reactions such as

C–X and allylic C–H activation. The insertion products

₃x

h -C₅Me_{5 2}ZrCH₂CH Me CH₂XR MeB C₆F₅

XsO, RsEt; 3: XsS, RsMe are incapable of

0.50 mmol, 75% of yellow crystals of 2. The

effecting alkene polymerisation. Addition of AlMe₃re-

crystals contain non-coordinating diethylether, which

was removed for spectroscopic and elemental analyses

₃x Ž .

generates

h -C₅Me_{5 2}ZrMe MeB C₆F₅

known polymerisation catalyst. Destabilisation of the

metallacyle, e.g., by using longer spacers between the

olefinic and the thio ether function or by introducing

more steric bulk on the thio ether part R of the alkene

CH₂sCHXR may lead to higher catalytic activity.

This is under investigation at the moment.

by powdering the solid followed by evacuation -0.05

mm Hg . ¹H NMR CD₂Cl₂

3.74 m,

CH CH₃C H₂O, 1 H , 3.48 m, CH₃C H₂O, 2H , 3.11

m, CH CH₃C H₂O, 1 H , 2.60 m, C H CH₃CH₂,

1H , 2.38 t, Js12.8 Hz, ZrC H₂CH CH₃, 1 H , 2.03

s, C₅C H_{3 5}, 15H , 1.97 s, C₅C H_{3 5}, 15 H , 1.29 t,

Js7.0 Hz, OCH₂C H₃, 3H , 0.93 d, Js6.4 Hz,

CH₂CH C H₃, 3H , 0.47 bs, BC H₃, 3H , 0.12 bd,

J s 12.4 Hz, ZrC H₂CH CH₃, 1H . ¹³C NMR

3. Experimental

CD₂Cl₂d 148.8 d, J_CFs236 Hz, C₆F₅, 137.9 d,

J_CFs241 Hz, C₆F₅, 136.6 d, J_CFs256 Hz, C₆F₅,

3.1. General considerations

. .

126.0 s, C₅CH₃, 125.6 s, C₅CH₃, 83.3 t,

J_CHs151 Hz, CH CH₃CH₂O , 70.1 t, J_CH⁵s146 Hz,

All experiments were performed under nitrogen us-

d, J_{C H}s 115 H z,

O C H C H

CH ₂C H CH ₃CH ₂

34.7

ing standard Schlenk, glovebox Braun MB200 and

vacuum line techniques. Solvents and reagents like ally-

methylether and allymethylsulfide were distilled from

N a – K alloy and stored under nitrogen.

22.4 q, J_CHs 127 Hz,

. .

OCH₂CH₃, 12.6 q, J_CHs128 Hz, C₅CH₃, 11.9

q, J_{C H}s 127 H z,

bs, B C H

11.2

11.0 q, J_CHs 125 Hz,

CH ₂CH C H ₃CH ₂

C₅CH₃. The ZrCH₂resonance was not assigned

Dichloromethane-d₂was stored under nitrogen over 3 A

. .

₃x

molecular sieves.

h -C₅Me_{5 2}ZrMe MeB C F

⁶w⁵

due to overlap with other signals in the region ds70y

was prepared according to a published procedure 14 .

Polymerisation grade ethene and propene were supplied

by DSM and used without further purification. 1-Hexene

6 0 p p m ; fo r c o m p a riso n se e

h -

C₅Me_{5 2}ZrCH₂CH₃THF

Ref. 11 . ¹⁹F NMR

w xx

x^q

CD₂Cl₂d-134.94 d, J_FFs20.3 Hz, o-F , y167.23

Merck was filtered over alumina, distilled from CaH₂

and degassed prior to use. NMR spectra were recorded

Ž¹⁹

t, J_FFs20.3 Hz, p-F , y169.81 d, J_FFs18.0 Hz,

m-F . Anal. Found: C, 54.35; H, 4.82; Zr, 9.22. Calc.

on Varian Gemini 200 F, 188 MHz , Varian VXR-300

for C₄₅H₄₆BF₁₅OZr: C, 54.60; H, 4.68; Zr, 9.22.

