Synthesis and characterization of 1- and 2-(ω-alken-1-yl)indenes, their lithium salts and dichlorozirconium(IV) complexes

Journal of Organometallic Chemistry 579 (1999) 356–372

Synthesis and characterization of 1- and 2-(v-alken-1-yl)indenes, their

ꢀ

lithium salts and dichlorozirconium(IV) complexes

a,

a

b

Herbert Schumann *, Dirk F. Karasiak , Stefan H. M u¨ hle , Ronald L. Halterman ,

c

Walter Kaminsky , Ulrich Weingarten

a

Institut f u¨ r Anorganische und Analytische Chemie der Technischen Uni6ersit a¨ t Berlin, Straße des 17 Juni 135, D-10623 Berlin, Germany

b

Department of Chemistry and Biochemistry, Uni6ersity of Oklahoma, 620 Parrington O6al, Norman, OK 73019, USA

c

Institut f u¨ r Technische und Makromolekulare Chemie, Uni6ersit a¨ t Hamburg, Bundesstraße 45, D-20146 Hamburg, Germany

Received 16 November 1998; received in revised form 17 November 1998

Abstract

A series of new 1-, 2-, and multi-substituted indenes has been synthesized and characterized. The reaction of indenyl lithium or

,7-dimethylindenyl lithium with alkenyl bromides yielded a mixture of 1- and 3-allylindene (1), 3-(3-buten-1-yl)indene (2),

-(4-penten-1-yl)indene (3), 3-allyl-4,7-dimethylindene (4), 3-(3-buten-1-yl)-4,7-dimethylindene (5), as well as 3-(4-penten-1-yl)-4,7-

4

3

dimethylindene (6). The 2-substituted indenes 2-allylindene (7), 2-(3-buten-1-yl)indene (8), 2-(4-penten-1-yl)indene (9), 2-allyl-4,7-

dimethylindene (10), 2-(3-buten-1-yl)-4,7-dimethylindene (11), and 2-(4-penten-1-yl)-4,7-dimethylindene (12) were prepared by

PdCl (DPPF) or NiCl (DPPE) catalyzed cross-coupling reactions of the appropriate Grignard reagents with 2-bromoindene or

2

-bromo-4,7-dimethylindene. Alkenylation of 3-methylindenyl lithium and 2,4,7-trimethylindenyl lithium produced 1-(3-buten-1-

yl)-3-methylindene (13) or 1-(3-buten-1-yl)-2,4,7-trimethylindene (14), respectively. The indene derivatives 1–14 react with n-butyl

lithium in hexane yielding the corresponding lithium salts 1a–14a. Zirconium tetrachloride reacts with 1a, 2a, 4a–6a and 11a–14a

under formation of the corresponding bis(indenyl)zirconium dichloride complexes 1b, 2b, 4b–6b and 11b–14b. All compounds

1

13

1

were characterized by elemental analysis, H and C{ H}-NMR spectroscopy and mass spectrometry, 5b and 12b also by single

crystal X-ray structural analysis. 1b, 4b–6b and 11b–13b are active catalysts for the polymerization of ethene and propene.

©

Keywords: Alkenylindenes; Alkenylindenyl lithium salts; Alkenyl indenyl zirconium complexes; Ethene polymerization; Propene

polymerization

thanidocene complexes as effective catalysts especially

1. Introduction

for the polymerization of alkenes [2] is considerably

restricted by their high sensitivity to air and moisture.

The use of donor substituted cyclopentadienyl or in-

denyl ligands was expected to reduce this sensitivity by

additional coordination of the metal without consider-

able reduction of their catalytic capabilities. The ﬁrst

donor substituted ligand, an ether functionalized cy-

clopentadienyl ligand, was published by Qian et al. in

In recent years, indenyl complexes of the group 4

metals and of the lanthanides were studied very inten-

sively due to their ability to catalyze a multitude of

reactions like polymerization, hydrogenation, or epoxi-

dation [1]. However, the potential of the lan-

ꢀ

Dedicated to Professor Dr Helmut Werner on the occasion of his

1

986 [3] followed by the synthesis of several other

6

5th birthday.

Corresponding author. Tel.: +49-30-31423984; fax: +49-30-

donor substituted cyclopentadienyl [4] and indenyl [5]

derivatives. In fact, the presence of strong donor atoms

such as nitrogen [6] or oxygen [4d, 4f, 5d, 7] in the

*

3

1422168.

E-mail address: schumann@chem.tu-berlin.de (H. Schumann)

PII: S0022-328X(99)00026-1

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

357

substituting groups of the soft indenyl or cyclopentadi-

enyl ligands caused the formation of reasonably stable

lanthanidocene complexes, but it pointed out that they

were no longer active catalysts for the polymerization

of alkenes [8]. Obviously, the additional coordination of

the donor atom to the metal blocks the active site of the

catalyst irreversibly.

A solution of the problem was expected from the use

of ligands substituted by weaker donor systems such as

alkenyl groups. In 1988, Okuda used 1-(3-butenyl)-

Scheme 1.

2

,3,4,5-tetramethylcyclopentadiene as a ligand in metal-

locenes [9]. Though the ﬁrst alkenylindene,

-allylindene, was described already in 1964 [10] fol-

The indenyl lithium salts 1a to 6a were obtained by

reacting the indenes 1 to 6 with an excess of n-BuLi in

hexane at room temperature (Scheme 2). The salts are

insoluble in hexane and can be isolated by ﬁltration and

puriﬁed by washing with hexane to remove excess n-

BuLi and unreacted indene. The colorless salts, which

are very sensitive towards oxygen and moisture, are

soluble readily in diethyl ether and THF.

3

lowed by instructions for its improved synthesis from

allylbromide and indenylmagnesium bromide or in-

denyllithium [11], until now, there are no systematic

studies on indenyl systems substituted by alkenyl

groups of varying chain length and at different sites.

Another point of interest was to get better results in

zirconocene-catalyzed polymerizations by variation of

the substituents on the indenyl ring, e.g. to get com-

plexes of higher catalytic activity, a control of the

molecular weight, the molecular weight distribution, the

stereochemistry and the melting points of the polymers.

Examples for such successful modiﬁcations were the

introduction of alkyl substituents on the 2-position of

the ﬁve-membered indenyl ring which resulted in higher

molecular weights and higher melting points for

polypropylene [12] or the additional substitution on the

The alkenylindenes 1 to 6 and their lithium salts 1a

to 6a were charaterized by elemental analysis, H-

1

13

1

NMR, C{ H}-NMR and mass spectra. The methyl

groups of the 4,7-dimethyl-1-alkenylindenyl lithium

compounds 4a, 5a, and 6a exhibit two clearly separated

1

13

1

diagnostic signals in the H and C{ H}-NMR spectra.

4- or 7-positions of the indene which inﬂuenced the

activity of the catalyst and the regiocontrol of the

polymer or the mechanism of oleﬁn insertion [12d, 12e,

13].

Here we report a general method for the preparation

of 1-, 2- and 3-alkenylindenes and of their lithium salts

as well as the synthesis of some alkenylindenyl zirco-

nium complexes and their potential for the polymeriza-

tion of oleﬁns. Corresponding lanthanide complexes

will be the subject of a following paper.

Scheme 2.

2.2. [2-(ꢀ-alken-1-yl)indenyl]lithium compounds

2

-substituted indenes can be prepared either by nu-

2

. Synthesis and properties

cleophilic addition of organometals to 2-indanone fol-

lowed by dehydration; or by nickel or palladium

catalyzed coupling of Grignard reagents with 2-bro-

moindene [14]. Since the ﬁrst pathway affords the de-

sired products very often with only low yields due to

the competing deprotonation of 2-indanone, we used

the cross-coupling route. The ability of the Grignard

reagents to deprotonate the bromoindene is apparently

much lower than its ability to undergo the coupling

reaction.

The starting compounds 2-bromoindene and 2-

bromo-4,7-dimethylindene [15] are easy to obtain by

bromination of indene or 4,7-dimethylindene [16] with

N-bromosuccinimide in water–DMSO followed by

acid-catalyzed dehydration of the respective 2-bromo-

2.1. [1-(ꢀ-alken-1-yl)indenyl]lithium compounds

The reaction of allyl bromide, 4-bromo-1-butene or

-bromo-1-pentene with indenyllithium or 4,7-

5

dimethylindenyllithium in THF at 20°C yields the cor-

responding 3-alkenylindenes 1 to 6 (Scheme 1). If the

reactions were conducted at 0°C or below 0°C, mixtures

of the 1- and 3-positional isomers are formed, whereas

at higher reaction temperatures the more stable 3-

alkenylindenes predominate or are the lonely products.

We isolated the pure alkenylindenes by fractional distil-

lation as colorless or light yellow, distillable liquids

with yields ranging from 69 to 88%.

358

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

Scheme 3.

Scheme 5.

indan-1-ol derivative formed in the ﬁrst step of the

reaction (Scheme 3) [17]. Since the efﬁciency of the

subsequent coupling with alkenylmagnesium halides

highly depends on the purity of the 2-bromoindenes,

they had to be puriﬁed by ﬂash chromatography and

fractional distillation.

Treatment of the carefully puriﬁed bromoindenes

with alkenylmagnesium halides in the presence of cata-

lysts afforded successfully the 2-alkenylindenes 7 to 12

The 2-alkenylindenes as well as their lithium salts

were characterized by elemental analysis, H-NMR,

C{ H}-NMR and mass spectra. The NMR spectra of

the 2-alkenyl(indenyl)lithium compounds differ signiﬁ-

cantly from those of the 1-alkenyl(indenyl)lithium

derivatives. The C₂₆symmetry of the 2-substituted com-

pounds caused the appearance of only one signal for

the two hydrogen atoms on the ﬁve-membered ring of

the indene and also only one signal for the 4,7-dimethyl

groups in 10a, 11a and 12a.

1

13

1

(

Scheme 4). The 2-allylindenes 7 and 10 were prepared

from 2-bromoindene or 2-bromo-4,7-dimethylindene

and allylmagnesium chloride in the presence of

PdCl (DPPF) in THF at room temperature for 72 h.

2

The yields varied between 25 and 35%. The reaction

failed when the nickel chloride catalyst was used, prob-

ably due to the formation of unreactive allylnickel

2

.3. [1-(3-buten-1-yl)-3-methylindenyl]lithium and

[1-(3-buten-1-yl)-2,4,7-trimethylindenyl] lithium

complexes [18]. The NiCl (DPPE) catalyzed coupling of

2

A mixture of 3-(3-butenyl)-1-methylindene and 1-(3-

butenyl)-3-methylindene (13) were prepared in an al-

most quantitative yield by using 1-methylindenyllithium

2-bromoindene or 2-bromo-4,7-dimethylindene with 3-

butenyl- or 4-pentenylmagnesium bromide produced

2

-(3-buten-1-yl)indene (8), 2-(4-penten-1-yl)indene (9),

-(3-buten-1-yl)-4,7-dimethylindene (11), or 2-(4-pen-

[

19] and 4-bromo-1-butene in THF at 0°C. Deprotona-

tion of the mixture with n-BuLi in hexane produced

0% of [1-(3-buten-1-yl)-3-methylindenyl]lithium (13a)

Scheme 6).

,4,7-Trimethylindene, synthesized according to liter-

ten-1-yl)-4,7-dimethylindene (12) with yields of 38–

4%.

The 2-alkenylindenes 7 to 12 reacted with excess

4

(

6

2

n-BuLi in hexane at room temperature with precipita-

tion of the corresponding indenyl lithium salts 7a to

ature methods [12d], was transformed into 2,4,7-

trimethylindenyllithium (Scheme 7) which reacted with

12a (Scheme 5).

Scheme 4.

Scheme 6.

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

359

Scheme 7.

Scheme 9.

4

-bromo-1-butene to give 3-(3-buten-1-yl)-2,4,7-

1

trimethylindene (85% yield) (14). Treatment of 14 with

n-BuLi afforded [1-(3-buten-1-yl)-2,4,7-trimethylin-

denyl]lithium (14a) (82% yield) (Scheme 8).

The H-NMR spectra of 1b, 2b and 4b to 6b show

two dd-signals for the CH groups of the ﬁve membered

ring of the indenyl ligand indicating an equimolar

mixture of DL/meso diastereomers. There are no at-

tempts made to separate the diastereomeric mixtures by

crystallization. In the low-temperature NMR spectrum

of 5b, recorded at −70°C, the signals are only shifted,

but not separated with respect to rotational isomers.

The zirconocenes 11b to 12b do not form diastereomers

and show no hindered rotation in the NMR at −50°C.

2

.4. Bis(alkenylindenyl)zirconium dichloride complexes

^A^d^dⁱ^tⁱ^oⁿ^o^f^Z^r^C^l4 to ethereal solutions of the

alkenylindenyl lithium salts 1a, 2a, 4a to 6a, or 11a to

4a (1:2 mole ratio) at room temperature and in the

1

dark produced the bis(alkenylindenyl)zirconium dichlo-

ride complexes 1b, 2b, 4b to 6b, or 11b to 14b with

yields ranging from 29 to 62% (Scheme 9). The freshly

prepared yellow colored complexes, among which only

In the case of the complexes 13b and 14b only

D,L

diastereomers could be detected by NMR. The mass

spectra of the complexes 1, 2, and 6 indicate fragmenta-

tion processes with elimination of HCl which are al-

ready known from other complexes of the group 4 and

group 9 elements [20]. The mass spectroscopic results

prove that the HCl elimination process is independent

of the number of carbon atoms of the substituent.

5b is appreciable stable towards air and moisture, are

all soluble in polar solvents and to some extent also in

hexane and pentane. The solubility in hexane is low for

complexes containing indenyl ligands with short alkenyl

chains in the 1-position, but increases up to 1 g/10 ml

hexane for long-chain alkenyl groups in the 2-position

of the indenyl ligand.

