Ph-functionalised phosphanylalkyl(silyl)cyclopentadienyl ligands: Synthesis and catalytic properties of [{(η5-C5H4)CMe2 PHtBu}MCl3] (M = Ti, Zr) and [{(η5-C5H4</s

Article abstract of DOI:10.1016/S0277-5387(02)01212-3

The silylated phosphanylsilylcyclopentadienes 1- and 3-SiMe₃-1-SiMe₂PHRC₅H₄ [R = Ph (1), Cy (2)] and phosphanylalkylcyclopentadienes 1-, 2- and 3-CMe₂PH^tBu-1-SiMe₃C₅ H

Full text of DOI:10.1016/S0277-5387(02)01212-3

Polyhedron 21 (2002) 2445ꢁ2450
/
www.elsevier.com/locate/poly
PH-functionalised phosphanylalkyl(silyl)cyclopentadienyl ligands:
Synthesis and catalytic properties of [{(h5-C5H4)CMe2PHtBu}MCl3]
(Mꢀ
/
Ti, Zr) and [{(h5-C5H4)SiMe2PHR}ZrCl3] (Rꢀ
/
Ph, Cy)
Thomas Koch a, Evamarie Hey-Hawkins a,*, Mercedes Galan-Fereres b, Moris S. Eisen b
a Institut fur Anorganische Chemie der Universitat, Johannisallee 29, D-04103 Leipzig, Germany
¨
¨
b Department of Chemistry and Institute of Catalysis Science and Technology, Technion-Israel Institute of Technology, Haifa 32000, Israel
Received 27 June 2002; accepted 22 August 2002
Dedicated to Professor Dr Rudiger Mews on the occasion of his 60th birthday
¨
Abstract
The silylated phosphanylsilylcyclopentadienes 1- and 3-SiMe3Ã
ylcyclopentadienes 1-, 2- and 3-CMe2PHtBuÃ
1-SiMe3C5H4 (3) were prepared from LiPHR and 1-SiMe3Ã
PHtBuCMe2C5H4] and SiMe3Cl, respectively. Complexes 1 and 2 react with ZrCl4 to give [{(h5-C5H4)SiMe2PHR}ZrCl3] [Rꢀ
(4), Cy (5)], and 3 reacts with MCl4 with formation of [{(h5-C5H4)CMe2PHtBu}MCl3] [Mꢀ
Ti (6), Zr (7)]. Complexes 1ꢁ7 were
characterised by NMR and IR spectroscopy and mass spectrometry. Complexes 4ꢁ7 were studied in the catalytic polymerisation of
/
1-SiMe2PHRC5H4 [Rꢀ
/
Ph (1), Cy (2)] and phosphanylalk-
1-SiMe2ClC5H4 and Li[1-
Ph
/
/
/
/
/
/
ethene and propene with activation by methylalumoxane (MAO) as cocatalyst.
# 2002 Elsevier Science Ltd. All rights reserved.
Keywords: PH-functionalised phosphanylalkyl(silyl)cyclopentadienyl ligands; Zirconium complexes; Titanium complexes; Polymerisation studies
1. Introduction
in the polymerisation and copolymerisation of olefins
[6]. These studies were also extended to phospholyl
ligands (C) [7].
After the discovery of a-olefin polymerisation [1],
numerous metallocene and monocyclopentadienyl deri-
vatives with different steric and electronic properties
were synthesised and employed as catalysts in polymer-
isation reactions.
Ansa-metallocene dichlorides A of Ti, Zr, and Hf,
especially chiral ones, are important catalysts for
isotactic polymerisation of olefins with promotion by
methylalumoxane (MAO). Therefore, intensive research
is being carried out towards the synthesis of improved
While numerous cyclopentadienyl ligands with O-
and N-functionalised side-chains are known, the num-
ber of cyclopentadienes with a P-functionalised alkyl or
silyl side-chain is still small [8], and we have only
recently reported on the first compounds in which the
P atom bears a reactive substituent (e.g. PH) [9,10].The
lithium salts [Li(tmeda)]2[PhPCMe2(C5H4)] [11] and
catalysts [2ꢁ5].