¹H, 300 MHz; C, 75.4 Mhz and Varian Unity 500

Ž¹

H, 500 MHz spectrometers at ambient temperatures.

¹H NMR spectra were assigned via COSY analysis.

[ (

3 . 3 .

S y n t h e s i s

o f

Chemical shifts for H and ¹³C NMR are referenced to

)

(

)

][

(

) ] ( )

C₅Me_{5 2}ZrCH₂CH Me CH₂SMe MeB C₆F₅3

internal solvent resonances and are reported relative to

tetramethylsilane. ¹⁹F NMR shifts are referenced to

₃x Ž . Ž

0.52 g, 0.58

h -C₅Me_{5 2}ZrMe MeB C₆F₅

external a,a,a-trifluorotoluene y63.8 ppm . GC

analyses were carried out on a Hewlett-Packard

HP5890-A instrument equipped with a HP-1 30 m=

0.53 mm capillary column. GC-MS measurements were

performed on a Ribermag R10-10C equipped with a CP

Sil 5 CB 25 m=0.32 mm capillary column. Elemental

analyses were carried out at the Micro-Analytical De-

mmol was dissolved in 20 ml of toluene. 3-Methylthio-

1-propene 66 mL, 0.60 mmol was added at once,

resulting in an orange oil. After 15 min, the volatiles

were removed in vacuo. The orange residue was stripped

with 3=10 ml pentane and washed with 2=10 ml

pentane. The resulting solid was dried in vacuum 0.05

mm Hg for 30 min to give an orange–yellow powder

(

)

E.A. Bijpost et al.rJournal of Organometallic Chemistry 551 1998 159–164

163

0.26 g, 0.25 mmol, 43% . H NMR CD₂Cl₂d 2.86

F 000 s1050. Besides compound 2, the crystal also

contains non-coordinating diethylether molecules in a

1:2 ratio with the zirconium complex. Data were col-

lected on an Enraf-Nonius CAD-4F diffractometer an

m, C H₂S, 2H , 2.72 m, C H CH₃, 1H , 2.34 t,

Js6.4 Hz, ZrC H₂CH, 1H , 2.29 s, SCH₃, 3H , 2.03

s, C₅C H_{3 5}, 15H , 1.98 s, C₅C H_{3 5}, 15H , 0.98 d,

Js6.0 Hz, CH₂CH C H₃, 3H , 0.47 bs, BC H₃, 3H ,

on-line liquid nitrogen cooling system 15 at 130 K

y0.78 dt, Js12.8 Hz, Js2.8 Hz, ZrC H₂CH, 1H .

with Mo Ka ls0.71073 A . Unit cell parameters and

C NMR CD₂Cl₂d 148.6 d, J_CFs222 Hz, C₆F₅,

orientation matrix were determined from a least-squares

137.8 d, J_CFs242 Hz, C₆F₅, 136.7 d, J_CFs258 Hz,

treatment of the SET4 16 setting angles of 22 high

order reflections. The unit cell was identified as tri-

clinic, space group P1. Reduced cell calculations did not

indicate any higher metric lattice symmetry 17 and

examination of the final atomic coordinates of the struc-

ture did not yield extra metric symmetry elements 18–

20 .

The structure was solved by Patterson methods and

extension of the model was accomplished by direct

methods applied to difference structure factors using the

. .

C₆F₅, 125.7 s, C₅CH₃, 74.8 ZrCH₂, 52.3

CH₂S , 38.7 CH₃S , 28.0 CH CH₃

. .