3

. Molecular structures of 5b and 12b

The molecular structures of bis[1-(3-buten-1-yl)-4,7-

dimethylindenyl]zirconium dichloride (5b) and bis[2-(4-

penten-1-yl)-4,7-dimethylindenyl]zirconium dichloride

(

12b) were determined by single crystal X-ray diffrac-

tion. Suitable crystals were obtained by recrystallization

from hexane. The crystallographic data and reﬁnement

parameters are listed in Table 1, the molecular struc-

tures are shown in Fig. 1 (5b) and Fig. 2 (12b). In

contrast to our expectations, in both complexes the

double bonds of the ligand-bonded alkenyl groups do

not coordinate the zirconium atom. In 12b, the double

Scheme 8.

360

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

Table 2

bonds are even turned away from the metal center. The

alkenyl groups do not signiﬁcantly change the struc-

tural parameters of the bis(indenyl) core. For both

compounds, the bond distances Zr–Cl and Zr–Cp

Polymerization results obtained with 1b, 4b–6b, and 11b–13b at 30°C,

−

1

2

1

min

bar monomer pressure, 200 ml toluene, [MAO]=2g l , [Zr]=1×

−6

−1

−6

−1

0

mol l

(ethylene) and 5×10

mol l

(propylene), t_P_o_l=60

f

(

Cp=centroid of the 5-membered ring of the indenyl

^Mn^b

^Tm^c

^D^Hm^d

Metallocene

Monomer

Activity^a

system) as well as the bond angles Cp–Zr–Cp and

Cl–Zr–Cl are of the order estimated already for other

bridged and unbridged zirconium complexes [1b,1k].

1

4

5

6

1

b

1b

2b

3b

Ethylene

170 000

16 000

11 000

18 000

14 000

27 000

80 000

268 000

591 000

551 000

493 000

604 000

742 000

353 000

140 160

143 158

141 157

138 154

140 140

138 143

142 165

4

. Catalytic activity

The complexes 1b, 4b to 6b, and 11b to 13b were

tested as catalytic for the polymerization of ethylene

and propylene in the presence of methylaluminoxane

MAO) as a cocatalyst at 30°C. The results of these

1

4b

5b

6

1

b

Propylene

500

B10

10

B10

250

150

10

5100

14 000

e

n.d.

b

10 100

17 000

7200

(

1b

2b

3b

investigations are summarized in Table 2.

4200

a

b

c

d

e

f

In kgPol/(molZr*h).

−1

In g mol

In °C.

.

Table 1

Crystal data and structure reﬁnement for 5b and 12b

In J g⁻¹.

n.d.: not determined.

All PP products were atactic.

5

b

12b

Empirical formula

C₃₀H₃₄ZrCl (C H ) 0.5 [C₃₂H₃₈ZrCl₂]

2 7 8

−

1

Formula weight (g mol )648.87

292.40

3

At least two ways are known to modify a catalytic

Crystal size (mm ) and

color

0.36×0.30×0.06;

yellow

0.54×0.48×0.36;

orange

system: changing the substituent of the indenyl rings or

bridging the ligands. The positive electronic and steric

effects affected by the substituent can change the nature

and activity of the catalyst and, in turn, the ratio of the

polymer chain propagation/termination rates [12a, 12d,

13, 22]. Concerning the inﬂuence of the metallocene

substitution patterns on activity and polymer molecular

weight, all new complexes observed this theory. Com-

plex 1b was determined to have an activity of 170 000

Crystal system

Space group

Monoclinic

Orthorhombic

Pcan

8.633(2)

16.803(5)

19.751(4)

2864.9(12)

P2 /c

1

˚

a (A)

10.196(2)

25.692(9)

13.198(2)

3268(2)

109.02(2)

4

1.319

1352

0.524

193(2)

˚

b (A)

˚

c (A)

˚

3

V (A )

i (°)

Z

8

D_c_a_l_c(g cm⁻³)

F(000)

1.356

1216

−

1

v(Mo–K ) (mm⁻1₎

kg PE (mol Zr×h)

to 12b with an activity of 27 000 kg PE (mol Zr×h)

and an M =268 000 in contrast

0.589

193(2)

0.71069

452q553

2.70

n

a

−

1

T (K)

˚

Radiation (Mo–K ) (A) 0.71069

a

and M =742 000. In the case of the propylene poly-

n

2

q range (°)

352q553

2.70

(0.80+0.35 · tan h) (0.90+0.35 · tan h)

4962

4748

merization this theory does not ﬁt; no systematic line is

found here. The good polymerization results of the new

unbridged zirconocenes are on the same order as the

activities and molecular weights of known bridged zir-

conium complexes [1], i.e. [Me Si(2,4,7-Me Ind) ]ZrCl ,

Aperture (mm)

Scan angle (°)

Reﬂections collected

Reﬂections unique

2944

1893

Reﬂections observed, I= 2233

|(I)

2

3

2

i

[

Me Si(2-Me-4,6- PrInd) ]ZrCl

or

PhInd) ]ZrCl . The highest activity of the ethylene

2 2

[Me Si(2-Me-4-

2

Data/Restraints/Parameter 4748/32/355

2941/0/161

0.0508/0.0942

0.1184/0.1423

1.050

R₁_o_b_s_e_r_v_e_d_/_a_l_l_d_a_t_aa

0.0813/0.1966

0.1161/0.1323

1.012

b

polymerization was reached with the systems 1b and

13b [1f, 1j, 23]. In addition it could be proposed that

the methyl groups of the 4,7-substituted ligands stabi-

lize the active center by an a-agostic interaction [1f].

These facts might give the explanation for much higher

molecular weights obtained with 4,7-methyl-substituted

indenyl zirconocenes. 11b and 12b give the highest

molecular weights, because of the absence of the meso

wR₂observed/all data

Goodness-of-ﬁt^c

Absorption correction/

min/max

Dz_m_i_n_/_m_a_x

difabs/0.737/1.578

−0.825/0.554

−0.344/0.679

a

R =ꢀ(ꢁF ꢁ−ꢁF ꢁ)/ꢀꢁF ꢁ).

1

o

c

o

b

c

2

2 1/2

wR =[ꢀw(ꢁF ꢁ−ꢁF ꢁ) /ꢀwꢁF ꢁ ]

.

2

o

c

o

2

1/2

GOOF=[ꢀw(ꢁF ꢁ−ꢁF ꢁ) /(n−p)]

.

o

c

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

361

˚

Fig. 1. ORTEP plot [21] of 5b. Selected bond distances (A) and angles (°), estimated standard deviations in parentheses; Cp(1) and Cp(2) deﬁne

the centroids of the indenyl ring atoms C(101)–C(103), C(108), C(109) and C(201)–C(203), C(208), C(209), respectively: Zr–Cl(1) 2.439(3),

Zr–Cl(2) 2.422(3), Zr–Cp(1) 2.233(5), Zr–Cp(2) 2.232(4), Cp(1)–Zr–Cp(2) 130.2(2), Cp(1)–Zr–Cl(1) 106.9(2), Cp(1)–Zr–Cl(2) 105.8(2),

Cp(2)–Zr–Cl(1) 105.6(2), Cp(2)–Zr–Cl(2) 106.4(2), Cl(1)–Zr–Cl(2) 97.20(8), plane Cp(1)–plane Cp(2) 58.1(3).

isomers.

The

complex

bis[2-(3-buten-1-yl)-4,7-

formed on a Perkin–Elmer 240 C elemental analyser.

Mass spectra were determined on a Varian MAT 311 A

spectrometer using electron impact (standard 70 eV,

otherwise speciﬁed).

dimethylindenyl]zirconium dichloride (11b) showed two

other important effects: it yields a low M /M as well

W

n

as a high propylene activity resulting in a molecular

weight of 17 000. It is furthermore worth noticing that

the increase in length of the alkenyl side chain from

four carbons for 11b to ﬁve carbons for 12b causes a

change of the polydispersity. While not forming a

trend, this change does indicate some signiﬁcant inﬂu-

ence of the side chain on the polymerization and chain

termination processes. The results reported by Way-

mouth [24] that 2-substituted indenyl zirconium dichlo-

rides produce isotactic polypropylen and that they are

more effective catalysts than complexes with 1-substi-

tuted indenyl ligands is conﬁrmed for the catalytic

activity of 11b and 12b.

5.2. Substituted 1-alkenyl-indenyl compounds

5.2.1. 1-Allyl-1H-indene and 3-Allyl-1H-indene [11a]

(1)

Indenyllithium (4.93 g, 40.38 mmol) was dissolved in

THF (80 ml) and the colorless solution was cooled to

0°C. Allyl chloride (3.71 g, 48.46 mmol) was added

slowly to the solution and the mixture was stirred for

48 h at 20°C. The solvent was removed under reduced

pressure, and water (20 ml) was added. The water layer

was extracted several times with Et O and the organic

2

layer was dried over MgSO . Fractional distillation

4

yielded 1 as a colourless liquid (4.33 g, 69%). B.p.:

54–56°C/0.2 mbar. Two double-bond isomers (3-allyl-

5. Experimental

and 1-allylindene) were evident in the NMR spectra.

1

5.1. General comments

H-NMR (CDCl , 400 MHz): 1-Ally-1H-indene: 7.53–

3

7

.26 (m, 4H, CH aromat.), 6.90 (dd, J=1.8 Hz, 1H,

All operations were performed under a dry nitrogen

ꢀCH), 6.60 (dd, J=1.8 Hz, 1H, CHꢀ), 6.0–5.85 (m,

atmosphere using standard Schlenk techniques. All the

working up procedures of the hydrocarbons were car-

ried out without protection by nitrogen. Solvents were

dried over sodium/benzophenone and distilled prior to

use. The NMR spectra were recorded on a Bruker

ARX 200 or a Bruker ARX 400 spectrometer. Proton

and carbon assignments were generally made based on

COSY and HETCOR spectra. CH analyses were per-

1H, CHꢀCH ), 5.25–5.11 (m, 2H, CHꢀCH ), 3.59 (dd,

2

J=6.2 Hz, 1H, CH), 2.70 (m, J=6.1 Hz, 1H, CH₂),

2.35 (m, J=6.1 Hz, 1H, CH ). 3-Ally-1H-indene: 7.53–

2

7.26 (m, 4H, CH aromat.), 6.32 (s, 1H, CHꢀC), 6.2–

6.05 (m, 1H, CHꢀCH ), 5.25–5.11 (m, 2H, CHꢀCH ),

2

13

1

3.41 (m, 4H, CH₂). C{ H}-NMR (CDCl , 100.64

3

MHz): 144.40 (C), 142.43 (C), 138.93 (C), 135.56

(CHꢀCH ), 128.85 (CHꢀC), 125.94 (CH aromat.),

2

362

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

˚

Fig. 2. ORTEP plot [21] of 12b. Selected bond distances (A) and angles (°) estimated standard deviations in parentheses; Cp(1) and Cp(1)% deﬁne

the centroids of the indenyl ring atoms C(1)–C(3), C(8), C(9) and C(1)%–C(3)%, C(8)%, C(9)%, respectively: Zr–Cl(1) 2.415(2), Zr–Cp(1) 2.242(2),

Cp(1)–Zr–Cp(1)% 131.76(7), Cp(1)–Zr–Cl(1) 106.83(6), Cp(1)–Zr–Cl(1)% 105.01(6), Cl(1)–Zr–Cl(1)% 95.69(10), Cp(1)–Cp(1)% 52.74(11). Symmetry

1

2

transformation (%): x, −y+1, −z+ .

+

1

24.70 (CH aromat.), 123.69 (CH aromat.), 119.21 (CH

(CH ). LRMS (24°C): m/z 170 (33) [M] , 142 (12)

2

+

aromat.), 116.25 (ꢀCH ), 37.68 (CH ), 32.41 (CH ).

LRMS (19°C): m/z 156 (32) [M] , 155 (16) [C H ] ,

1

[C H ] , 141 (16) [C H ] , 129 (100) [C H ] , 128

2

+

11 10

11

9

10

9

+

+ +

10 8 9 8 9 7

+

(74) [C H ] , 116 (39) [C H ] , 115 (39) [C H ] .

12

11

+

41 (21) [C H ] , 128 (25) [C H ] , 116 (32)

Anal. Found: C, 90.33; H, 8.20. C H (170.25 g

1

9

10

8

13 14

+

−1

[C H ] , 115 (100) [C H ] . Anal. Found: C, 92.26; H,

mol ) (2) Calc.: C, 91.71; H, 8.29%.

9

8

9

7

−

1

7

.74. C H (156.23 g mol ) (1). Calc.: C, 91.06; H,

1

2

12

7.66%.

5.2.3. 3-(4-Penten-1-yl)-1H-indene (3)

5.2.2. 3-(3-Buten-1-yl)-1H-indene (2)

The procedure described above for the synthesis of 2

Indenyllithium (4.52 g, 37.03 mmol) was dissolved in

was followed with indenyllithium (2.43 g, 19.9 mmol)

and 5-bromo-1-pentene (2.97 g, 19.9 mmol) in THF (50

ml) to yield after fractional distillation 3 as a light

THF (50 ml). To the solution was added slowly 4-

bromo-1-butene (5 g, 37.03 mmol). The reaction mix-

ture was stirred 12 h at 20°C. The THF was removed

under reduced pressure and the residue was mixed with

diethyl ether (70 ml) and water (30 ml). The water

phase was extracted diethyl ether (3×10 ml). The

yellow liquid (2.61 g, 71%). B.p.: 91–95°C/0.1 mbar.