/
Recently, monocyclopentadienyl derivatives B in
which the cyclopentadienyl ring has a heteroatom-
functionalised side-chain were prepared and employed
* Corresponding author. Tel.: ꢂ
/
49-341-9736-151; fax: 49-341-9739-
[Li(tmeda)][R2PCMe2(C5H4)] (Rꢀ
Me2PHMes*C5Me4H and its dipotassium salt,
[K2(THF)4(1-SiMe2PMes*C5Me4)]2 (Mes*ꢀ
2,4,6-tBu3-
/Ph, Me) [12], 1-Si-
319
E-mail addresses: hey@rz.uni-leipzig.de (E. Hey-Hawkins),
chmoris@techunix.technion.ac.il (M.S. Eisen).
/
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 2 1 2 - 3

2446
T. Koch et al. / Polyhedron 21 (2002) 2445ꢁ2450
/
C6H2) [13] have been structurally characterised. Such
compounds should be useful precursors for dianionic
bifunctional ligands in transition metal chemistry. In
addition, the presence of a P-containing group is
advantageous for reactivity studies by 31P NMR spec-
troscopy.
We have previously reported the synthesis of the PH-
functionalised ferrocene derivatives rac-[Fe{(h5-
C5H4)CMe2PHR}2] (RꢀPh, Mes) [14] and the metal-
/
ð2Þ
3 as colourless (1, 2) or yellow (3)
oil. The different constitutional isomers could not be
locene derivatives [{(h5-C5H4)CMe2PHR}2ZrCl2] and
[{(h5-C5H4)CMe2PHR}2TiCl] (Rꢀ
slowly decompose on recrystallisation from THF, Et2O
/Ph, Bu). The latter
t
Work-up yielded 1ꢁ
/
or toluene with formation of [{(h5-C5H4)2CMe2}MCl2]
separated by distillation [19]. Compounds 1ꢁ3 were
/
characterised by NMR (1H, 31P) and IR spectroscopy
and mass spectrometry. In the MS, molecular-ion peaks
were observed, and the peak of 100% intensity was due
(Mꢀ
/
Zr, Ti) and (PR)n (Rꢀ
/
Ph, nꢀ
/
4ꢁ
/
6; Rꢀt
/
Bu, nꢀ
/
4) and PH2R [15].
We now report the synthesis of the first stable
monosubstituted PH-functionalised phosphanylalkyl-
and phosphanylsilylcyclopentadienyl complexes of
Group 4 metals, namely, [{(h5-C5H4)SiMe2PHR}ZrCl3]
t
to m/zꢀ
/
Mꢂꢃ
/
PHR (Rꢀ
/
Ph, Cy, Bu).
Compounds 1 and 2 react with ZrCl4 in toluene to
give [{(h5-C5H4)SiMe2PHR}ZrCl3] [Rꢀ
Ph (4), Cy (5);
Eq. (3)], and 3 reacts with MCl4 with formation of [{(h5-
C5H4)CMe2PHtBu}MCl3] [Mꢀ
Ti (6), Zr (7); Eq. (4)].
/
[Rꢀ
[Mꢀ
/
Ph (4), Cy (5)] and [{(h5-C5H4)CMe2PHtBu}MCl3]
/
/
Ti (6), Zr (7)] and their activity in the polymerisa-
As SiMe3Cl is eliminated, the mixture of constitutional
isomers (see Eqs. (1) and (2)) can be employed in these
tion of ethene and propene. Recently, Erker et al.
reported the synthesis and catalytic properties in the
polymerisation of olefins of the constrained-geometry
reactions. Compounds 4ꢁ7 can be recrystallised from
/
catalysts [{(h5-C5H4)CMe2PCy}M(NR2)2] (Mꢀ
/
Ti,
Et) [16]. Hou et al. reported the
synthesis of [{(h5-C5Me4)SiMe2PMes*}Ln(L)n] (Lnꢀ
Sm: LꢀTHF, nꢀ1 or 3; LꢀMeOCH2CH2OMe, nꢀ
2; LꢀPO(NMe2)3, nꢀ2; LnꢀYb, LꢀTHF, nꢀ3)
and the polymerisation of ethene, o-caprolactone and
1,3-butadiene with the SmIIꢁ
mono-THF complex [13].
dichloromethane or THF; the complexes are almost
insoluble in non-coordinating and non-polar solvents,
and this indicates association in the solid state (pre-
sumably by chloro bridges, cf. [{(h5-C5H4)2CH2CH2-
PPh2}ZrCl3] [20]) and adduct formation in THF (cf.
