Some reactions of Cp*TiMe2(OAr) and Cp*TiMe(CF3SO3)(OAr) with 5-hexen-1-ol and 3-buten-1-ol, structural analysis for Cp*Ti(CF3SO3)[OCH2 (CH2)3CH=CH2](OAr) (

Article abstract of DOI:10.1016/S1387-7003(03)00035-2

Reaction of Cp*TiMe(CF₃SO₃)(OAr) (2, OAr = O-2, 6-ⁱ Pr₂ C₆H₃) with 5-hexen-1-ol in n-hexane gave Cp*Ti(CF₃SO₃)[OCH₂ (CH₂)₃CH=CH_2<

Full text of DOI:10.1016/S1387-7003(03)00035-2

Inorganic Chemistry Communications 6 (2003) 517–522
www.elsevier.com/locate/inoche
Some reactions of CpꢀTiMe2ðOArÞ and CpꢀTiMeðCF3SO3ÞðOArÞ
with 5-hexen-1-ol and 3-buten-1-ol,structural analysis
for CpꢀTiðCF3SO3Þ½OCH2ðCH2Þ CH@CH2ŠðOArÞ
3
ðOAr ¼ O-2; 6-i Pr2 C6H3Þ
*
Kotohiro Nomura ,Yumiko Hatanaka
Graduate School of Materials Science, Nara Institute of Science and Technology (NAIST), 8916-5Takayama, Ikoma, Nara 630-0101, Japan
Received 21 December 2002; accepted 17 January 2003
Abstract
Reaction of CpꢀTiMeðCF3SO3ÞðOArÞ (2,OAr ¼ O-2; 6-i Pr2 C6H3) with 5-hexen-1-ol in n-hexane gave CpꢀTiðCF3SO3Þ½OCH2
ðCH2Þ3CH@CH2ŠðOArÞ (3) exclusively (94% yield). 3 was very stable upon heating,and the structural analysis has been made by X-
ray crystallography. Reaction of CpꢀTiMe2ðOArÞ with both 5-hexen-1-ol and 3-buten-1-ol have also been explored.
Ó 2003 Elsevier Science B.V. All rights reserved.
Keywords: Titanium complex; Alken-1-ol; Half-titanocene; Olefin polymerization
1. Introduction
plex from the reaction of CpꢀTiMe2ðOArÞ (1) with
Ph3CBðC6F5Þ4 [17].
Non-bridged half-metallocene type group IV transi-
tion metal complexes of the type,Cp 0MðLÞX2
(Cp0 ¼ cyclopentadienyl group; M ¼ Ti,Zr,Hf; L ¼ an-
Polymerization of non-conjugated diene attracts
considerable attention not only because cyclopolymer-
ization took place if ordinary metallocene type com-
plexes [18] or a half-metallocene type complex [11c] were
used as catalyst precursors,but also because function-
alization of polyolefin would be attained by simple
modification if one olefinic bond of the diene was re-
mained as the side chain during polymerization. It has
also been known that Cp2ZrðOCMe2CH2CH2CH@
CH2Þþ was isolated and the olefinic double bond was
coordinated to the centered metal [19]. This result would
be indicative for the above cyclopolymerization. In this
paper,we wish to introduce some reactions of
CpꢀTiMe2ðOArÞ (1) and CpꢀTiMeðCF3SO3ÞðOArÞ (2)
with 5-hexen-1-ol and 3-buten-1-ol,and structural
analysis for CpꢀTiðCF3SO3Þ½OCH2ðCH2Þ3CH@CH2Š
ðOArÞ (3).
ionic ligand such as OAr,NR 2,NPR 3,NCR
;
2
X ¼ halogen,alkyl) [1–15],have attracted considerable
attention as the new type of olefin polymerization cat-
alysts,because these types of complexes would exhibit
unique characteristics as olefin polymerization catalysts
that are different from both ordinary metallocene type
and so-called Ôconstrained geometryÕ (hybrid Ôhalf-me-
talloceneÕ) type catalysts. We reported that (cyclopen-
tadienyl)(aryloxo)titanium(IV) complexes
–
MAO
catalyst system exhibited unique characteristics espe-
cially for both ethylene/a-olefin and ethylene/styrene
copolymerizations [3,16]. Concerning their mechanistic
studies,we reported synthesis and structural analysis for
CpꢀTiMeðCF3SO3ÞðOArÞ (2,OAr ¼ O-2; 6-i Pr2 C6H3),
although we could not isolate the cationic methyl com-
2. Results and discussion
* Corresponding author. Tel.: +81-743-72-6041; fax: +81-743-72-
6049.
E-mail address: nomurak@ms.aist-nara.ac.jp (K. Nomura).
It was revealed that 2 prepared from 1 by treating
with CF3SO3H reacted with 1.0 equivalent of 5-hexen-1-
1387-7003/03/$ - see front matter Ó 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S1387-7003(03)00035-2