1

H-NMR (CDCl , 200 MHz): 7.40 (m, 4H, CH aro-

3

mat.), 6.28 (t, J=1.7 Hz, 1H, ꢀCH), 5.93 (m, 1H,

CHꢀCH ), 5.09 (m, 2H, CHꢀCH ), 3.40 (d, J=2.0 Hz,

2

combined organic layers were dried over MgSO . The

2H, CH ), 2.62 (m, 2H, CH CH ), 2.24 (m, 2H,

2 2 2

4

13

1

solvent was evaporated under reduced pressure to yield

CH CH ), 1.88 (m, 2H, CH CH ). C{ H}-NMR

2 2 2 2

2

as light yellow liquid (5.44 g, 86%). B.p.: 81–83°C/0.1

(CDCl , 50.32 MHz): 145.47 (C), 144.49 (C), 144.28

3

1

mbar. H-NMR (C D , 200 MHz): 7.30 (m, 4H, CH

(C), 138.68 (CHꢀCH ), 127.80 (CH aromat.), 125.92

6

2

aromat.), 5.97 (t, J=1.7 Hz, 1H, ꢀCH), 5.83 (m, 1H,

(CH aromat.), 124.42 (CH aromat.), 123.69 (CH aro-

CHꢀCH ), 5.02 (m, 2H, CHꢀCH ), 3.05 (dd, J=2.3

mat.), 118.91 (CHꢀ), 114.72 (CHꢀCH ), 37.66 (CH ),

2

Hz, 2H, CH ), 2.48 (m, 2H, CH CH ), 2.35 (m, 2H,

33.62 (CH CH ), 27.17 (CH CH ), 27.10 (CH CH ).

2

2 2 2 2 2 2

+

1

3

1

+

CH CH ). C{ H}-NMR (C H , 50.32 MHz): 145.72

LRMS (24°C): m/z 184 (18) [M] , 169 (7) [C H ] ,

13 13

2

6

+

11 9 10 10

+

(C), 144.69 (C), 144.16 (C), 138.55 (CHꢀCH ), 127.90

(CH aromat.), 126.35 (CH aromat.), 124.91 (CH aro-

141 (12) [C H ] , 130 (27) [C H ] , 128 (25)

2

+

[C H ] , 115 (18) [C H ] . Anal. Found: C, 90.97; H,

10 8 9 7

−

1

mat.), 123.98 (CH aromat.), 119.35 (CHꢀ), 114.88

8.73. C H (184.28 g mol ) (3). Calc.: C, 91.25; H,

14

16

(

CHꢀCH ), 37.79 (CH CH ), 32.42 (CH CH ), 27.44

8.75%.

2

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

363

5

.2.4. 3-Allyl-4,7-dimethyl-1H-indene (4)

Analogous to the preparation of 1, 4,7-dimethylin-

(C), 144.31 (C), 143.49 (C), 142.90 (C), 138.57

(CHꢀCH₂), 129.56 (CH aromat.), 128.24 (CHꢀ),

126.11 (CH aromat.), 114.87 (CHꢀCH ), 36.41 (CH ),

dene (6.5 g, 43.29 mmol) in THF (50 ml) and allyl

chloride (4.64 g, 60.61 mmol) gave after fractional

2

33.98 (CH CH ), 30.62 (CH CH ), 29.02 (CH CH ),

2

distillation 4 as a colourless liquid product (5.59 g,

20.04 (CH ), 18.26 (CH ). LRMS (24°C): m/z 212 (23)

3 3

1

+

7

0%). B.p.: 62–68°C/0.2 mbar. H-NMR (CDCl , 200

[M] , 197 (15) [C H ] , 183 (5) [C H ] , 171 (10)

15 17 14 15

3

+ +

13 15 12 14 11 11

+

MHz): 7.11–7.00 (m, 2H, CH aromat.), 6.97 (dd, J=

[C H ] , 158 (100) [C H ] , 143 (77) [C H ] ,

+

1

5

.9 Hz, 1H, ꢀCH), 6.62 (dd, J=1.9 Hz, 1H, CHꢀ),

141 (40) [C H ] , 129 (39) [C H ] , 128 (56)

11 9 10 9

+

.79 (m, 1H, CHꢀCH ), 5.10 (m, 2H, CHꢀCH ), 3.65

[C H ] , 115 (38) [C H ] . Anal. Found: C, 90.03;

2

10

8

9

7

−

1

(

m, 1H, CH), 3.02 (m, 1H, CH ), 2.47 (s, 3H, CH ),

H, 9.42. C H (212.33 g mol ) (6) Calc.: C, 90.51;

2

3

16 20

1

3

1

2

.45 (s, 3H, CH ), 2.25 (m, 1H, CH ). C{ H}-NMR

H, 9.49%.

3

2

(

1

CDCl , 50.32 MHz): 144.54 (C), 143.12 (C), 138.37

CHꢀCH₂), 135.88 (CHꢀ), 129.17 (CH aromat.),

27.95 (CHꢀ), 126.72 (CH aromat.), 116.00

3

5.2.7. (1-Allylindenyl)lithium (1a)

A solution of 3-allylindene (4.33 g, 27.72 mmol) in

hexane (100 ml) was cooled to 0°C and n-butyllithium

(1.6 M in hexane, 24 ml, 38.81 mmol) was added

slowly. The suspension was stirred 12 h at 20°C,

ﬁltered and the solid was washed with hexane (150

ml). The white solid was dried under reduced pressure

to yield 1a as a white solid (3.74 g, 83%). M.p.: 157°C.

(

1

CH ꢀCH), 49.77 (CH), 33.72 (CH ), 18.80 (CCH ),

2

3

+

8.22 (CCH ). LRMS (21°C): m/z 184 (41) [M] , 169

3

+

13 13 12 13

+

(

22) [C H ] , 157 (18) [C H ] , 143 (100)

+ +

11 11 10 8 9 7

+

[C H ] , 128 (73) [C H ] , 115 (51) [C H ] . Anal.

−

1

Found: C, 90.52; H, 8.71. C H (184.28 g mol

(

)

1

4

16

4). Calc.: C, 91.25; H, 8.75%.

1

H-NMR (C D N, 400 MHz): 8.03 (m, 2H, CH aro-

5

.2.5. 3-(3-Buten-1-yl)-4,7-dimethyl-1H-indene (5)

The procedure described above for the synthesis of

was followed with (4,7-dimethylindenyl)lithium (5.56

mat.), 7.34 (t, J=2.6 Hz, 1H, CH), 7.08 (m, 2H, CH

aromat.), 6.82 (t, J=2.6 Hz, 1H, CH), 6.55 (m, 1H,

CHꢀCH ), 5.40 (d, J=17.0 Hz, 1H, ꢀCH trans), 5.03

2

g, 37.03 mmol) and 4-bromo-1-butene (5.00 g, 37.03

mmol) in THF (50 ml) to yield 5 as a yellow liquid

(d, J=9.8 Hz, 1H, CHꢀCH cis), 4.24 (d, J=6.6 Hz,

13 1

2

2H, CH₂).

C{ H}-NMR (C D N, 100.64 MHz):

5 5

1

(

6.45 g, 88%). B.p.: 76–78°C/0.1 mbar. H-NMR

143.00 (CHꢀ), 131.40 (C), 128.85 (C), 118.97 (CH aro-

mat.), 118.73 (CH aromat.), 116.86 (CH), 111.75 (CH

(

C D , 200 MHz): 6.97 (d, J=7.6 Hz, 1H, CH aro-

6

mat.), 6.89 (d, J=7.5 Hz, 1H, CH aromat.), 6.01 (t,

aromat.), 111.10 (CH aromat.), 110.81 (ꢀCH ), 104.03

2

J=1.8 Hz, 1H, ꢀCH), 5.86 (m, 1H, CHꢀCH ), 5.03

(C), 91.74 (CH), 34.90 (CH ). LRMS (26°C): m/z 162

2

+

12 12 11 9

+

(

2

m, 2H, CHꢀCH ), 2.91 (dd, J=2.2 Hz, 2H, CH ),

(0.11) [M] , 156 (45) [C H ] , 141 (24) [C H ] ,

2

+

.70 (m, 2H, CH CH ), 2.39 (s, 3H, CH ), 2.35 (m,

128 (100) [C H ] , 115 (62) [C H ] . Anal. Found:

10 8 9 7

2

3

1

3

1

−1

H, CH CH ), 2.13 (s, 3H, CH ). C{ H}-NMR

C, 88.61; H, 6.81. C H Li (162.16 g mol ) (1a)

2

3

12 11

(

C D , 50.32 MHz): 146.27 (C), 144.24 (C), 142.81

Calc.: C, 88.88; H, 6.84%.

6

(

C), 138.62 (CHꢀCH ), 129.69 (CH aromat.), 128.30

2

(

CHꢀ), 126.14 (CH aromat.), 114.87 (CHꢀCH ), 36.42

5.2.8. [1-(3-Buten-1-yl)indenyl]lithium (2a)

2

CH ), 33.47 (CH CH ), 30.55 (CH CH ), 20.00 (CH ),

The deprotonation described for the preparation of

1a using 2 (5.44 g, 31.95 mmol) and n-BuLi (20 ml,

31.95 mmol) in hexane (80 ml) gave 2a as a white

2

3

+

1

(

8.26 (CH ). LRMS (24°C): m/z 198 (34) [M] , 183

10) [C H ] , 157 (100) [C H ] , 142 (47)

3

+

14 15 12 13

+

1

[C H ] , 141 (42) [C H ] , 129 (27) [C H ] , 128

solid (5.06 g, 90%). M.p.: 143°C. H-NMR (C D O,

1

10

11

9

10

9

4

8

+

(

26) [C H ] , 115 (23) [C H ] . Anal. Found: C,

200 MHz): 7.26 (m, 2H, CH aromat.), 6.44 (m, 2H,

1

0

8

9

7

−

1

8

9.94; H, 9.08. C H (198.31 g mol ) (5) Calc.: C,

CH aromat.), 6.34 (d, J=3.2 Hz, 1H, ꢀCH), 6.00 (m,

1

5

18

9

0.85; H, 9.15%.

1H, CHꢀCH ), 5.68 (d, J=3.2 Hz, 1H, CHꢀ), 5.01

2

(

m, 2H, CHꢀCH ), 2.91 (t, J=8.2 Hz, 2H, CH CH ),

2

13 1

5

.2.6. 3-(4-Penten-1-yl)-4,7-dimethyl-1H-indene (6)

The procedure described above for the synthesis of

was followed with 4,7-dimethylindene (5.04 g, 33.55

2.44 (q, J=8.2 Hz, 2H, CH CH ). C{ H}-NMR

2 2

(C D O, 50.32 MHz): 141.68 (CHꢀCH ), 129.39 (C),

4

8

2

127.21 (C), 119.45 (CH aromat.), 117.36 (CH aro-

mat.), 115.45 (CH aromat.), 113.74 (CH aromat.),

mmol) and 5-bromo-1-pentene (5 g, 33.55 mmol) in

THF (50 ml) to obtain after distillation 6 as a yellow

liquid (5.82 g, 82%). B.p.: 82–83°C/0.1 mbar. H-

112.95/112.76 (CHꢀCH ), 106.49 (C), 87.72 (CHꢀ),

2

1

37.92 (CH CH ), 29.17 (CH CH ). LRMS (24°C): m/z

2

+

NMR (C D , 200 MHz): 6.95 (m, 2H, CH aromat.),

176 (0) [M] , 170 (39) [C H ] , 158 (17) [C H ] ,

142 (27) [C H ] , 141 (75) [C H ] , 129 (100)

11 10 11 9

[C H ] , 128 (68) [C H ] , 116 (20) [C H ] , 115

6

13 14 12 14

+

6

4

2

.02 (t, J=1.7 Hz, 1H, ꢀCH), 5.65 (m, 1H, CHꢀCH₂),

+

.98 (m, 2H, CHꢀCH ), 2.93 (d, J=2.2 Hz, 1H, CH ),

2

10

9

10

8

9

8

+

.45 (m, 2H, CH CH ), 2.26 (s, 3H, CH ), 2.24 (s, 3H,

(26) [C H ] . Anal. Found: C, 87.99; H, 7.39.

2

3

9 7

−

1

CH ), 2.04 (m, 2H, CH CH ) 1.65 (m, 2H, CH CH ).

C H Li (176.19 g mol ) (2a) Calc.: C, 88.62; H,

3

2

13 13

1

3

1

C{ H}-NMR (C D , 50.32 MHz): 146.76 (C), 145.50

7.44%.

6

364

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

13

1

5.2.9. [1-(4-Penten-1-yl)indenyl]lithium (3a)

CH₃). C{ H}-NMR (C D N, 100.64 MHz): 141.29

5 5

The deprotonation described for the preparation of

a using 3 (2.61 g, 19.9 mmol) and n-BuLi (17.4 ml,

3.88 mmol, 1.6 M) in hexane (100 ml) was carried out

at 20°C for 12 h. After ﬁltration, the solid was washed

with hexane (100 ml) and dried in vacuo at 0.1 mbar to

yield 3a as a white solid (3.56 g, 94%). M.p.: 120°C.

(CHꢀCH ), 131.31 (C), 126.17 (C), 124.94 (CCH ),

2

3

1

2

124.15 (CCH ), 117.79 (CH), 113.88 (CH aromat.),

3

112.82 (ꢀCH ), 112.34 (CH aromat.), 109.24 (C), 90.30

2

(CH), 40.68 (CH CH ), 31.78 (CH CH ), 22.43 (CH ),

2

3

+

20.23 (CH ). LRMS (38°C): m/z 204 (0) [M] , 198 (33)

3

+

[C H ] , 183 (9) [C H ] , 157 (100) [C H ] , 144

1

5

18

14 15

12 13

1

+

11 12 11 11 11 10

+

H-NMR (C D N, 200 MHz): 8.02 (m, 2H, CH aro-

(32) [C H ] , 143 (14) [C H ] , 142 (47) [C H ] ,

5

+

mat.), 7.32 (d, J=3.2 Hz, 1H, ꢀCH), 7.06 (m, 2H, CH

aromat.), 6.79 (d, J=3.2 Hz, 1H, CHꢀ), 5.99 (m, 1H,

CHꢀCH ), 5.01 (m, 2H, CHꢀCH ), 3.44 (t, J=7.3 Hz,

141 (29) [C H ] , 129 (10) [C H ] , 128 (12)

11 9 10 9

[C H ] , 115 (11) [C H ] . Anal. Found: C, 87.51; H,

8.31. C H Li (204.24 g mol ) (5a) Calc.: C, 88.21; H,

+

10

8

9

7

−

1

2

15 17

2

(

H, CH CH ), 2.39 (q, J=7.2 Hz, 2H, CH CH ), 2.16

8.39%.