[{(h5-C5Me4)2CH2CH2PPh2}ZrCl3(THF)] [21]). Com-
Rꢀ
/
Me; Mꢀ
/
Zr, Rꢀ
/
/
/
/
/
/
/
/
/
/
/
/
pounds 4ꢁ
red (7) microcrystalline powders in good to moderate
yields (45ꢁ80%). Compounds 4 and 5 are only moder-
/7 are obtained as yellow (4), white (5, 6) or
/
ately air sensitive, while 6 and 7 are more so, and
all complexes decompose with formation of phosphine
2. Results and discussion
2.1. Synthesis
The general synthetic method for the preparation of a
monocyclopentadienyl metal trichloride complex of
Group 4 metals is the elimination of SiMe3Cl [17].
Occasionally, this method can also be employed for the
synthesis of metallocene derivatives. We therefore pre-
pared the silylated phosphanylsilyl- and phosphanylalk-
ð3Þ
ylcyclopentadienes 1- and 3-SiMe3Ã
/
1-SiMe2PHRC5H4
1-
1-Si-
[Rꢀ
/
Ph (1), Cy (2)] and 1-, 2- and 3-CMe2PHtBuÃ
/
SiMe3C5H4 (3) from LiPHR and 1-SiMe3Ã
/
Me2ClC5H4 [18] (Eq. (1)) and Li[1-PHtBuCMe2C5H4]
and SiMe3Cl (Eq. (2)), respectively.
ð4Þ
ð1Þ

T. Koch et al. / Polyhedron 21 (2002) 2445ꢁ
/2450
2447
(PH2R).
Compounds 4ꢁ
13C, 31P) and IR spectroscopy and mass spectrometry.
Compounds 4, 5 and 7 [4: ꢃ 200.9 Hz); 5:
117.1 (1JPÃH
was already observed for related constrained-geometry
catalysts with N-functionalised side-chains [6e].
The activities of complexes 4 and 7 are slightly higher
than those of the constrained-geometry complexes and
on the same order of magnitude as those of the Cp/
phosphanido Group 4 complexes [14]. Regarding pro-
/
7 were characterised by NMR (1H,
/
ꢀ
/
ꢃ
/
121.6 (1JPÃH
ꢀ
/
201.0 Hz); 7: 36.7 ppm (1JPÃH
ꢀ
/
213.4 Hz)] exhibit a doublet in the 31P NMR spectrum
(in [D8]THF), which is shifted to low field by approxi-
pene, the activity attained by complexes 4ꢁ7 is far lower
/
than that observed with metallocene complexes [2,6e].
mately 1ꢁ
[1: ꢃ
121.6 (1JPÃH
(1JPÃH
/
12 ppm relative to the starting materials 1ꢁ
201.0 Hz) and ꢃ122.3 ppm
124.9 (1JPÃH
191.2 Hz) and
189.5 Hz); 3: 25.2 (d of dec,
/
3
/
ꢀ
/
/
ꢀ
/
204.1 Hz); 2: ꢃ
/
ꢀ
/
ꢃ
/
127.6 ppm (1JPÃH
ꢀ
/
4. Experimental
1JPÃH
ꢀ
/
196.7 Hz, JPÃH
ꢀ
/
12.1 Hz), 19.2 (d, JPÃH
ꢀ
/
3
1
1
198.4 Hz) and 13.1 ppm (d of dec, JPÃH
3JPÃH
12.2 Hz)]. This indicates that there is no
interaction between the phosphanyl group and the
ꢀ199.5 Hz,
/
All experiments were carried out under purified dry
Ar. Solvents were dried and freshly distilled under Ar.
The NMR spectra were recorded at 25 8C in C6D6 or
[D8]THF with an AVANCE DRX 400 spectrometer
ꢀ
/
transition metal. In contrast, 6 [ꢃ
/
6.8 ppm (1JPÃH
ꢀ
/
282.5 Hz)] exhibits a doublet in the 31P NMR spectrum
(in [D8]THF) which is shifted to high field relative to the
starting material 3, and the coupling constant increased
by approximately 85 Hz.
1
(Bruker): H NMR: internal standard solvent (C6H6 or
THF), external standard SiMe4; 13C NMR: external
standard SiMe4, internal standard solvent; 31P NMR:
external standard 85% H3PO4. The IR spectra were
For 4ꢁ7, only peaks for the monomeric complexes
/
recorded on a Perkinꢁ
spectrometer in the range 350ꢁ
/
Elmer System 2000 FT-IR
4000 cmꢃ1. The mass
were observed in the mass spectra. While the formation
of monomeric molecules is rather unlikely, this suggests
that readily cleavable dimers are probably present rather
than oligomers.