518
K. Nomura, Y. Hatanaka / Inorganic Chemistry Communications 6 (2003) 517–522
Scheme 1.
ol to give CpꢀTiðCF3SO3Þ½OCH2ðCH2Þ3CH@CH2Š
ðOArÞ (3) as red microcrystals in exclusive yield (94%
ligand) and TiAO(2) (1.769 A,in alkoxo ligand). The
ꢀ
bond distance was also somewhat longer than that in 2
[1.978 A,17],but shorter than those for ½CpꢀTiFðl-FÞ
isolated yield,Scheme 1). 3 was identified by 1H and 13
C
ꢀ
ꢀ
NMR as well as by elemental analysis. The reaction of 2
with 1.0 equivalent of 3-buten-1-ol gave the similar red
microcrystals,and was also identified as Cp ꢀTi
ðCF3SO3ÞðOCH2CH2CH@CH2ÞðOArÞ (4) by 1H and
13C NMR as well as by elemental analysis. These com-
plexes were stable at room temperature,and no de-
compositions would have occurred if the n-hexane
solution was warmed to 50 °C for several hours.
The red prism microcrystals were grown from a
concentrated hot n-hexane solution containing 3 upon
standing,and the structure was determined by X-ray
crystallography using a RIGAKU RAXIS-RAPID Im-
aging Plate diffractometer with graphite monochro-
mated Mo-Ka radiation. The ortep drawing is shown in
Fig. 1 and the selected bond lengths and bond angles are
summarized in Table 1.
ðl-OSO2-p-C6H4CH3ފ (2.070 and 2.094 A) [20]. The
2
result shows that CF3SO3 ligand coordinates relatively
weak to titanium and the complex might thus possess a
cationic character in some extent or would be 16e spe-
cies. TiAO(1) bond distance in the aryloxo ligand (1.806
ꢀ
ꢀ
A) was somewhat longer than those in 2 (1.778 A) and 1
ꢀ
ꢀ
ꢀ
(1.790 A) as well as Cp TiCl2ðOArÞ (1.772 A) [b,17].
ꢀ
TiAO(2) bond distance (1.769 A) is within the expected
range [21].
It was also revealed that the bond angle of TiAOAC
(in phenyl,165.0 °) is still larger than those of other re-
lated complexes (162.3–163.1°) that consisted of differ-
ent cyclopentadienyl or aryloxo groups [b,17], and
somewhat smaller than those in 2 (166.2°), 1 (168.7°)
and CpꢀTiCl2ðOArÞ (173.0°). The present result would
thus also suggest that both Cpꢀ and the aryloxo ligand
containing two isopropyl groups in 2,6-position steri-
cally forces the unique bond angle,which leads to more
O ! Tip donation into the titanium.
3 folds tetrahedral geometry around the titanium and
ꢀ
TiAO(3) bond distance (2.006 A) in CF3SO3 ligand was
ꢀ
longer than those both in TiAO(1) (1.806 A,in aryloxo
It should be noted that the bond distance in the
olefinic bond in alkoxo ligand [corresponded to
ꢀ
C(27)AC(28)] was 1.21 A,and the structure clearly
shows that the olefinic bond does not coordinate to ti-
tanium. This result is a good agreement from resonances
of olefinic protons in 1H NMR spectrum that the NMR
parameters of the vinyl groups for 3 and 4 were un-
changed from the free olefin values. Although this is not
an exact cationic species,the structure observed here
should be an interesting contrast to Cp2ZrðOCMe2CH2
CH2CH@CH2Þþ [19].
Since reactions of 2 with 5-hexen-1-ol and 3-buten-1-
ol took place cleanly to afford 3 and 4 in exclusive yields,
similar reactions with the dimethyl complex (1) were
also explored. The reaction of 1 with 1.0 equivalent of 5-
hexen-1-ol in n-hexane (at )30 °C to room temperature,
3 h) took place cleanly,affording yellow tan residue after
removing solvent from the reaction mixture. The 1H and
13C NMR spectra showed that one methyl group con-
sumed with OH group (confirmed by the decrease in
protons at 0.81 ppm ascribed to TiAMe),strongly sug-
gesting the formation of CpꢀTiMe½OCH2ðCH2Þ3CH@
CH2ŠðOArÞ (5) exclusively. An attempt to isolate the
pure microcrystals was not successful,but the 1H NMR
spectrum of the resultant tan residue after a standard
purification procedure (passing through Celite pad after
Fig. 1. ORTEP drawing for CpꢀTiðCF3SO3Þ½OCH2ðCH2Þ3CH@CH2Š
ðOArÞ (3). Thermal ellipsoids are drawn at a 50% probability level,and
hydrogen atoms were omitted for clarity.