2

1

2 2 5 5

3

1

q, J=7.3 Hz, 2H, CH CH ). C{ H}-NMR (C D N,

5

1

0.32 MHz): 140.48 (CHꢀCH ), 131.05 (C), 128.74 (C),

5.2.12. [1-(4-Penten-1-yl)-4,7-dimethylindenyl]lithium

(6a)

2

16.35 (C), 118.92 (CH aromat.), 118.28 (CH aromat.),

16.84 (CH aromat.), 113.50 (ꢀCH ), 110.82 (CH aro-

The deprotonation described for the preparation of

1a using 6 (5.82 g, 27.41 mmol) and n-BuLi (17.1 ml,

27.41 mmol) in hexane (100 ml) gave 12 as a white solid

2

mat.), 110.21 (CH), 91.09 (CH), 34.55 (CH CH ), 32.85

2

(

CH CH ), 29.18 (CH CH ). LRMS (27°C): m/z 190

0) [M] , 184 (26) [C H ] , 169 (8) [C H ] , 141

15) [C H ] , 130 (100) [C H ] , 115 (22) [C H ] .

2 2 2 2

+

1

(5.85 g, 98%). M.p.: 183°C. H-NMR (C D O, 200

1

4

16

13 11

4

8

+

MHz): 6.15 (m, 2H, CH aromat.), 6.11 (d, J=3.3 Hz,

1

9

10 10

9

7

Anal. Found: C, 88.13; H, 7.93. C H Li (190.21 g

mol ) (3a) Calc.: C, 88.40; H, 7.95%.

1H, ꢀCH), 5.95 (m, 1H, CHꢀCH ), 5.57 (d, J=3.3 Hz,

1

4

15

2

−

1

1H, CHꢀ), 4.99 (m, 2H, CHꢀCH ), 2.94 (t, J=7.5 Hz,

2

H, CH CH ), 2.60 (s, 3H, CH ), 2.34 (s, 3H, CH ),

2 2 3 3

5

.2.10. [1-Allyl-4,7-dimethylindenyl]lithium (4a)

The deprotonation described above for the synthesis

2.16 (q, J=7.3 Hz, 2H, CH CH ), 1.68 (q, J=7.3 Hz,

2H, CH CH ). C{ H}-NMR (C D O, 50.32 MHz):

2 2 4 8

2 2

13

1

of 1a was carried out with 4 (5.59 g, 30.33 mmol) and

140.70 (CHꢀCH ), 128.66 (C), 126.30 (CCH ), 125.37

2

3

n-BuLi (26 ml, 42.46 mmol) in hexane (100 ml) to give

(CCH ), 123.74 (C), 116.35 (C), 114.93 (CH aromat.),

3

1

4

a as a white solid (5.29 g, 92%). M.p.: 162°C. H-

114.74 (CH aromat.), 113.79 (ꢀCH ), 109.00 (CH),

2

NMR (C D N, 400 MHz): 7.30 (m, 1H, CH aromat.),

87.63 (CH), 34.96/34.68 (CH CH ), 30.75 (CH CH ),

5

2

6

1

.82 (m, 1H, CH aromat.), 6.80 (m, 1H, ꢀCH), 6.75 (m,

22.16 (CH₃aromat.), 19.86 (CH₃aromat.). LRMS

+

H, CHꢀ), 6.61 (m, 1H, CHꢀCH ), 5.30 (d, J=17.0

(24°C): m/z 218 (0) [M] , 197 (10) [C H ] , 183 (2)

2

16 20

+

Hz, 1H, CHꢀCH₂trans), 5.06 (d, J=8.8 Hz, 1H,

CHꢀCH cis), 4.37 (d, J=5.2 Hz, 2H, CH ), 3.06 (s,

[C H ] , 170 (7) [C H ] , 158 (100) [C H ] , 143

14 15 13 14 12 14

(41) [C H ] , 141 (18) [C H ] , 128 (15) [C H ] ,

115 (8) [C H ] . Anal. Found: C, 87.58; H, 8.71.

C H Li (218.27 g mol ) (6a) Calc.: C, 88.05; H,

+

2

11 11

11

9

10

8

1

3

1

+

3

1

H, CH ), 2.79 (s, 3H, CH ). C{ H}-NMR (C D N,

3

5

9 7

−

1

00.64 MHz): 144.94 (CHꢀ), 131.54 (C), 126.64 (C),

25.19 (C), 124.28 (C), 118.47 (CH), 114.11 (CH aro-

16

19

8.77%.

mat.), 112.64 (CH aromat.), 111.02 (ꢀCH ), 106.51 (C),

2

9

0.59 (CH), 36.76 (CH ), 22.51 (CCH ), 20.30 (CCH ).

5.3. Substituted 2-alkenyl indenyl compounds

2

3

+

LRMS (22°C): m/z 190 (0.11) [M] , 184 (55)

+

[

(

C H ] , 169 (27) [C H ] , 157 (8) [C H ] , 143

5.3.1. 2-Bromo-4,7-dimethylindan-1-ol

1

4

16

13 13

12 13

+

100) [C H ] , 128 (29) [C H ] , 115 (9) [C H ] .

To a stirred solution of DMSO (142 ml) and water

(6.46 g, 0.36 mol) was added 4,7-dimethylindene (26.94

g, 0.187 mol) at 22°C. Afterwards N-bromosuccinimide

1

11

10

8

9

7

Anal. Found: C, 88.05; H, 7.92. C H Li (190.21 g

1

4

15

−

1

mol ) (4a) Calc.: C, 88.40; H, 7.95%.

(

33.8 g, 0.19 mol) was added slowly. The suspension

5

(

.2.11. [1-(3-Buten-1-yl)-4,7-dimethylindenyl]lithium

5a)

The deprotonation described for the preparation of

a using 5 (6.45 g, 32.52 mmol) and n-BuLi (20.3 ml,

2.52 mmol) in hexane (80 ml) gave 5a as a white solid

was stirred 12 h and poured into water (250 ml). The

whole solution was extracted with ether (4×50 ml).

The combined organic layers were dried over MgSO₄

and concentrated under reduced pressure to give a

1

3

1

creme-colored solid (38.5 g, 85%). M.p.: 92°C. H-

1

(

6.52 g, 98%). M.p.: 205°C. H-NMR (C D N, 400

NMR (CDCl , 400 MHz): 7.02 (d, J=7.7 Hz, 1H, CH

5

3

MHz): 7.23 (d, J=3.3 Hz, 1H, CH aromat.), 6.73 (d,

J=3.4 Hz, 1H, CH aromat.), 6.71 (d, J=3.4 Hz, 1H,

aromat.), 6.97 (d, J=7.6 Hz, 1H, CH aromat.), 5.41

(m, 1H, CHOH), 4.42 (q, J=6.4 Hz, 1H, CHBr), 3.63

ꢀ

CH), 6.69 (d, J=3.4 Hz, 1H, ꢀCH), 6.27 (m, 1H,

(dd, J=6.4 Hz, 1H, CH ), 3.14 (dd, J=3.5 Hz, 1H,

2

CHꢀCH ), 5.18 (m, 1H, ꢀCH₂trans), 5.01 (m, 1H,

CH ), 2.39 (s, 3H, CH ), 2.20 (s, 3H, CH ), 2.00 (d,

2

3

1

3

1

ꢀ

CH cis), 3.65 (t, J=7.8 Hz, 2H, CH CH ), 3.03 (s,

J=6.8 Hz, 1H, OH). C{ H}-NMR (CDCl , 100.64

2

3

H, CH ), 2.71 (q, J=8 Hz, 2H, CH CH ), 2.77 (s, 3H,

MHz): 139.28 (C), 139.09 (C), 132.77 (C), 131.50 (C),

3

2

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

365

130.32 (CH aromat.), 129.11 (CH aromat.), 83.33

5.3.4. 2-(3-Buten-1-yl)-1H-indene (8)

(

1

2

(

1

CHOH), 54.24 (CHBr), 39.90 (CH ), 18.44 (CH ),

To a solution of 3-butenylmagnesium bromide (5.31

g, 33.33 mmol) and 2-bromoindene (3.25 g, 16.67

mmol) in THF (80 ml) at 0°C was added dropwise

2

3

+

81

7.88 (CH ). LRMS (65°C): m/z 242 (71) [M( Br)] ,

3

7

9

+

79

+

40 (71) [M( Br)] , 161 (100) [C H O Br] , 144

1

13

+

23) [C H ] , 143 (65) [C H ] , 128 (19) [C H ] ,

NiCl (DPPE) (1.06 g, 2.0 mmol) in THF (20 ml). The

1

13

11 11

10

8

2

+

15 (20) [C H ] . Anal. Found: C, 54.75; H, 5.42.

reaction mixture was stirred 12 h at 20°C. The mixture

was poured into 1 N HCl (100 ml). The water phase

was extracted with ether and the combined organic

phases were washed with brine, dried over MgSO₄,

concentrated and puriﬁed by ﬂash chromatography. A

colourless liquid was obtained by fractional distillation.

9

7

−

1

C H OBr (241.13 g mol ) Calc.: C, 54.79; H, 5.43%.

1

13

5

.3.2. 2-Bromo-4,7-dimethyl-1H-indene

The crude 2-bromo-4,7-dimethylindan-1-ol (38.5 g,

.159 mol) was reﬂuxed with p-toluenesulfonic acid

monohydrate) (1.5 g, 7.9 mmol) in toluene (200 ml) for

2 h using a Dean–Stark water trap to remove water.

0

(

7

1

Yield 1.6 g (38%). B.p.: 65°C/0.2 mbar. H-NMR

(CDCl , 400 MHz): 7.24 (m, 4H, CH aromat.), 6.53 (s,

3

After cooling down, the reaction mixture was ﬁltered.

The ﬁltrate was concentrated and puriﬁed by ﬂash

chromatography with petroleum ether. The solvent was

removed and the residue further puriﬁed by fractional

1H, ꢀCH), 5.88 (m, 1H, CHꢀCH ), 5.05 (m, 2H,

2

CHꢀCH ), 3.32 (s, 2H, CH ), 2.56 (t, J=7.6 Hz, 2H,

2

CH CH ), 2.38 (dt, J=7.2, 7.2 Hz, 2H, CH CH ).

2

13

1

C{ H}-NMR (CDCl , 100.64 MHz): 145.17 (C),

3

distillation to yield a white solid (29.6 g, 83%). M.p.:

143.24 (C), 141.61 (C), 136.25 (CHꢀCH ), 131.05 (CH

2

1

8

9–90°C. H-NMR (CDCl , 400 MHz): 7.02 (t, J=1.6

aromat.), 128.48 (CH aromat.), 126.14 (CH aromat.),

3

Hz, 1H, ꢀCH), 6.96 (d, J=7.6 Hz, 1H, CH aromat.),

125.75 (CH aromat.), 113.70 (CHꢀCH ), 108.30 (CHꢀ),

2

6

.88 (d, J=7.6 Hz, 1H, CH aromat.), 3.47 (s, 2H,

34.76 (CH CH ), 31.21 (CH CH ), 28.52 (CH ). LRMS

2

1

3

1

+

CH ), 2.34 (s, 3H, CH ), 2.27 (s, 3H, CH ). C{ H}-

(30°C): m/z 170 (25) [M] , 129 (100) [C H ] , 127

(10) [C H ] , 115 (16) [C H ] . Anal. Found: C,

10 7 9 7

91.53; H, 8.27. C H (170.25 g mol ) (8). Calc.: C,

2

3

10 9

+

NMR (CDCl , 100.64 MHz): 142.51 (C), 141.15 (C),

3

−

1

(

1

31.65 (CHꢀ), 129.72 (C), 128.04 (CH aromat.), 126.97

C), 126.16 (CH aromat.), 124.00 (C), 44.73 (CH₂),

8.20 (CH ), 18.09 (CH ). LRMS (24°C): m/z 224 (18)

13

14

91.71; H, 8.29%.

3

+

3

8

1

79

+

[M( Br)] , 222 (18) [M( Br)] , 143 (100) [C H ] ,

5.3.5. 2-(4-Penten-1-yl)-1H-indene (9)

11

+

141 (14) [C H ] , 128 (34) [C H ] , 115 (15)

The procedure described above for the synthesis of 8

was followed using 4-pentenylmagnesium bromide (3.14

g, 18.11 mmol), 2-bromoindene (2.35 g, 12.07 mmol)

1

9

10

8

+

9 7 11 11

[C H ] . Anal. Found: C, 59.16; H, 4.96. C H Br

−

1

(

223.11 g mol ) Calc.: C, 59.22; H, 4.97%.

and NiCl (DPPE) (0.64 g, 1.21 mmol) in THF (100 ml).

2

5

.3.3. 2-Allyl-1H-indene (7)

Allylmagnesium chloride (41.02 ml, 82.04 mmol) was

9 resulted as a light yellow liquid (Yield 1.42 g, 64%).