/
spectra were recorded with an MAT-212 (Finnigan), EI
MS, 70 eV. The m.p. were determined in sealed
capillaries under Ar and are uncorrected.
LiPHPh [23], LiPHCy [24], Li[1-PHtBuCMe2C5H4]
[15], and 1-SiMe3Ã
/
1-SiMe2ClC5H4 [18] were prepared
according to literature procedures.
3. Polymerisation studies
4.1. 1- and 3-SiMe3Ã
/
1-SiMe2PHPhC5H4 (1)
The complexes 4ꢁ7 were studied in the catalytic
/
polymerisation of ethene, propene and styrene with
activation by MAO (1000-fold excess, in toluene) as
cocatalyst. No reaction was observed with styrene,
which was rather unexpected as related side-chain-
functionalised monocyclopentadienyl complexes of Ti
exhibit good catalytic properties [22]. Presumably,
LiPHPh (4.10 g, 35 mmol) was suspended in n-C6H14
(150 ml) and cooled to ꢃ20 8C. Then 1-SiMe3Ã1-
/
/
SiMe2ClC5H4 (8.10 g, 35 mmol) was added, and the
reaction mixture warmed to ambient temperature. The
mixture was stirred for 1 day, filtered, the solvent
evaporated in vacuo and the resulting yellow oil distilled
under reduced pressure (65ꢁ
give 6.5 g (61%) of 1 as a colourless oil.
1H NMR (C6D6): dꢀ
0.05 (s, 18H, CH3 in SiMe3, 2
isomers), 0.01 (d, 6H, CH3 in SiMe2, JPÃH
/
75 8C, 2ꢄ
/
10ꢃ2 Torr) to
complexes 4ꢁ
/
7 are destroyed by MAO (attack at the
PÃSi or PÃC bond with concomitant decomposition of
/
/
the complexes) at the elevated temperatures employed
(60 8C). However, ethene and propene are readily
polymerised with formation of high-density polyethy-
lene and polypropylene (Table 1); the elastomeric
/
ꢃ
/
3
ꢀ
/
2.4, 2
2.8 Hz, 2
isomers), 3.10 (br s, 1H, CH in C5H4, 1 isomer), 3.20 (d,
2H, PH, 1JPÃH
192.6 Hz, 2 isomers), 6.44 (m, 2H, CH
3
isomers), 0.02 (d, 6H, CH3 in SiMe2, JPÃH
ꢀ
/
properties of the latter indicate a PꢁM interaction
/
ꢀ
/
during the polymerisation process. Similar behaviour
in C5H4, 2 isomers), 6.48 (m, 1H, CH in C5H4, 1
isomer), 6.75 (m, 4H, CH in C5H4, 2 isomers), 7.01 (m,
Table 1
6H, o- and p-CH in Ph, 2 isomers), 7.26 (t, 4H, m-CH
3
in Ph, JHÃH
ꢀ
/
5.4 Hz, 2 isomers).*31
P NMR (C6D6):
/
Activity of 4ꢁ7 in the polymerisation of propene
/
1
1
dꢀ
Hz.*
PHPh]), 73 (65%, SiMe3), and fragmentation products
thereof.*
IR (KBr): n¯ (cmꢃ1): 2352 st (nPH), 1622 m,
1484 m (nCÄC).*Anal. Calc. for C16H25PSi2 (304.51):
/
ꢃ
/
121.6, d, JPÃH
ꢀ
/
201 Hz; ꢃ
/
122.3, d, JPÃH
ꢀ
/
204
Complex
Ratio MAO:cat. Activity for polypropylene
(g molꢃ1 hꢃ1
/
EI MS: m/z 304 (45%, [Mꢂ]), 195 (100%, [Mꢂꢃ
/
)
4
5
6
7
300
300
300
300
0.86ꢄ103
/
2.61ꢄ103
0.84ꢄ103
8.20ꢄ103
/
/
C 63.1, H 8.3, P 10.2; Found: C 56.8 (due to silicon
carbide formation), H 8.1, P 9.3%.