17.7

CH CH₃, 12.0 C₅CH₃, 10.6 bs, BCH₃. ¹⁹F

NMR CD₂Cl₂d-134.91 d, J_FFs20.3 Hz, o-F ,

y166.80 t, J_FFs20.3 Hz, p-F , y169.50 t, J_FF

19.2 Hz, m-F . Anal. Found: C, 52.58; H, 4.57. Calc.

for C₄₄H₄₄BF₁₅SZr: C, 53.28; H, 4.47.

3.4. General procedure for attempts to polymerise func-

tionalised 1-alkenes.

program DIRDIF 21 . The positional and anisotropic

thermal displacement parameters for the non-hydrogen

atoms were refined with block-diagonal least-squares

In a drybox h -C₅Me_{5 2}ZrMe₂5.1 mg, 13 mmol

)

. Ž

Cp sh -C₅Me₅and B C₆F₅6.5 mg, 13 mmol

. w x

procedures CRYLSQ 22 minimising the function Q

<. x

were placed in an ampoule and were dissolved in 0.4 ml

of bromobenzene or toluene to give a yellow solution.

s Ý_hw F_oy k F_c. A subsequent difference

Fourier synthesis resulted in the location of most of the

hydrogen atom positions, but also showed some density

which could be correlated to a, over an inversion

centre, disordered solvent molecule of diethylether. No

discrete model could be fitted in this density. The

BYPASS procedure 23 was used to take into account

the electron density in the potential solvent area, which

resulted in an electron count of 22.3 in a volume of 207

A in the unit cell. The hydrogen atoms were included

The functionalised alkene 200 equivalents was then

added to the catalyst solution. The ampoule was sealed

and placed in a thermostated bath at a fixed temperature

25–1008C . After 5 days, the reaction mixture was

quenched with methanol and passed over a column of

silica. The resulting mixture was analyzed with GC and

GC-MS.

3.5. General procedure for pre-complexation of 2 and 3

by Lewis acids under ethene atmosphere

in the refinement riding on their carrier atoms with their

positions calculated by using sp²or sp³hybridisation

at the C-atom as appropriate with a fixed C–H distance

Ž .

In a drybox 10 mmol of 2 3 and 10 mmol of Lewis

of 0.98 A. Final refinement on F_oby full-matrix

w xw . x

Ph₃C B C₆F₅,

acid MgCl₂, AlCl₃, B C₆F₅

block-diagonal least-squares techniques with anisotropic

thermal displacement parameters for the non-hydrogen

atoms and one overall common thermal displacement

factor for the hydrogen atoms converged at R_Fs0.079

AlMe₃were placed in an NMR tube equipped with a

Young valve and dissolved in 0.4 ml CD₂Cl₂. The

NMR tube was taken out of the drybox and attached to

the high-vacuum line. The solution was cooled to

y1968C. The tube was evacuated and brought under

wRs0.088 ; WsD for 6023 reflections with I)2.5

Ž .

s I and 569 parameters. Unit weights were used

throughout the refinement. The peaks in the final differ-

ence Fourier map calculations showed residual electron

densities of no chemical significance. Neutral atom

ethene ;1 atm . The mixture was then warmed to

room temperature. The reaction was monitored by NMR

spectroscopy. When no further reaction was observed,

the mixture was quenched with methanol and passed

over a column of silica. The soluble organic fraction

was analyzed by GC-MS.

scattering factors 24 were used and anomalous disper-

sion factors 25 were included in F . All calculations

were carried out on the HP9000r735 computer at the

University of Groningen with the programme packages

[(

3.6. Crystal data and structure determination of h -

Xtal 26 , PLATON 27 calculation of geometric data

and a locally modified version of the programme

PLUTO preparation of illustrations .

)

(

)

]

M e

(

Z r C H C H M e C H O E t

) ²][

]

( )

[

MeB C₆F₅

C₄H₁₀O

0.5

C₄₅H₄₆BF₁₅OZr C₄H₁₀O _0.5, M_rs1026.93, triclinic

⁸A. Meetsma, 1992. Extended version of the program PLUTO.