1

B.p.: 90–92°C/0.2 mbar. H-NMR (CDCl , 400 MHz):

3

dissolved in THF (50 ml). In a separate ﬂask a suspen-

sion of 2-bromoindene (4.0 g, 9.0 mmol) and

6.85 (m, 4H, CH aromat.), 6.60 (s, 2H, CH), 5.90 (m,

1H, CHꢀCH ), 5.09 (m, 1H, ꢀCH trans), 5.03 (m, 1H,

2

PdCl (DPPF) (0.841 g, 1.03 mmol) in THF (50 ml) was

ꢀCH cis), 3.20 (s, 2H, CH ), 2.40 (t, J=7.2 Hz, 2H,

2

prepared and added slowly to the Grignard solution at

CH CH ), 2.19 (dt, J=7.2, 7.2 Hz, 2H, CH CH ), 1.80

2 2 2 2

1

13

0°C. The reaction mixture was stirred 72 h at 20°C. The

(tt, J=7.2, 7.2 Hz, 2H, CH CH ). C{ H}-NMR

2 2

mixture was poured into 1 N HCl (100 ml) and was

extracted with ether. The combined organic phases

(CDCl , 100.64 MHz): 148.43 (C), 142.84 (C), 140.48

3

(C), 138.55 (CHꢀCH ), 128.83 (C), 127.60 (ꢀCH),

2

were washed with brine and dried over MgSO . The

126.59 (C), 124.93 (CH aromat.), 122.72 (CH aromat.),

4

concentrated mixture was puriﬁed by ﬂash chromatog-

raphy followed by fractional distillation to give the

114.62 (ꢀCH ), 39.85 (CH ), 32.45 (CH CH ), 30.67

2

(CH CH ), 28.22 (CH CH ). LRMS (28°C, 12eV): m/z

2

+

product as a colourless liquid. Yield 0.8 g (25%). B.p.:

184 (100) [M] , 169 (14) [C H ] , 157 (63)

13 12

1

+

5

5–57°C/0.2 mbar. H-NMR (CDCl , 400 MHz): 7.22

[C H ] , 143 (34) [C H ] , 128 (25) [C H ] .

12 13 11 11 10 8

3

(

m, 4H, CH aromat.), 6.55 (s, 1H, ꢀCH), 5.85 (m, 1H,

Anal. Found: C, 91.03; H, 8.70. C H (184.28 g

mol ) (9). Calc.: C, 91.25; H, 8.75%.

14 16

−

1

CHꢀCH ), 5.03 (m, 2H, CHꢀCH ), 3.35 (s, 2H, CH ),

3

2

1

3

1

.23 (d, J=7.2 Hz, 2H, CH CH). C{ H}-NMR

2

(

1

3

CDCl , 100.64 MHz): 145.14 (C), 144.62 (C), 142.66

5.3.6. 2-Allyl-4,7-dimethyl-1H-indene (10)

3

C), 135.21 (CHꢀCH ), 131.70 (CH aromat.), 129.59

This compound was prepared in the same manner as

7 from 2-bromo-4,7-dimethylindene (2.0 g, 9.0 mmol),

allylmagnesium chloride (9.0 ml, 18.0 mmol) in THF

2

CHꢀ), 128.43 (CH aromat.), 126.58 (CH aromat.),

25.86 (CH aromat.), 115.90 (CHꢀCH ), 38.12 (CH ),

2

4.89 (CH CH). LRMS (12eV, 50°C): m/z 156 (100)

(50 ml) and in the separate ﬂask PdCl (DPPF) (0.367 g,

2

+

[

(

M] , 141 (16) [C H ] , 128 (32) [C H ] , 115 (62)

C H ] . Anal. Found: C, 91.46; H, 7.68. C H

156.23 g mol ) (7). Calc.: C, 92.26; H, 7.74%.

0.45 mmol) in THF (50 ml). After all puriﬁcation steps

1

9

10

8

+

10 was isolated as a colourless liquid. Yield 0.5 g (30%).

9

7

12 12

−

1

B.p.: 72–75°C/0.2 mbar. H-NMR (CDCl , 400 MHz):

3

366

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

7

.02 (d, J=7.2 Hz, 1H, CH aromat.), 6.90 (d, J=7.6

(CH CH ), 18.31/18.20 (CH aromat.). LRMS (26°C,

2 2 3

+

Hz, 1H, CH aromat.), 6.69 (t, J=1.6 Hz, 1H, ꢀCH),

6

12 eV): m/z 212 (100) [M] , 197 (12) [C H ] , 170

1

5

17

+

13 12 12 13

+

.40 (m, 1H, CHꢀCH ), 5.17 (m, 2H, CHꢀCH ), 3.31

(57) [C H ] , 157 (41) [C H ] . Anal. Found: C,

90.46; H, 9.47. C H (212.33 g mol ) (12). Calc.: C,

2

−

1

(

d, J=7.2 Hz, 2H, CH CH), 3.26 (s, 2H, CH ), 2.43 (s,

2

16 20

13

1

3

1

H, CH ), 2.34 (s, 3H, CH ). C{ H}-NMR (CDCl ,

90.51; H, 9.49%.

3

00.64 MHz): 147.34 (C), 143.76 (C), 141.66 (C), 136.41

(

1

(

1

CHꢀCH ), 129.87 (C), 127.60 (CHꢀ), 126.85 (C),

5.3.9. 2-Allylindenyllithium (7a)

2

25.58 (CH aromat.), 125.12 (CH aromat.), 116.00

n-BuLi (1.6 M in hexane, 4.8 ml, 7.68 mmol) was

added slowly to a solution of 7 (0.8 g, 5.12 mmol) of in

hexane (50 ml). A suspension formed during 12 h at

20°C. The mixture was ﬁltered and the solid was

washed with hexane (30 ml). The white solid was dried

CHꢀCH ), 40.12 (CH ), 35.92 (CH CH), 18.29 (CH ),

2

3

8.17 (CH ). LRMS (12 eV, 52°C): m/z 184 (100)

3

+

[

(

M] , 169 (20) [C H ] , 144 (14) [C H ] , 143 (75)

C H ] . Anal. Found: C, 90.52; H, 8.71. C H

184.28 g mol ) (10). Calc.: C, 91.25; H, 8.75%.

1

3

13

11 12

+

1

11

14 16

−

1

under reduced pressure. Yield 0.80 g (97%). H-NMR

(

C D N, 400 MHz): 7.85 (m, 4H, CH aromat.), 6.74 (s,

5 5

5

.3.7. 2-(3-Buten-1-yl)-4,7-dimethyl-1H-indene (11)

The procedure described above for the synthesis of 8

2H, ꢀCH), 6.35 (m, 1H, CHꢀCH ), 5.06 (m, 2H,

2

13 1

CHꢀCH ), 3.58 (m, 2H, CH CH).

C{ H}-NMR

2

was followed using 3-butenylmagnesium bromide (5.3

g, 33.33 mmol) in THF (80 ml) at 0°C with a suspen-

(C D N, 100.64 MHz): 147.24 (CHꢀCH ), 143.24 (C),

5

2

142.55 (C), 140.21 (C), 133.61 (CH aromat.), 128.43

sion of NiCl (DPPE) (1.17 g, 2.22 mmol) and 2-bromo-

(CHꢀ), 128.33 (CH aromat.), 126.58 (CH aromat.),

2

4,7-dimethylindene (4.96 g, 22.22 mmol) in THF (30

125.43 (CH aromat.), 113.83 (CHꢀCH ), 34.65

2

+

ml). After puriﬁcation via fractional distillation the

(CH CH). LRMS (50°C): m/z 162 (0) [M] , 156 (56)

2

+

12 12 11 9 10 8

+

product was isolated as a light yellow liquid. Yield 2.34

[C H ] , 141 (32) [C H ] , 128 (44) [C H ] , 115

(35) [C H ] . Anal. Found: C, 88.72; H, 6.82. C H Li

9 7 12 11

(162.16 g mol ) (7a). Calc.: C, 88.88; H, 6.84%.

1

+

g (53%). B.p.: 80–88°C/0.2 mbar. H-NMR (CDCl ,

3

−

1

400 MHz): 7.00 (d, J=7.6 Hz, 1H, CH aromat.), 6.88

(

5

2

d, J=7.6 Hz, 1H, CH aromat.), 6.65 (s, 1H, ꢀCH),

.93 (m, 1H, CHꢀCH ), 5.08 (m, 2H, CHꢀCH ), 3.25 (s,

5.3.10. 2-(3-Buten-1-yl)indenyllithium (8a)

2

H, CH ), 2.65 (t, J=7.6 Hz, 2H, CH CH ), 2.45 (dt,

To a solution of 2-(3-buten-1-yl)-1H-indene (8) (1.6

g, 9.4 mmol) in hexane (40 ml) was added n-BuLi (2.46

M in hexane, 4.2 ml, 10.34 mmol) dropwise at 0°C. The

resulting suspension was stirred 12 h at 20°C. The

mixture was ﬁltered and the solid was washed with

hexane (30 ml). The white solid was dried under re-

2

J=7.6, 7.2 Hz, 2H, CH CH ), 2.41 (s, 3H, CH ), 2.34

2

3

1

3

1

(

s, 3H, CH₃). C{ H}-NMR (CDCl , 100.64 MHz):

3

1

48.88 (C), 143.78 (C), 141.08 (C), 138.19 (CHꢀCH₂),

29.70 (C), 127.58 (CHꢀCH ), 126.10 (C), 124.96 (CH

2

aromat.), 124.92 (CH aromat.), 114.85 (CHꢀ), 40.19

1

(

CH CH ), 33.24 (CH CH ), 30.84 (CH ), 18.32 (CH ),

duced pressure. Yield 1.3 g (78%) of 8a. H-NMR

2

3

+

1

8.21 (CH ). LRMS (25°C, 12 eV): m/z 198 (25) [M] ,

(C D , 400 MHz): 7.97 (m, 2H, CH aromat.), 7.00 (m,

3

6

+

57 (100) [C H ] , 143 (25) [C H ] . Anal. Found:

2H, CH aromat.), 6.72 (s, 2H, CH), 6.30 (m, 1H,

1

2

13

11

9

−

1

C, 90.67; H, 9.13. C H (198.31 g mol ) (11). Calc.:

CHꢀCH ), 5.08 (m, 2H, CHꢀCH ), 3.39 (t, J=8.0 Hz,

1

5

18

2

C, 90.85; H, 9.15%.

2H, CH CH ), 2.91 (dt, J=7.2, 8.0 Hz, 2H, CH CH ).

2 2 2 2

13

1

C{ H}-NMR (C D , 100.64 MHz): 141.70 (CHꢀCH ),

6

2

5.3.8. 2-(4-Penten-1-yl)-4,7-dimethyl-1H-indene (12)

134.49 (C), 131.85 (C), 121.24 (C), 128.30 (CH aro-

mat.), 113.35 (CHꢀCH₂), 93.95 (CHꢀ), 38.21

(CH CH ), 32.78 (CH CH ). LRMS (26°C): m/z 176

Analogous to the preparation of 9 but using 4-pen-

tenylmagnesium bromide (3.14 g, 18.11 mmol), 2-

bromo-4,7-dimethylindene (2.69 g, 12.07 mmol) and

2

+

(0) [M] , 170 (20) [C H ] , 129 (98) [C H ] , 128

(29) [C H ] , 115 (20) [C H ] . Anal. Found: C,

88.50; H, 7.41. C H Li (176.19 g mol ) (8a). Calc.:

13

14

10

9

+

10 8 9 7

+

NiCl (DPPE) (0.64 g, 1.21 mmol) in THF (100 ml) gave

2

−

1

6

2 as a light yellow liquid. Yield 1.54 g (60%). B.p.:

13

1

05–110°C/0.2 mbar. H-NMR (CDCl , 400 MHz):

C, 88.62; H, 7.44%.

3

.97 (d, J=7.2 Hz, 1H, CH aromat.), 6.85 (d, J=7.2

Hz, 1H, CH aromat.), 6.64 (s, 1H, CH), 5.87 (m, 1H,

5.3.11. 2-(4-Penten-1-yl)indenyllithium (9a)

CCꢀCH ), 5.06 (m, 1H, ꢀCH₂trans), 5.00 (m, 1H,

Analogous to the preparation of 8a but using 9 (1.42

g, 7.71 mmol) and n-BuLi (1.6 M in hexane, 5.3 ml,

8.53 mmol) in hexane (100 ml) gave 9a as a white solid

2

ꢀ

CH cis), 3.22 (s, 2H, CH ), 2.54 (t, J=7.2 Hz, 2H,

2

CH CH ), 2.39 (s, 3H, CH aromat.), 2.31 (s, 3H, CH

2

3

1

aromat.), 2.14 (dt, J=7.6, 7.2 Hz, 2H, CH CH ), 1.74

(1.39 g, 95%). H-NMR (C D N, 400 MHz): 6.92 (m,

2

5

1

3

1

(

1

4

tt, J=7.6, 7.2 Hz, 2H, CH CH ). C{ H}-NMR

4H, CH aromat.), 6.62 (s, 2H, CH), 5.97 (m, 1H,

2

CDCl , 100.64 MHz): 149.57 (C), 143.94 (C), 141.48

CHꢀCH ), 5.08 (m, 1H, ꢀCH₂trans), 4.98 (m, 1H,

3

2

C), 138.61 (CHꢀCH ), 129.85 (C), 127.62 (ꢀCH),

ꢀCH cis), 3.31 (t, J=7.4 Hz, 2H, CH CH ), 2.39 (m,

2

13

1

26.65 (C), 124.93/124.85 (CH aromat.), 114.75 (ꢀCH₂),

2H, CH CH ), 2.25 (m, 2H, CH CH ). C{ H}-NMR

2 2 2 2

0.10 (CH ), 33.45 (CH CH ), 30.76 (CH CH ), 28.31

(C D N, 100.64 MHz): 141.02 (CHꢀCH ), 131.10 (C),

2

5

2

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

367

1

3

1

30.66 (C), 114.41 (ꢀCH ), 112.30 (CH aromat.), 112.27

CH CH ), 2.23 (m, 2H, CH CH ). C{ H}-NMR

2 2 2 2

2

(

CH aromat.), 92.88 (CH), 34.41 (CH CH ), 32.65

(C D N, 100.64 MHz): 140.31 (CHꢀCH ), 132.70 (C),

2

5

2

(

CH CH ), 32.20 (CH CH ). LRMS (26°C, 12 eV): m/z

130.66 (C), 123.56 (C), 113.61 (ꢀCH ), 112.30 (CH

2

+

1

90 (0) [M] , 184 (100) [C H ] , 169 (19) [C H ] ,

57 (87) [C H ] , 143 (21) [C H ] , 128 (15)

aromat.), 92.90 (CH), 34.46 (CH CH ), 32.72

1

4

16

13 12

2

+

(CH CH ), 32.32 (CH CH ), 20.46 (CH aromat.).