2448
T. Koch et al. / Polyhedron 21 (2002) 2445ꢁ2450
/
4.2. 1- and 3-SiMe3Ã
/
1-SiMe2PHCyÃ
/
C5H4 (2)
268 (25%, [Mꢂ]), 179 (100%, [Mꢂꢃ
SiMe3), and fragmentation products thereof.*
(KBr): n¯ (cmꢃ1): 2345 m (nPH), 1625 m, 1503 m (nCÄ
C).*Anal. Calc. for C15H29PSi (268.45): C 67.1, H
/
PHtBu]), 73 (100%,
/IR
LiPHCy (3.80 g, 31 mmol) was suspended in n-C6H14
(150 ml) and cooled to ꢃ50 8C. Then 1-SiMe3Ã1-
SiMe2ClC5H4 (8.00 g, 34 mmol) was added, and the
reaction mixture warmed to ambient temperature. The
mixture was stirred for 1 day, filtered, the solvent
evaporated in vacuo and the resulting yellow oil distilled
under reduced pressure (50ꢁ
give 4.1 g (43%) of 2 as a colourless oil.
1H NMR (C6D6): dꢀ
0.01 (s, 18H, CH3 in SiMe3, 2
/
/
/
/
10.9, P 11.5; Found: C 65.9, H 9.9, P 10.9%.
4.4. [{(h5-C5H4)SiMe2PHPh}ZrCl3] (4)
/
55 8C, 1ꢄ
/
10ꢃ2 Torr) to
ZrCl4 (1.33 g, 5.7 mmol) was suspended in C6H5CH3
(30 ml), and a solution of 1 (1.75 g, 5.8 mmol) in
C6H5CH3 (20 ml) was added dropwise. The reaction
mixture was stirred for 1 day, then the solvent was
evaporated in vacuo and the resulting residue washed
with n-C5H12 (30 ml) and extracted with THF to give
2.0 g (80%) of 4 as a yellow microcrystalline solid. M.p.:
/
ꢃ
/
3
isomers), 0.03 (d, 6H, CH3 in SiMe2, JPÃH
isomers), 0.04 (d, 6H, CH3 in SiMe2, JPÃH
ꢀ
/
3.0 Hz, 2
3
ꢀ
/
3.3 Hz, 2
isomers), 1.2ꢁ
/
2.1 (m, 22H, Cy, 2 isomers), 2.60 (d of d,
2H, PH, 1JPÃH
(br s, 1H, CH in C5H4, 1 isomer), 6.50 (m, 3H, CH in
ꢀ
/
191.0, 3JPÃH
ꢀ/6.4 Hz, 2 isomers), 2.91
150ꢁ
/
155 8C. 1H NMR ([D8]THF): dꢀ
/
0.54 (d, 3H,
4.9 Hz), 0.55 (d, 3H, CH3 in
C5H4, 2 isomers), 6.62 (m, 4H, CH in C5H4, 2
isomers).*31
3
CH3 in SiMe2, JPÃH
SiMe2, JPÃH
ꢀ
/
1
/
P NMR (C6D6): dꢀ
/
ꢃ
/
124.9, d, JPÃH
ꢀ
/
3
1
ꢀ
/
3.9 Hz), 2.62 (d, 1H, PH, JPÃH
ꢀ200.9
/
1
191.2 Hz; ꢃ
360 (27%, [Mꢂ]), 209 (100%, [Mꢂꢃ
SiMe3) and fragmentation products thereof.*
(KBr): n¯ (cmꢃ1): 2327 st (nPH), 1635 m, 1625 m (nCÄ
C).*Anal. Calc. for C20H33PSi2 (360.62): C 61.9, H
/
127.6, d, JPÃH
ꢀ
/
189.5 Hz.*
PHCy]), 73 (100%,
IR
/EI MS: m/z
Hz), 6.52 (m, 1H, CH in C5H4), 6.55 (m, 1H, CH in
C5H4), 6.58 (m, 1H, CH in C5H4), 6.61 (m, 1H, CH in
C5H4), 7.10 (m, 3H, CH in Ph), 7.11 (m, 2H, CH in
/
/
/
Ph).*13
2JPÃC
2.9 Hz), ꢃ
119.34 (s, 2C, C in C5H4), 121.95 (d, 2C, C in C5H4,
/
C NMR ([D8]THF): dꢀ
/
ꢃ
/
1.09 (d, 1C, CH3Si,
/
2
ꢀ
/
/
1.00 (d, 1C, CH3Si, JPÃC
ꢀ5.5),
/
10.1, P 10.0; Found: C 56.9 (due to silicon carbide
formation), H 9.5, P 8.9%.