K. Nomura, Y. Hatanaka / Inorganic Chemistry Communications 6 (2003) 517–522
519
Table 1
ꢀ
ꢀ
Selected bond distances (A) and angles (°) for Cp TiðCF3SO3Þ½OCH2ðCH2Þ3CH@CH2ŠðOArÞ (3)
ꢀ
Bond distances in (A)
TiAC(1) in Cpꢀ
TiAC(3) in Cpꢀ
TiAO(2)
SAO(3)
SAO(5) in CF3SO3
F(1)AC(29)
2.378(4)
2.330(4)
1.769(3)
1.477(3)
1.403(4)
1.262(7)
1.433(6)
1.418(6)
1.509(6)
1.480(9)
1.50(1)
TiAC(2) in Cpꢀ
2.376(4)
1.806(3)
2.006(3)
1.413(4)
1.828(7)
1.369(4)
1.412(6)
1.507(7)
1.487(7)
1.479(9)
1.21(1)
TiAO(1) in OAr
TiAO(3) in CF3SO3
SAO(4) in CF3SO3
SAC(29) in CF3SO3
O(1)AC(11) in OAr
C(1)AC(2) in Cpꢀ
C(1)AC(6) in Cpꢀ
C(5)AC(10) in Cpꢀ
C(24)AC(25)
O(2)AC(23)
C(2)AC(3) in Cpꢀ
C(2)AC(7) in Cpꢀ
C(23)AC(24)
C(26)AC(27)
C(27)AC(28)
Bond angles in (°)
103.8(1)
101.3(2)
88.4(2)
O(1)ATiAO(2)
O(2)ATiAO(3)
O(1)ATiAC(2)
O(2)ATiAC(1)
O(2)ATiAC(3)
O(3)ATiAC(2)
TiAO(1)AC(11)
TiAO(3)AS
O(1)ATiAO(3)
O(1)ATiAC(1)
O(1)ATiAC(3)
O(2)ATiAC(2)
O(3)ATiAC(1)
O(3)ATiAC(3)
TiAO(2)AC(23)
O(3)ASAC(29)
O(2)AC(23)AC(24)
101.7(1)
107.9(1)
104.0(1)
136.0(2)
85.4(1)
145.5(1)
101.2(2)
117.6(1)
165.0(2)
135.9(2)
124.3(3)
129(1)
140.4(1)
166.7(3)
103.0(3)
111.3(6)
TiAC(1)AC(6)
C(26)AC(27)AC(28)
the reaction mixture,and was placed in vacuo) showed
high purity of the expected product. No significant dif-
ferences were observed in the H NMR spectra if the
3. Experimental
1
All experiments were carried out under a nitrogen
atmosphere in a Vacuum Atmospheres drybox unless
otherwise specified. All chemicals used were reagent grade
and were purified by the standard purification proce-
dures. Anhydrous grade of n-hexane (Kanto Kagaku)
was transferred into a bottle containing molecular sieves
(mixture of 3A and 4A 1/16,and 13X) in the drybox under
nitrogen flow. Syntheses of CpꢀTiMe2 ðO-2; 6-i Pr2 C6H3Þ
(1) and CpꢀTiMeðCF3SO3ÞðO-2; 6-i Pr2 C6H3Þ (2) were
according to our previous report [b,17]. All 1H- and 13C-
NMR spectra were recorded on a JEOL JNM-LA400
measurement was taken at low temperature (in toluene-
d8, )70, )50 and )30 °C). The reaction with 3-buten-1-
ol was also explored,and the 1H and 13C NMR spectra
also suggest that the reaction took place affording
CpꢀTiMe½OCH2CH2CH@CH2ŠðOArÞ (6) with exclusive
yield. Although attempts to isolate these complexes as
pure microcrystals were not successful (or these prod-
ucts may exist as liquid under these conditions),the
resultant complexes were very stable at room tempera-
ture at least for several days,and no decomposed or
other products were observed on 1H NMR spectra if the
reaction mixture was warmed to 50 °C for several hours.
In addition,we assume that these olefinic double bonds
do not coordinate to the titanium metal,because no
1
spectrometer (399.65 MHz, H; 100.40 MHz, 13C). All
chemical shifts are given in ppm and are referenced to
tetramethylsilane,and all spectra were obtained in the
solvent indicated at 25 °C unless otherwise noted. All
deuterated NMR solvents were stored over molecular
sieves in the drybox.
1
differences were observed in their H NMR spectra es-
pecially in olefinic regions for 3–6 (4.8–6.0 ppm,Fig. 2)
in addition to the above experimental results. Although
attempts to isolate the cationic analogue like CpꢀTi
½OCH2CH2CH@CH2ŠðOArÞþ by removing methyl
group from 5 or by a replacement of CF3SO3 from 3
were not successful at this moment,we believe that re-
sults observed here would be an interesting contrast to
those performed by ordinary metallocene complexes.
The observed results are also in good agreement with the
result for polymerization of 1,5-hexadiene using Cpꢀ
TiCl2ðOArÞ – MAO catalyst system in which exclusive
selectivity for cyclopolymerization observed in the po-
lymerization using ordinary metallocene complexes was
not seen [22].
3.1. Synthesis for CpꢀTiðCF3SO3Þ½OCH2ðCH2Þ CH@CH2Š
3
ðOArÞ (3)
Into a chilled n-hexane solution (ca. 25 ml) containing 2
(326 mg,0.622 mmol),5-hexen-1-ol (1.0 equivalent to 2)
diluted with n-hexane (5 ml) was added at )30 °C. The
reaction mixture was warmed slowly to room tempera-
ture,and the mixture was stirred for 3 h. The reaction
mixture was passed through Celite pad,and the filter cake
was washed with hexane (10 ml). The combined filtrate
and the wash were taken to dryness under reduced pres-
sure to concentrate the total volume of 10 ml. The chilled