1

2

13

11 11

2 2 2 2 3

+

[C H ] . Anal. Found: C, 88.32; H, 7.93. C H Li

LRMS (26°C): m/z 218 (0) [M] , 212 (48) [C H ] ,

16 20

1

0

8

14 15

−

1

+

15 17 13 13

+

(

190.21 g mol ) (9a). Calc.: C, 88.40; H, 7.95%.

197 (13) [C H ] , 171 (12) [C H ] , 170 (57)

+

13 12 12 13 11 11

+

[

C H ] , 157 (100) [C H ] , 143 (22) [C H ] ,

+

11 9 10 8

+

5.3.12. 2-Allyl-4,7-dimethylindenyllithium (10a)

141 (26) [C H ] , 128 (12) [C H ] , 115 (10)

+

Following the representative procedure for the syn-

[C H ] . Anal. Found: C, 87.78; H, 8.74. C H Li

9 7 16 19

(218.28 g mol ) (12a). Calc.: C, 88.04; H, 8.77%.

−

1

thesis of 7a above, using 10 (0.50 g, 2.71 mmol) in

hexane (60 ml) and n-BuLi (1.6 M in hexane, 2.54 ml,

4

9

.07 mmol) 10a was isolated as a white solid (0.51 g,

5.4. Multiply substituted 1-alkenylindenyl compounds

1

8%). H-NMR (C D N, 400 MHz): 7.59 (s, 2H, CH

5

aromat.), 6.85 (s, 2H, ꢀCH), 6.43 (m, 1H, CHꢀCH₂),

5.4.1. 3-(3-Buten-1-yl)-1-methyl-1H-indene and

1-(3-buten-1-yl)-3-methyl-1H-indene (13)

5

6

1

.21 (m, 2H, CHꢀCH ), 3.57 (m, 2H, CH CH), 2.42 (s,

2

1

3

1

H, CH₃).

C{ H}-NMR (C D N, 100.64 MHz):

46.12 (CHꢀCH ), 141.76 (C), 136.39 (C), 127.25

To 1-methylindenyllithium (6.66 g, 48.9 mmol) [19] in

THF (50 ml) at 0°C was added 4-bromo-1-butene (6.60

g, 5.0 ml, 48.9 mmol) under stirring, which was contin-

ued for 12 h. The solvent was removed under reduced

pressure and the residue was quenched with water (10

ml) and extracted with diethyl ether (50 ml). The com-

5

2

(

CHꢀ), 126.12 (C), 125.63 (CH aromat.), 114.02

CHꢀCH ), 34.76 (CH CH), 18.10 (CH ). LRMS

2

+

3

+

45°C): m/z 190 (0) [M] , 184 (64) [C H ] , 169 (25)

14

16

+ +

13 13 11 12 11 11

+

[C H ] , 144 (28) [C H ] , 143 (48) [C H ] .

Anal. Found: C, 88.25; H, 7.92. C H Li (190.21 g

mol ) (10a). Calc.: C, 88.40; H, 7.95%.

bined organic phases were dried over MgSO , and the

1

4

15

4

−

1

solvent was evaporated yielding 13 as a yellow liquid.

1

Yield 8.53 g (95%). B.p.: 67–70°C/0.2 mbar. H-NMR

5

(

.3.13. 2-(3-Buten-1-yl)-4,7-dimethylindenyllithium

11a)

Following the procedure for the synthesis of 8a

above but using 2-(3-buten-1-yl)-4,7-dimethylindene

2.31 g, 11.65 mmol) in hexane (80 ml) and n-BuLi (1.6

(CDCl , 200 MHz): Isomer 1: 7.44–7.25 (m, 4H, CH

3

aromat.), 6.23 (m, 1H, CHꢀ), 5.95 (m, 1H, CHꢀCH₂),

5.02 (m, 2H, CHꢀCH ), 3.42 (m, 1H, CH), 2.62 (m, 1H,

2

CH CH ), 2.49 (m, 1H, CH CH ), 1.92 (m, 2H,

2

(

CH CH ), 1.32 (m, 3H, CH ),. Isomer 2: 7.44–7.25 (m,

2 2 3

M in hexane, 8.7 ml, 13.98 mmol) gave compound 11a

as a white solid (2.3 g, 97%). M.p.:\250°C. H-NMR

4H, CH aromat.), 6.22 (m, 1H, CHꢀ), 5.95 (m, 1H,

CHꢀCH ), 5.02 (m, 2H, CHꢀCH ), 3.42 (m, 1H, CH),

1

2

(

C D N, 200 MHz): 6.80 (s, 2H, CH aromat.), 6.66 (s,

2.62 (m, 1H, CH CH ), 2.49 (m, 1H, CH CH ), 2.16

5

2 2 2 2

1

13

2

H, CH), 6.33 (m, 1H, CHꢀCH ), 5.22 (m, 1H, ꢀCH₂

(m, 3H, CH ), 1.92 (m, 2H, CH CH ). C{ H}-NMR

3 2 2

2

trans), 5.03 (m, 1H, ꢀCH cis), 3.40 (t, J=6.5 Hz, 2H,

CH CH ), 2.93 (dt, J=6.5, 6.5, Hz, 2H, CH CH ), 2.84

(CDCl , 50.32 MHz): 148.29 (C), 145.59 (C), 138.91

2

3

(C), 138.70 (CHꢀCH ), 135.26 (CH), 126.15 (CH aro-

2

1

3

1

(

s, 6H, CH aromat.). C{ H}-NMR (C D N, 100.64

mat.), 124.70 (CH aromat.), 122.60 (CH aromat.),

118.87 (CH aromat.), 114.66 (CHꢀCH₂), 48.36

(CHCH ), 31.79 (CH ), 30.99 (CH ), 12.96 (CH ).

3

5

MHz): 141.37 (CHꢀCH ), 132.30 (C), 130.68 (C),

2

1

13.00 (ꢀCH ), 112.44 (CH aromat.), 93.05 (CH), 38.08

2

3

2

3

+

(

CH CH ), 32.65 (CH CH ), 22.48 (CH aromat.),

LRMS (24°C): m/z 184 (18) [M] , 169 (6) [C H ] ,

2

3

13 13

+

2

1

0.40 (CH aromat.). LRMS (24°C): m/z 204 (0) [M] ,

98 (20) [C H ] , 157 (53) [C H ] , 143 (82)

157 (9) [C H ] , 143 (97) [C H ] , 129 (55)

12 13 11 11

3

+

+ +

10 9 10 8 9 7

+

[C H ] , 128 (100) [C H ] , 115 (52) [C H ] , 42

1

5

18

12 13

+

[C H ] , 128 (100) [C H ] , 115 (11) [C H ] . Anal.

(74) [C H ] , 41 (44) [C H ] . Anal. Found: C, 91.25;

3 6 3 5

H, 8.60. C H (184.28 g mol ) (13). Calc.: C, 90.93;

1

11

10

8

9

7

−

1

−1

Found: C, 87.98; H, 8.36. C H Li (204.24 g mol

)

15

17

14 16

(

11a). Calc.: C, 88.21; H, 8.39%.

H, 8.51%.

5

.3.14. 2-(4-Penten-1-yl)-4,7-dimethylindenyllithium

5.4.2. 1-(3-Buten-1-yl)-3-methylindenyllithium (13a)

To a solution of 13 (3.0 g, 16.28 mmol) in hexane (40

ml) was added n-BuLi (1.6 M in hexane, 10.18 ml,

16.28 mmol) at 0°C. The reaction mixture was stirred

12 h at room temperature. The phases were separated

by decanting, the solid was washed with hexane (20 ml)

and then dried in vacuo to give 13a as a white solid.

(

12a)

Analogous to the preparation of 8a above but using

2 (1.51 g, 7.11 mmol) in hexane (100 ml) with n-BuLi

1

(

1.6 M in hexane, 5.3 ml, 8.53 mmol) gave 12a as a

1

white solid. Yield 1.54 g (99%). M.p.: 185°C. H-NMR

(

C D N, 400 MHz): 6.79 (s, 2H, CH aromat.), 6.64 (s,

5 5

1

2

H, CH), 6.01 (m, 1H, CHCH ), 5.11 (m, 1H, ꢀCH₂

Yield 1.23 g (40%). M.p.: 132°C. H-NMR (C D N,

2

5

trans), 4.95 (m, 1H, ꢀCH cis), 3.30 (t, J=7.4 Hz, 2H,

CH CH ), 2.83 (s, 6H, CH aromat.), 2.40 (m, 2H,

200 MHz): 7.98–7.90 (m, 2H, CH aromat.), 7.04–7.00

(m, 2H, CH aromat.), 7.13 (s, 1H, CH), 6.32 (m, 1H,

2

3

368

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

CHꢀ), 5.23–4.96 (m, 2H, ꢀCH cis, trans), 3.53 (t, J=6

129.57 (C), 126.84 (CCH ), 125.08 (CCH ), 122.79 (C),

3 3

2

Hz, 2H, CH CH ), 3.02 (s, 3H, CH ), 2.87 (m, 2H,

113.86 (CH aromat.), 112.73 (ꢀCH ), 111.78 (CH aro-

2

3

2

1

3

1

CH CH ). C{ H}-NMR (C D N, 50.32 MHz): 141.80

mat.), 106.72 (C), 92.61 (CH), 40.90 (CH CH ), 28.81

2

5

2

(

1

(

2

CHꢀ), 128.58 (C), 127.89 (C), 119.17 (CCH ), 116.66/

(CH CH ), 22.33 (CH ), 20.25 (CH aromat.), 15.31

(CH aromat.). LRMS (30°C): m/z 218 (0.11) [M] ,

3

2 2 3 3

+

16.53 (CH aromat.), 112.69 (ꢀCH ), 110.27/110.19

2

+

16 20 13 15

+

CH aromat.), 104.10 (C), 98.24 (CH), 38.56 (CH CH ),

212 (53) [C H ] ,171 (100) [C H ] , 156 (55)

2

+

9.58 (CH CH ), 14.24 (CH ). LRMS (23°C): m/z 190

[C H ] , 142 (24) [C H ] , 128 (15) [C H ] , 115

12 12 11 10 10 8

2

3

+

9 7 16 19

−1

(

0) [M] , 184 (25) [C H ] , 170 (6) [C H ] , 157

(13) [C H ] . Anal. Found: C, 87.17; H, 8.73. C H Li

1

4

16

13 14

+

(

7) [C H ] , 143 (100) [C H ] , 128 (64) [C H ] ,

(218.27 g mol ) (14a). Calc.: C, 88.05; H, 8.77%.

5.5. Bis-(1-alkenylindenyl)-zirconium complexes

1

2

13

11 11

10

8

+

1

15 (15) [C H ] . Anal. Found: C, 88.05; H, 7.91.

9 7

−

1

C H Li (190.21 g mol ) (13a). Calc.: C, 88.40; H,

1

4

15

7.95%.

5.5.1. Bis[1-allyl-indenyl]zirconium dichloride (1b)

5.4.3. 1-(3-Buten-1-yl)-2,4,7-trimethyl-1H-indene (14)

[(1-Allyl)indenyl]lithium (0.97 g, 6.00 mmol) was dis-

2

,4,7-Trimethylindene (2.86 g, 18.07 mmol) was dis-

solved in THF (50 ml) and n-BuLi (1.6 M in hexane,

1.3 ml, 18.07 mmol) was added dropwise at 0°C. After

solved in diethyl ether (60 ml). Zirconium tetrachloride

(0.69 g, 3 mmol) was added slowly to the solution and

the suspension was stirred 50 h in a darken ﬂask at

room temperature. The reaction mixture was ﬁltered

and the solvent removed under reduced pressure. The

solid residue was washed once with hexane (50 ml) and

1

stirring 12 h at 20°C, the solution was cooled to 0°C

and mixed with 4-bromo-1-butene (2.32 g, 17.18 mmol).

After 12 h at room temperature, the solvent was re-

moved under vacuo and the residue quenched with

water (20 ml) and diethyl ether (20 ml). The product

was extracted with ether (80 ml) and dried over MgSO₄.

4 was obtained after fractional distillation as a color-

less liquid. Yield 3.10 g (85%). B.p.: 98°C/0.1 mbar.

H-NMR (C D , 400 MHz): 6.96 (d, J=7.6 Hz, 1H,

CH aromat.), 6.83 (d, J=7.7 Hz, 1H, CH aromat.),

dried in vacuo to yield 1b as a yellow solid (0.74 g,

1

52%). M.p.: 82–85°C. H-NMR (CDCl , 400 MHz):

3

7.67 (m, 8H, CH aromat.), 7.35 (m, 8H, CH aromat.),

6.48 (d, J=3.2 Hz, 2H, CH), 6.18 (d, J=2.4 Hz, 2H,

CH), 6.02 (d, J=2.4 Hz, 2H, CH), 5.77 (d, J=3.2 Hz,

2H, CH), 6.22 (m, 2H, CHꢀCH ), 5.12 (m, 8H, ꢀCH ),

1

6

2

13

1

3.65 (m, 8H, CH₂). C{ H}-NMR (CDCl , 100.64

3

6

.46 (m, 1H, CH), 5.8–5.5 (m, 1H, CHꢀ), 4.90–4.80

MHz): 135.75/135.52 (CHꢀ), 127.42 (C), 126.34 (CH

aromat.), 126.15 (C), 125.55 (CH), 123.70 (CH aro-

mat.), 122.14 (CH aromat.), 120.63 (C), 120.49 (CH

(

2

m, 2H, ꢀCH ), 3.14 (t, 1H, CH), 2.26 (s, 3H, CH ),

2

3

.21 (s, 3H, CH ), 2.14 (m, 2H, CH ), 1.83 (s, 3H,

3 2

1

3

CH ), 1.52 (m, 2H, CH ). C{ H}-NMR (C D , 100.64

MHz): 147.25 (C), 144.33/144.19 (C), 139.13 (ꢀCH₂),

1

aromat.), 116.67/116.26 (ꢀCH ), 99.00 (CH), 32.40/

3

2

6

2

+

32.20 (CH ). LRMS (166°C): m/z 470 (18) [M] , 435

2

+

24 22 12 11 2

+

28.24 (C), 126.53 (C), 126.32/126.25 (CH aromat.),

14.21 (CHꢀ), 51.81 (CH ), 27.44 (CH CH ), 26.78

(16) [C H ZrCl] , 315 (100) [C H ZrCl ] , 280 (10)

+

1

[C H ZrCl] , 253 (20) [C H ZrCl] , 153 (11)

2

12 11

10

8

+ +

2 4 10 8 9 7

+

(

CH CH), 18.72 (CH ), 18.27 (CH aromat.), 14.98

[C H ZrCl] , 128 (14) [C H ] , 115 (14) [C H ] .