1
3JPÃC
22.0 Hz), 126.70 (d, 1C, C1 in C5H4, JPÃC
127.00 (s, 1C, p-C in Ph), 128.66 (d, 2C, m-C in Ph,
ꢀ
/
6.2 Hz), 126.32 (d, 1C, ipso-C in Ph, JPÃC
ꢀ
/
2
ꢀ12.8 Hz),
/
4.3. 1-, 2- and 3-CMe2PHtBuÃ
/
1-SiMe3C5H4 (3)
3JPÃC
Hz).*31
200.9 Hz.*
[MꢂꢃPHPh]), 122 (100%, C5H4SiMe2ꢂ), 109 (52%,
PHPhꢂ), and fragmentation products thereof.*
IR
(KBr): n¯ (cmꢃ1): 2351 s (nPH).*
Anal. Calc. for
ꢀ
/
5.8 Hz), 134.45 (d, 2C, o-C in Ph, JPÃC
ꢀ
/
14.4
117.1, d, JPÃH
EI MS: m/z 428 (2%, [Mꢂ]), 319 (32%,
2
Li[1-PHtBuCMe2C5H4] (1.00 g, 4.5 mmol) was dis-
solved in Et2O (25 ml), SiMe3Cl (0.6 ml, 5 mmol) was
added and the reaction mixture stirred for 12 h. LiCl
was filtered off, the solvent evaporated in vacuo and the
resulting yellow oil distilled under reduced pressure
1
/
P NMR ([D8]THF): dꢀ
/
ꢃ
/
ꢀ
/
/
/
/
/
(55 8C, 3ꢄ
yellow oil.
1H NMR (C6D6): dꢀ
SiMe3, 3 isomers), 0.98 (d, 9H, CH3 in Bu, JPÃH
/
10ꢃ3 Torr) to give 1.1 g (91%) of 3 as a
C13H16Cl3PSiZr (428.9): C 36.4, H 3.8, P 7.2; Found:
C 26.4 (due to silicon carbide formation), H 4.0, P 7.1%.
/
ꢃ0.09 (br s, 27H, CH3 in
/
t
3
ꢀ
/
8.5
8.7 Hz,
13.2 Hz, 1
t
3
Hz, 1 isomer), 1.07 (d, 9H, CH3 in Bu, JPÃH
1 isomer), 1.10 (d, 9H, CH3 in Bu, JPÃH
isomer), 1.34 (d, 3H, CH3 in CMe2, JPÃH
isomer), 1.36 (d, 3H, CH3 in CMe2, JPÃH
isomer), 1.43 (d, 3H, CH3 in CMe2, JPÃH
isomer), 1.45 (d, 3H, CH3 in CMe2, JPÃH
isomer), 1.48 (d, 3H, CH3 in CMe2, JPÃH
isomer), 1.56 (d, 3H, CH3 in CMe2, JPÃH
ꢀ
/
4.5. [{(h5-C5H4)SiMe2PHCy}ZrCl3] (5)
t
3
ꢀ
/
3
ꢀ
/
16.6 Hz, 1
16.6 Hz, 1
13.6 Hz, 1
10.1 Hz, 1
12.3 Hz, 1
ZrCl4 (1.80 g, 7.7 mmol) was suspended in C6H5CH3
(50 ml), and a solution of 2 (2.79 g, 7.8 mmol) in
C6H5CH3 (50 ml) was added dropwise. The reaction
mixture was stirred for 1 day, then the solvent was
evaporated in vacuo and the resulting residue washed
with n-C5H12 (30 ml) and extracted with THF to give
3
ꢀ
/
3
ꢀ
/
3
ꢀ
/
3
ꢀ
/
3
ꢀ7.6 Hz, 1
/
isomer), 3.08 (br s, 2H, CH in C5H4, 2 isomers), 3.31 (d,
2H, PH, 1JPÃH
197.4 Hz, 2 isomers), 3.49 (d, 1H, PH,
1JPÃH
199.5 Hz, 1 isomer), 5.98 (s, 2H, CH in C5H4, 1
2.0 g (58%) of 5 as white microcrystalline solid. M.p.:
1
ꢀ
/