Univ. of Groningen, The Netherlands, unpublished. W.D.S. Mother-

well, W. Clegg, 1978. PLUTO. Program for plotting molecular and

crystal structures. Univ. of Cambridge, England, unpublished.

Ž . Ž .

space group P1 with as10.742 3 , bs14.674 2 , cs

Ž .

14.827 3 A, a s 95.16 1 8, b s 102.20 1 8, g s

Ž .

96.42 1 8, Vs2254.5 8 A , Zs2, D_xs1.513 g cm

(

)

164

E.A. Bijpost et al.rJournal of Organometallic Chemistry 551 1998 159–164

w x

J.W. Lauher, R. Hoffmann, J. Am. Chem. Soc. 98 1976 1729.

K. Mashima, M. Yamakawa, H. Takaya, J. Chem. Soc., Dalton

Tables of crystal data, anisotropic thermal displace-

ment parameters, atomic coordinates, bond lengths, bond

angles and torsion angles have been deposited at the

Cambridge Crystallographic Data Centre.

Trans. 2851 1991 .

10 R.F. Jordan, C.S. Bajgur, R. Willett, B. Scott, J. Am. Chem.

Soc. 108 1986 7411.

11 Y.W. Alelyunas, Z. Guo, R.E. LaPointe, R.F. Jordan,

Organometallics 12 1993 544.

12 A.C. Legon, Chem. Rev. 80 1980 231.

Acknowledgements

13 K.H. Shaughnessy, R.M. Waymouth, J. Am. Chem. Soc. 117

1995 5873.

Financial support for this investigation by an Innova-

14 X. Yang, C.L. Stern, T.J. Marks, J. Am. Chem. Soc. 116 1994

tion Oriented Research Programme on Catalysis IOP-

10015.

15 F. van Bolhuis, J. Appl Cryst. 4 1971 263–264.

katalyse of the Dutch Ministry of Economic Affairs is

16 J.L. de Boer, A.J.M. Duisenberg, Acta. Cryst. A 40 1984

gratefully acknowledged.

C410.

17 A.L. Spek, J. Appl. Cryst. 21 1988 578.

18 Y. Le Page, J. Appl. Cryst. 20 1987 264.

References

19 Y. Le Page, J. Appl. Cryst. 21 1988 983.

20 A.L. Spek, Proc. 8th Eur. Crystallogr. Meet., Belgium, 1983.

w x

H.-H. Brintzinger, D. Fischer, R. Mulhaupt, B. Rieger, R.M.

21 P.T. Beurskens, G. Admiraal, G. Beurskens, W.P. Bosman, S.

Garcia-Granda, R.O. Gould, J.M.M. Smits, C. Smykalla, The

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Waymouth, Angew. Chem., Int. Ed. Engl. 34 1995 1143.

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w x

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7844.

22 R. Olthof-Hazekamp, CRYLSQ, Xtal3.2 Reference Manual.

S.R. Hall, H.D. Flack, J.M. Stewart Eds. , Universities of

Western Australia, Geneva and Maryland, Lamb, Perth, 1992.

w x

M.R. Kesti, G.W. Coates, R.M. Waymouth, J. Am. Chem. Soc.

114 1992 9679.

23 P. van der Sluis, A.L. Spek, Acta Cryst. A 46 1990 194.

24 D.T. Cromer, J.B. Mann, Acta Cryst. A 24 1968 321.

25 D.T. Cromer, D. Liberman, J. Chem. Phys. 53 1970 1891.

26 S.R. Hall, H.D. Flack, J.M. Stewart Eds. , Xtal3.2 Reference

Manual. Universities of Western Australia, Geneva and Mary-

land, Lamb, Perth, 1992.

w x

W.E. Piers, P.J. Shapiro, E.E. Bunel, J.E. Bercaw, Synlett 74

1990 .

w x

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10015.

w x

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27 A.L. Spek, Acta Cryst. A 46 1990 C–34.

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