2

3

+

(

CH aromat.). LRMS (24°C): m/z 212 (31) [M] , 171

Anal. Found: C, 60.76; H, 4.67. C H ZrCl (472.57 g

24 22 2

3

+

−1

(

81) [C H ] , 156 (67) [C H ] , 141 (48) [C H ] ,

mol ) (1b). Calc.: C, 61.00; H, 4.69%.

1

3

15

12 12

11

9

+

10 8 9 7

+

1

8

9

28 (28) [C H ] , 115 (32) [C H ] . Anal. Found: C,

9.90; H, 9.63. C H (212.33 g mol ) (14). Calc.: C,

−

1

5.5.2. Bis[1-(3-buten-1-yl)indenyl]zirconium dichloride

(2b)

1

6

20

0.51; H, 9.49%.

To a stirred solution of [1-(3-buten-1-yl)indenyl]-

5.4.4. 1-(3-Buten-1-yl)-2,4,7-trimethylindenyllithium

lithium (0.70 g, 4.0 mmol) and Et O (50 ml) was added

2

(

14a)

To a solution of 14 (3.46 g, 16.30 mmol) in hexane

100 ml) at 0°C was added n-BuLi (1.6 M in hexane,

0.2 ml, 16.30 mmol). The reaction mixture was stirred

zirconium tetrachloride (0.47 g, 2.0 mmol). The reac-

tion mixture was stirred 30 h at room temperature. The

suspension was ﬁltered and the ﬁltrate evaporated to

dryness. The yellow solid was washed with pentane (20

ml) and hexane (20 ml) to obtain after drying in vacuo

2b as a yellow solid. Yield 0.38 g (38%). M.p.: 150°C.

(

1

at room temperature for 12 h. The phases were sepa-

rated by decanting, the solid was washed with hexane

(

solid (2.93 g, 82%). M.p.: 175–180°C. H-NMR

(

1

50 ml) and then dried in vacuo yielding 14a as a white

H-NMR (C D N, 200 MHz): 7.30 (m, 16H, CH aro-

5

1

mat.), 6.69 (d, J=3.2 Hz, 2H, CH), 6.32 (d, J=3.2 Hz,

2H, CH), 6.27 (d, J=3.2 Hz, 2H, CH), 6.00 (d, J=3.2

C D N, 400 MHz): 6.70 (s, 2H, CH aromat.), 6.53 (s,

5 5

1

5

H, CH), 6.27 (m, 1H, CHꢀ), 5.22 (m, 1H, ꢀCH trans),

Hz, 2H, CH), 5.84 (m, 4H, CHꢀCH ), 4.99 (m, 8H,

2

13

1

.03 (m, 1H, ꢀCH₂cis), 3.56 (t, J=7.8 Hz, 2H,

ꢀCH ), 3.15 (m, 8H, CH ), 2.43 (m, 8H, CH ). C{ H}-

2

CH CH ), 3.06 (s, 3H, CH ), 2.83 (s, 3H, CH aromat.),

NMR (C D N, 50.32 MHz): 137.81/137.75 (CHꢀ),

2

3

5

2

.79 (s, 3H, CH aromat.), 2.71 (m, 2H, CH CH ).

126.18 (C), 126.00 (CH aromat.), 125.36 (C), 124.64

(CH), 123.70 (CH aromat.), 123.24 (CH

3

2

1

3

1

C{ H}-NMR (C D N, 100.64 MHz): 141.24 (CHꢀ),

5

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

369

aromat.), 122.63 (C), 120.43 (CH aromat.), 115.20/

50.32 MHz): 137.82/137.74 (CHꢀCH ), 133.34 (C),

2

1

15.13 (ꢀCH ), 99.26/99.18 (CH), 34.05/33.90 (CH ),

133.12 (C), 132.65 (CCH ), 132.46 (CCH ), 126.99/

2

3

90

2

7.74/27.41 (CH ). LRMS (25°C): m/z 498 (3) [M( Zr,

126.86 (CH aromat.), 126.15/126.11 (CH aromat.),

126.04 (C), 118.83/118.36 (CH), 115.24/115.18 (ꢀCH₂),

97.48/96.37 (CH), 35.21/35.00 (CH CH ), 30.28/30.22

2

3

5

+

94

35

+

Cl)] , 335 (31) [C H

Zr Cl Cl] , 333 (69)

1

3

13

37

9

4

35

+

90

35

+

[C H

Zr Cl ] , 331 (99.9) [C H

Zr Cl Cl] ,

1

3

13

2

13 13

37

35

2

9

2

0

35

+

94

+

3

2

29 (100) [C H

95 (15) [C H

Zr Cl ] , 297 (9) [C H

Zr Cl] , 293 (23) [C H

Zr Cl] ,

(CH CH ), 20.52/18.55 (CH aromat.). LRMS (161°C):

1

3

13

9

2

+

13 12

2

3

35

90

35

+

90

35

37

+

Zr Cl] ,

m/z

556

(8)

[M( Zr, Cl, Cl)] ,

554

Zr Cl Cl] ,

(8)

1

3

12

0

13 12

90

9

35

+

35

+

90

35

+

90

35 37

+

90 (7) [C H Zr Cl Cl] , 288 (5) [C H Zr Cl ] ,

[M( Zr, Cl, Cl)] , 359 (99) [C H

1

0

8

37

35 37

10

8

2

90

15 17

9

0

+

90

15 17 2 15 16

35

+

77 (13) [C H Zr Cl Cl] , 275 (13) [C H Zr

357 (100) [C H

Zr Cl ] , 323 (10) [C H -

9

7

9

7

3

5

+

94

35

+

90

37

+

90

35

+

Cl ] , 205 (12) [C H Zr Cl ] , 203 (20) [C H

Zr Cl Cl] , 201 (22) [C H Zr Cl ] , 128 (17)

Zr Cl] , 321 (15) [C H

Zr Cl] , 318 (10)

2

3

5

2

90

3

5

15 16

9

0

35 37

+

35

+

90

35

37

3

35 37

+

90

35

+

[C H

Zr Cl Cl] , 316 (9) [C H

Zr Cl ] , 203

3

5

2

12 12

2

+

90

+

35

+

[C H ] , 115 (8) [C H ] . Anal. Found: C, 62.12; H,

(7) [C H₅Zr Cl Cl] , 201 (8) [C H Zr Cl ] , 128

(14) [C H ] , 115 (9) [C H ] . Anal. Found: C, 64.58;

H, 6.12. C H ZrCl (556.75 g mol ) (5b). Calc.: C,

1

0

8

9

7

3

5

2

−

1

+

10 8 9 7

+

5

.20. C H ZrCl (500.62 g mol ) (2b). Calc.: C, 62.38;

2

6

26

2

−

1

H, 5.23%.

3

0

34

2

6

4.72; H, 6.16%.

5.5.3. Bis[(1-allyl)-4,7-dimethylindenyl]zirconium

dichloride (4b)

5.5.5. Bis[1-(4-penten-1-yl)-4,7-dimethyl-

indenyl]zirconium dichloride (6b)

To a mixture of [1-(4-penten-1-yl)-4,7-dimethylin-

denyl]lithium (0.96 g, 4.4 mmol) and zirconium tetrachlo-

The procedure described for the preparation of 1b

using [(1-allyl)-4,7-dimethylindenyl]lithium (1.14 g, 6.0

mmol) and zirconium tetrachloride (0.69 g, 3 mmol) in

Et O (60 ml) gave 4b as a yellow solid (0.8 g, 50%). M.p.:

ride (0.47 g, 2.0 mmol) was added slowly Et O (60 ml).

2

1

15–118°C. H-NMR (CDCl , 400 MHz): 6.93 (m, 8H,

The suspension was stirred for 48 h. After ﬁltration and

evaporation of the solvent, the yellow solid was puriﬁed

by washing with hexane (20 ml) to yield 6b (0.70 g, 60%).

3

CH aromat.), 6.37 (d, J=3.2 Hz, 2H, CH), 6.14 (d,

J=2.5 Hz, 2H, CH), 6.12 (d, J=2.5 Hz, 2H, CH), 5.62

1

(

d, J=3.2 Hz, 2H, CH), 6.02 (m, 4H, CHꢀCH ), 5.10

M.p.: 148–151°C. H-NMR (C D N, 400 MHz): 6.71

2

5

(

m, 8H, ꢀCH ), 3.81 (m, 8H, CH ), 2.66 (s, 24H, CH ),

(m, 8H, CH aromat.), 6.60 (d, J=3.2 Hz, 2H, ꢀCH), 6.50

(d, J=3.2 Hz, 2H, ꢀCH), 6.40 (d, J=3.2 Hz, 2H, ꢀCH),

6.04 (d, J=3.2 Hz, 2H, ꢀCH), 5.90 (m, 4H, CHꢀCH₂),

5.05 (m, 8H, ꢀCH ), 3.32 (m, 8H, CH CH ), 3.04 (s, 12H,

2

3

1

3

1

2

.40 (s, 12H, CH₃). C{ H}-NMR (CDCl , 100.64

3

MHz): 136.94/136.84 (CHꢀ), 129.00 (C), 128.19 (C),

1

26.86 (CH aromat.), 126.14 (CH aromat.), 122.43 (C),

2

20.13/119.55 (CH), 116.44/116.29 (ꢀCH ), 97.33/96.94

CH aromat.), 2.70 (s, 12H, CH aromat.), 2.13 (m, 8H,

2

3

13

1

(

CH), 20.56 (CH ), 18.88/18.78 (CH ). LRMS (80°C):

CH CH ), 1.74 (m, 8H, CH CH ). C{ H}-NMR

2 2 2 2

2

3

+

m/z 526 (18) [M] , 490 (9) [C H ZrCl] , 455 (11)

(C D N, 100.64 MHz): 138.65/138.33 (CHꢀCH ), 133.35

2

8

30

5

2

+

[

(

C H Zr] , 343 (97) [C H ZrCl ] , 307 (28)

C H ZrCl] , 281 (20) [C H ZrCl] , 184 (21)

C H ] , 153 (14) [C H ZrCl] , 128 (16) [C H ] , 115

9) [C H ] . Anal. Found: C, 63.10; H, 5.68.

(C), 133.16 (C), 132.60 (CCH ), 132.49 (CCH ), 126.89/

2

8

29

14 15

2

3 3

+

126.78 (CH aromat.), 125.93/125.74 (CH aromat.),

119.01 (C), 118.40/118.07 (CH), 113.80/112.22 (ꢀCH₂),

97.62/96.56 (CH), 35.32/35.16 (CH CH ), 33.56/33.24

1

4

14

12 12

+

1

4

16

2

4

10

8

+

9

7

2

−

1

C H ZrCl (528.68 g mol ) (4b). Calc.: C, 63.61; H,

(CH CH ), 30.49/30.30 (CH CH ), 20.43/19.12 (CH

2

8

30

2

3

5

.72%.

aromat.).

LRMS

(183°C):

m/z

584

(10)

90

35

37

+

90

35

+

[M( Zr, Cl, Cl)] , 582 (10) [M( Zr, Cl, Cl] , 373

9

0

35 37

+

90 35

16 19 2

+

5

.5.4. Bis[1-(3-buten-1-yl)-4,7-dimethylindenyl]-

(80) [C H

Zr Cl Cl] , 371 (75) [C H

Zr Cl ] ,

16

19

90

37

+

90

35

+

zirconium dichloride (5b)

1-(3-buten-1-yl)-4,7-dimethylindenyl)lithium (0.82 g,

.0 mmol) was dissolved in Et O (60 ml) and zirconium

337 (6) [C H

Zr Cl] , 335 (9) [C H

Zr Cl] ,

1

6

18

16 18

90

35 37

+

[

319

(11)

[C H Zr Cl Cl] ,

317

(9)

Zr Cl ] , 283 (9) [C H Zr Cl] , 281 (14)

12 12

12

13

9

0

35

+

90

37

+

4

[C H

2

12 13

2

90

35

+

tetrachloride (0.47 g, 2.0 mmol) was added slowly. The

suspension was stirred 72 h in a dark ﬂask at room

temperature. The mixture was ﬁltered and the solvent

removed under reduced pressure. The yellow–brown

residue was washed with hexane (20 ml). By decantation

and subsequent vacuum drying 5b was isolated as a

[C H

Zr Cl] , 128 (19) [C H ] , 115 (11) [C H ] .

12

10

8

9

7

Anal. Found: C, 65.62; H, 6.42. C H ZrCl (584.79 g

3

2

38

2

−

1

mol ) (6b). Calc.: C, 65.73; H, 6.55%.