145 8C. H NMR ([D8]THF): dꢀ
/
0.63 (d, 3H, CH3 in
3
ꢀ
/
SiMe2, JPÃH
3JPÃH
PH, 1JPÃH
(m, 2H, CH in C5H4).*31
ꢀ
/
4.3 Hz), 0.64 (d, 3H, CH3 in SiMe2,
isomer), 6.05 (s, 1H, CH in C5H4, 1 isomer), 6.15 (s, 1H,
CH in C5H4, 1 isomer), 6.36 (s, 2H, CH in C5H4, 1
isomer), 6.63 (s, 1H, CH in C5H4, 1 isomer), 6.65 (s, 1H,
CH in C5H4, 1 isomer), 6.80 (s, 1H, CH in C5H4, 1
ꢀ
/
6.1 Hz), 1.18ꢁ
191.1 Hz), 6.57 (m, 2H, CH in C5H4), 6.64
P NMR ([D8]THF): dꢀ
201.0 Hz.*EI MS: m/z 434 (7%,
[Mꢂ]), 319 (45%, [Mꢂꢃ
PHCy]), 122 (100%,
C5H4SiMe2ꢂ), 115 (82%, PHCyꢂ), and fragmentation
products thereof.*
IR (KBr): n¯ (cmꢃ1): 2403 m
(nPH).*Anal. Calc. for C13H22Cl3PSiZr (434.95): C
/
1.85 (m, 11H, Cy), 2.59 (d, 1H,
ꢀ
/
/
/
1
ꢃ
/
121.6, d, JPÃH
ꢀ
/
/
isomer), 6.81 (s, 1H, CH in C5H4, 1 isomer).*31
/
P
196.7 Hz,
198.4 Hz; 13.1, d of
/
1
NMR (C6D6): dꢀ
/
25.2, d of dec, JPÃH
ꢀ
/
1
3JPÃH
ꢀ
/
12.1 Hz; 19.2, d, JPÃH
ꢀ
/
/
1
3
dec, JPÃH
ꢀ
/
199.5 Hz, JPÃH
ꢀ
/
12.2 Hz.*EI MS: m/z
/
/

T. Koch et al. / Polyhedron 21 (2002) 2445ꢁ
/2450
2449
35.9, H 5.1, P 7.1; Found: C 27.3 (due to silicon carbide
formation), H 4.9, P 6.5%.
4.8. Polymerisation experiments
All manipulations of air-sensitive materials were
performed with the rigorous exclusion of oxygen and
moisture in flamed Schlenk-type glassware on a dual-
manifold Schlenk line, or interfaced to a high vacuum
(10ꢃ5 Torr) line, or in a nitrogen-filled Vacuum Atmo-
spheres glove box with a medium-capacity recirculator
4.6. [{(h5-C5H4)CMe2PHtBu}ZrCl3] (6)
ZrCl4 (1.00 g, 4.3 mmol) was suspended in C6H5CH3
(50 ml), and a solution of 3 (1.15 g, 4.3 mmol) in
C6H5CH3 (10 ml) was added dropwise. The reaction
mixture was stirred for 12 h, then the solvent was
evaporated in vacuo and the resulting residue washed
with n-C5H12 (30 ml) and extracted with THF to give
(1ꢁ/2 ppm O2). Argon, ethene, propene and nitrogen
gases were purified by passage through a MnO oxygen-
˚
removal column and a Davison 4 A molecular sieve
column. Styrene (Spectrum) was freshly distilled under
vacuum from CaO. All solvents for vacuum-line manip-
ulations were stored in vacuo over Na/K alloy in
resealable bulbs.
The polymerisation experiments were conducted in a
100 ml flamed heavy-wall glass round-bottom reaction
flask attached to a high-vacuum line. In a typical
0.76 g (45%) of 6 as white microcrystalline solid. M.p.:
1
105 8C. H NMR ([D8]THF): dꢀ
/
1.03 (d, 9H, CH3 in
tBu, JHÃH
Hz), 1.54 (d, 3H, CH3C, JPÃH
PH, 1JPÃH
294.9 Hz), 6.31 (m, 1H, CH in C5H4), 6.53
(m, 1H, CH in C5H4), 6.55 (m, 1H, CH in C5H4), 6.63
(m, 1H, CH in C5H4).*13
C NMR ([D8]THF): dꢀ
ꢀ
/
13.2 Hz), 1.46 (d, 3H, CH3C, JPÃH
ꢀ
/
8.1
3
3
3
ꢀ
/
11.2 Hz), 3.54 (d, 1H,
ꢀ
/
/
/
experiment, 10 mg of 4ꢁ
amount of MAO (MAO:cat.ꢀ
/
7 and the corresponding
1:300) were charged to
t
2
30.04 (d, 3C, CH3 in Bu, JPÃC
ꢀ
/
5.5 Hz), 33.02 (d,
/
1
1C, C(CH3)2, JPÃC
1JPÃC
11.9 Hz), 33.64 (d, CH3C, JPÃC
34.30 (d, CH3C, JPÃC
ꢀ
/
8.1 Hz), 33.20 (d, 1C, C(CH3)3,
the flask containing a magnetic stir bar. The reaction
vessel was connected to a high-vacuum line, pumped
down and back-filled three times with Ar. Then the flask
was re-evacuated, and a measured quantity of C6H5CH3
(5 ml) was vacuum transferred into the reaction flask
from Na/K. Then gaseous ethene or propene was
condensed into the vessel through a gas-purification
column. The flask was warmed to room temperature,
and the pressure was continuously measured by means
of a manometer. Rapid stirring of the solution was
initiated, and after a measured time interval (2 h), the
polymerisation was quenched by releasing the excess
pressure of ethene or propene and immediately injecting
a methanol/HCl mixture. The polymer product was
collected by filtration, washed with C6H14 and C3H6O
and dried under vacuum for several hours.
2
ꢀ
/
ꢀ
/
4.3 Hz),
2
ꢀ
/
5.8 Hz), 115.39 (s, 1C, C in
C5H4), 119.01 (s, 1C, C in C5H4), 119.78 (s, 1C, C in
C5H4), 119.82 (s, 1C, C in C5H4), 129.71 (d, 1C, C1 in
2
C5H4, JPÃC
6.8, d, 1JPÃH
ꢀ
/
10.2 Hz).*31
/
P NMR (d8-THF): dꢀ
EI MS: m/z 392 (3%, [Mꢂ]),
PHtBu]), 107 (80%, C5H4CMe2ꢂ), and
IR (KBr): n¯ (cmꢃ1):
Anal. Calc. for C12H20Cl3PZr (392.84):
/
ꢃ
/
ꢀ
/
282.5 Hz.*
/
303 (11%, [Mꢂꢃ
fragmentation products thereof.*
2379 m (nPH).*
/
/
/
C 36.7, H 5.1, P 7.9; Found: C 34.3, H 4.9, P 7.5%.
4.7. [{(h5-C5H4)CMe2PHtBu}TiCl3] (7)
TiCl4 (1.50 g, 7.9 mmol) was suspended in C6H5CH3
(50 ml), and a solution of 3 (2.11 g, 7.9 mmol) in
C6H5CH3 (20 ml) was added dropwise. The reaction
mixture was stirred for 12 h, then the solvent was
evaporated in vacuo and the resulting residue washed
with n-C5H12 (30 ml) and extracted with C6H5CH3 to
Acknowledgements
give 1.85 g (67%) of 7 as a red microcrystalline solid.
We gratefully acknowledge financial support from the
Deutsche Forschungsgemeinschaft, the German-Israeli-
Foundation grant no. I-142/95 and the Fonds der
Chemischen Industrie.
1
M.p.: 82ꢁ
/
86 8C. H NMR ([D8]THF): dꢀ
/
0.92 (d, 9H,
12.0 Hz), 1.69 (m, 6H, CH3C), 3.50
212.6 Hz), 6.26 (m, 2H, CH in
C NMR
CH3 in tBu, 3JHÃH
ꢀ
ꢀ
/
1
(d, 1H, PH, JPÃH
/
C5H4), 6.93 (m, 2H, CH in C5H4).*13
/
t
2
([D8]THF): dꢀ
/
31.07 (d, 3C, CH3 in Bu, JPÃC
ꢀ
/
12.8
19.2 Hz), 33.12 (d,
10.1 Hz), 35.37 (s, CH3C), 37.20
(s, CH3C), 121.09 (s, 2C, C in C5H4), 122.64 (d, 1C, C1
1
Hz), 31.45 (d, 1C, C(CH3)2, JPÃC
ꢀ
/
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