5.5.6. Bis[2-(3-buten-1-yl)-4,7-dimethylindenyl]-

zirconium dichloride (11b)

[2-(3-Buten-1-yl)-4,7-dimethylindenyl]lithium (0.50 g,

1

yellow solid (0.54 g, 49%). M.p.: 200–205°C. H-NMR

(

CDCl , 400 MHz): 6.89 (m, 8H, CH aromat.), 6.25 (d,

2.45 mmol) was dissolved in Et O (60 ml). Zirconium

3

2

J=3.2 Hz, 2H, ꢀCH), 6.04 (d, J=3.2 Hz, 2H, ꢀCH),

tetrachloride (0.28 g, 1.22 mmol) was added slowly to the

stirring solution. The reaction mixture was stirred for 48

h at 25°C in a darkened ﬂask. The suspension was ﬁltered

and the yellow solid washed with hexane (20 ml). Yellow

crystals of 11b were obtained from hexane (20 ml) at

5

3

2

.98 (d, J=3.2 Hz, 2H, ꢀCH), 5.85 (m, 4H, CHꢀCH₂),

.56 (d, J=3.2 Hz, 2H, ꢀCH), 5.05 (m, 8H, ꢀCH₂),

.3–2.9 (m, 8H, CH CH ), 2.65 (s, 24H, CH aromat.),

2

3

13

1

.40–2.27 (m, 8H, CH CH ). C{ H}-NMR (C D N,

2

5

370

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

1

13

1

−

(

4

2

28°C. Yield 0.37 g (54%). M.p.: 58–61°C. H-NMR

C{ H}-NMR (CDCl , 50.32 MHz): 145.12 (CHꢀ),

3

C D N, 400 MHz): 6.97 (s, 4H, CH aromat.), 6.67 (s,

H, ꢀCH), 5.83 (m, 2H, CHꢀCH ), 5.03 (m, 4H, ꢀCH ),

.70 (m, 4H, CH CH ), 2.50 (s, 12H, CH aromat.), 2.31

138.83 (C), 128.90 (C), 126.25 (CH aromat.), 124.85 (CH

aromat.), 123.85 (CH), 121.15/120.94 (CH aromat.),

118.90 (CCH ), 113.80 (ꢀCH ), 109.10 (C), 37.50

(CH CH ), 29.13 (CH CH ), 12.75 (CH ). LRMS

(190°C): m/z 528 (3) [M( Zr, Cl, Cl)] , 526 (3)

5

2

3

2

1

3

1

(

m, 4H, CH CH ). C{ H}-NMR (C D N, 100.64

2

5

2 2 2 2 3

37

90

35

+

MHz): 139.24 (CHꢀCH ), 138.54 (C), 131.17 (C), 128.68

2

90

35

+

94

35 37

+

(

3

C), 125.79 (CH aromat.), 115.00 (ꢀCH ), 104.12 (CH),

[M( Zr, Cl, Cl)] , 345 (97) [C H

Zr Cl Cl] ,

2

14 15

94

35

14 15 2 13 13

+

3.08 (CH CH ), 30.85 (CH CH ), 18.78 (CH aromat.).

343 (100) [C H

Zr Cl ] , 331 (10) [C H -

2

3

37

90

35

+

90

35 37

+

90

13 2

35

+

LRMS (58°C): m/z 556 (100) [M( Zr, Cl, Cl)] , 554

Zr Cl Cl] , 329 (11) [C H

Zr Cl ] , 305 (12)

13

9

0

35

+

90

37

+

94

35

+

92

35

+

(

5

91) [M( Zr, Cl, Cl)] , 521 (16) [C H

19 (16) [C H

Zr Cl] ,

[C H

Zr Cl] , 303 (12) [C H

Zr Cl] , 203 (14)

3

0

34

11 11

90

11 11

9

0

35

+

90

35 37

+

90

35

3 3 5 2

+

Zr Cl] , 359 (45) [C H

Zr Cl -

[C H₅Zr Cl Cl] , 201 (16) [C H Zr Cl ] , 128

(30) [C H ] , 115 (17) [C H ] . Anal. Found: C, 60.32;

10 8 9 7

H, 5.81. C H ZrCl (528.68 g mol ) (13b). Calc.: C,

63.61; H, 5.72%.

3

0

34

15 17

+

90

35

+

Cl] , 357 (43) [C H

H₁₆Zr Cl] , 321 (16) [C H

H₁₃Zr Cl Cl] , 317 (9) [C H

Zr Cl ] , 323 (10) [C

1

5

17

2

15

9

0

37

+

90

35

+

−1

Zr Cl] , 319 (14) [C

15

16

12

28 30

2

9

0

35 37

+

90

35

+

Zr Cl ] . Anal.

12

13

2

−

1

Found: C, 64.60; H, 6.13. C H ZrCl (556.75 g mol

)

30

34

2

(

11b). Calc.: C, 64.72; H, 6.16%.

5.5.9. Bis[1-(3-buten-1-yl)-2,4,7-trimethylindenyl]-

zirconium dichloride (14b)

Analogous to the preparation of 11b, ZrCl (0.47 g, 2.0

5.5.7. Bis[2-(4-penten-1-yl)-4,7-dimethylindenyl]-

4

zirconium dichloride (12b)

mmol) was added slowly to a solution of [1-(3-buten-1-

yl)-2,4,7-trimethylindenyl]lithium (0.87 g, 4.0 mmol) in

Analogously to the preparation of 11b, [2-(4-penten-1-

yl)-4,7-dimethylindenyl]lithium (0.50 g, 2.29 mmol) in

Et O (60 ml) was treated with ZrCl (0.27 g, 1.15 mmol).

Et O (50 ml). 14b was isolated from hexane (30 ml) at

2

−28°C as a yellow solid (0.34 g, 29%). M.p.: 128–132°C.

2

4

1

12b was obtained from hexane (30 ml) at −28°C as

H-NMR (C D N, 400 MHz): 7.02 (d, J=7.6 Hz, 4H,

5

1

yellow crystals (0.42 g, 62%). M.p.: 88–90°C. H-NMR

CH aromat.), 6.90 (d, J=7.6 Hz, 4H, ꢀCH aromat.),

(

4

2

C D N, 400 MHz): 6.90 (m, 4H, CH aromat.), 6.68 (s,

H, ꢀCH), 5.84 (m, 2H, CHꢀCH ), 5.04 (m, 4H, ꢀCH ),

.63 (t, J=7.7 Hz, 4H, CH CH ), 2.52 (s, 12H, CH

6.34 (s, 4H, CH), 5.94 (m, 4H, CHꢀCH ), 5.06 (m, 8H,

5

2

ꢀCH ), 2.73 (m, 8H, CH CH ), 2.52 (s, 12H, CH ), 2.30

2

3

(m, 8H, CH CH ) 2.21 (s, 12H, CH aromat.), 1.96 (s,

2

3

2 2 3

1

13

aromat.), 2.03 (q, J=7.0 Hz, 4H, CH CH ), 1.65 (q,

12H, CH₃aromat.). C{ H}-NMR (C D N, 100.64

5 5

2

1

3

1

J=7.5 Hz, 4H, CH CH ). C{ H}-NMR (C D N,

MHz): 213.31 (CHꢀCH ), 143.37 (C), 141.78 (C), 138.46

2

5

2

1

00.64 MHz): 138.14 (CHꢀCH ), 136.99 (C), 131.27 (C),

(CCH3), 138.21 (CCH ), 129.68 (CH aromat.), 128.88

2

3

1

28.41 (C), 125.63 (CH aromat.), 114.95 (ꢀCH ), 104.09

(C), 124.81 (CH aromat.), 114.57 (ꢀCH ), 110.03 (C),

2

(

CH), 33.12 (CH CH ), 30.75 (CH CH ), 30.54

97.77 (CH), 34.24 (CH CH ), 26.27 (CH CH ), 19.13/

2

(

CH CH ), 19.08 (CH3 aromat.). LRMS (73°C): m/z 584

3) [M( Zr, Cl, Cl)] , 582 (2) [M( Zr, Cl, Cl)] ,

17.79 (CH aromat.), 13.46 (CH ). LRMS (151°C): m/z

2

0

3 3

+

9

35

37

+

90

35

+

90

35

37

90

584 (7) [M( Zr, Cl, Cl)] , 582 (7) [M( Zr,

9

0

35 37

+

35

+

90

35 37

+

3

73 (53) [C H

Zr Cl Cl] , 371 (53) [C H

Cl, Cl)] , 373 (98) [C H

Zr Cl Cl] , 371 (100)

1

6

19

16 19

9

0

35

90

37

+

90

35

+

90

37

+

Zr Cl ], 337 (7) [C H

Zr Cl] , 335 (10)

[C H

Zr Cl ] , 335 (15) [C H

Zr Cl] , 295 (9) [C H Zr Cl] , 293 (7)

Zr Cl] , 128 (6) [C H ] , 115 (7) [C H ] .

Zr Cl] , 333 (14)

2

16 18

16 19

2

+

16 18

9

0

35

+

90

35 37

+

35

37

+

[C H

Zr Cl] , 319 (6) [C H

Zr Cl Cl] , 317

1

6

18

12 13

16 18

13 14

9

0

35

+

90

37

+

35

+

(

6) [C H

Zr Cl ] , 283 (4) [C H

Zr Cl] , 281

1

2

13

2

12 12

13 14

10

8

9

7

9

0

35

+

Zr Cl] , 128 (9) [C H ] , 115 (8)

Anal. Found: C, 65.58; H, 6.49. C H ZrCl (584.79 g

1

+

2

12

10

8

32 38 2

−1

[C H ] . Anal. Found: C, 65.72; H, 6.53. C H ZrCl

mol ) (14b). Calc.: C, 65.73; H, 6.55%.

.6. X-ray crystallographic analyses

Suitable crystals of 5b and 12b were obtained from

9

7

32 38

2

−

1

(

584.79 g mol ) (12b). Calc.: C, 65.73; H, 6.55%.

5

.5.8. Bis[1-(3-buten-1-yl)-3-methylindenyl]zirconium

dichloride (13b)

3b was prepared from ZrCl (0.44 g, 2.0 mmol) and

1

hexane. An Enraf–Nonius CAD-4 automatic diffrac-

4

˚

[1-(3-buten-1-yl)-3-methylindenyl]lithium (0.76 g, 4.0

tometer (v-2q scan, u=0.71096 A, variable scan time 45

mmol) in THF (50 ml) by the method described for 11b.

The solution was stirred 60 h at 25°C. The solvent were

removed under reduced pressure and the residue was

s) controlled by a Compaq Deskpro 386s and ﬁtted with

a liquid nitrogen low-temperature device was used for the

intensity measurements. The unit cell parameters were

obtained from the angles of 25 reﬂections in the range

of 3°B2qB21° for 5b and 13°B2qB34° for 12b.

Reﬂections were scanned with variable scan time, de-

pending on intensities, with 2/3 of the time used for

scanning the peak and 1/6 measuring each the left and

the right background. The intensities of three check

reﬂections monitored every 2 h showed only statistical

ﬂuctuations during the data collection. The crystal ori-

dissolved in Et O (50 ml). The yellow solution was

2

isolated by ﬁltration and the solvent removed in vacuo.

The solid was washed with hexane (15 ml) to yield 13b

as a yellow solid (0.39 g, 37%). M.p.: 142–145°C.

1

H-NMR (CDCl , 200 MHz): 7.34 (m, 16H, CH aro-

3

mat.), 6.73 (d, J=3.2 Hz, 2H, CH), 6.43 (d, J=3.2 Hz,

2

H, CH), 5.91 (m, 4H, CHꢀCH ), 5.05 (m, 8H, ꢀCH ),

2

.54 (m, 8H, CH ), 2.23 (m, 8H, CH ), 1.42 (s, 12H, CH ).

2

3

H. Schumann et al. / Journal of Organometallic Chemistry 579 (1999) 356–372

371

entation was checked every 200 intensity measurements

by scanning 3 reﬂections. A new orientation matrix was

automatically calculated from a list of 25 recentered

reﬂections in case the angular change was greater than

were prepared in 10 mm tubes as 10 wt% solutions of

the polymer in perchlorobutadiene/tetrachloroethane-

d₂. Molecular weights and molecular weight distribu-

tions were determined by gel permeation chroma-

tography on a Waters 150-C instrument (trichloroben-

zene, 135°C) using a PL-EMD-960 evaporation light

scattering detector. Differential scanning calorimetry

was performed on a Mettler–Toledo DSC 821e instru-

0.1%. The raw data were corrected for Lorentz, polar-

ization and adsorption effects [25]. Reﬁnements in

space group P2 /c (5b) and Pcan (12b) were successful.

1

The positions of the Zr atoms were determined from

three-dimensional Patterson syntheses (SHELXS86) [26].

The calculated difference Fourier map (SHELXL93) [27]

revealed all other missing non-hydrogen atoms. All

non-hydrogen atoms were reﬁned anisotropically. The

C–H hydrogen atoms were calculated in idealized posi-

−

1

ment at a heating rate of 20°C min . The values

obtained in the second run are reported.

Acknowledgements

˚

2

tions (C–H=0.96 A, U =0.08 A ). Scattering factors

iso

were taken from references [28–30]. The ﬁnal residual

of least squares is R=8.13% for 5b and R=5.08% for

This work was ﬁnancially supported by the Fonds

der Chemischen Industrie, the Deutsche Forschungsge-

meinschaft, the Alexander von Humboldt Stiftung (Re-

12b. Data reduction was performed using a IBM RISC

System/6000, 340 [25]. All other calculations were un-

dertaken with (SHELXL93) [27]. The geometrical aspects

of the structure were analyzed by using the PLUTON

program [31]. Further details of the crystal structure

investigation are available on request from the Fachin-

formationszentrum Karlsruhe GmbH, D-76344 Eggen-

stein-Leopoldshafen (FRG), on quoting the depository

number CSD-410454 for 5b and CSD-410455 for 12b.

search

Fellowship

for

R.L.H.)

and

the

Partnerschaftsprogramm TU Berlin–University of

Oklahoma.

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Article Doi

Synthesis and characterization of 1- and 2-(ω-alken-1-yl)indenes, their lithium salts and dichlorozirconium(IV) complexes

DOI: 10.1016/S0022-328X(99)00026-1

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