520
K. Nomura, Y. Hatanaka / Inorganic Chemistry Communications 6 (2003) 517–522
2
ð JCAF ¼ 319 Hz),123.0,123.5,129.0,138.0,138.7,159.1
ppm. E.A. Calcd for C29H43F3O5 STi: C,57.23%; H,
7.12%; N,0%. Found: C,57.36%; H,7.25%; N,0.02%.
Red prism microcrystals were grown from a concentrated
hot n-hexane solution upon standing,and the resultant
microcrystals were used for the crystal structure analysis.
3.2. Synthesis for CpꢀTiðCF3ÞðSO3ÞðOCH2CH2CH@CH2Þ
ðOArÞ (4)
The synthetic procedure for 4 was the same as that for
3 except that 2 (352 mg,0.671 mmol) and 3-buten-1-ol
(1.0 equivalent of 2) in place of 5-hexen-1-ol were used.
The chilled ()30 °C) n-hexane solution gave red micro-
crystals (1st crop,355 mg),and the chilled concentrated
solution from the mother liquor gave the second crop (44
mg). Yield 90%. 1H NMR (C6D6): d 7.03 (d,2H, J ¼ 7:3
Hz,C H3),6.95 (t,1H, J ¼ 7:7 Hz,C H3),5.69 (m,1H,
6
6
CH2@CHA),5.02 (dd or m,1H,C H2@CHA),5.00 (dd or
m,1H,C H2@CHA),4.62 and 4.40 (m,2H, ACH2OTi),
3.15 (m,2H, ðCH3Þ2CHA),2.41 (m,2H),1.80 (s,15H,
C5Me5),1.27 (d,6H, J ¼ 6:6 Hz, ðCH3Þ2CHA),1.19 (d,
6H, J ¼ 7:0, ðCH3Þ2CHA) ppm. 13C NMR (C6D6): d
11.2,24.0,24.2,28.8,37.7,117.3,120.2 ( 2JCAF ¼ 318 Hz),
123.1,123.5,129.3,134.2,138.1,159.1 ppm. E.A. Calcd
for C27H39F3O5 STi: C,55.86%; H,6.77%. Found (1): C,
55.94%; H,6.91%. Found (2): C,55.56%; H,6.83%.
3.3. Reaction of 1 with 5-hexen-1-ol
Into a chilled n-hexane solution (ca. 25 ml) dissolved
in 1 (384 mg,0.984 mmol),5-hexen-1-ol (1.0 equivalent
to 1) diluted with n-hexane (5 ml) was added at )30 °C.
The reaction mixture was warmed slowly to room tem-
perature,and the mixture was stirred for 3 h. The re-
action mixture was passed through Celite pad,and the
filter cake was washed with hexane (10 ml). The com-
bined filtrate and the wash were taken to dryness under
reduced pressure to afford yellow tan residue after re-
moving low boiling point compounds (463 mg,esti-
mated crude yield only by the weight was 99%). 1H
NMR (C6D6): d 7.11 (d,2H, J ¼ 7:7 Hz,C 6H3),6.97 (t,
Fig. 2. 1H NMR spectra (in C6D6,4.8–6.0 ppm) for (a) Cp ꢀTi
ðCF3SO3Þ½OCH2ðCH2Þ3CH@CH2ŠðOArÞ (3),(b) Cp ꢀTiðCF3 SO3Þ
½OCH2CH2CH@CH2ŠðOArÞ (4),and for (c) the reaction product of 1
with 5-hexen-1-ol,and (d) the reaction product of 1 with 3-buten-1-ol.
1H, J ¼ 7:5 Hz,C H3),5.76 (m,1H,CH 2@CHA),5.00
6
(dd or m,1H,C H2@CHA),4.95 (dd or m,1H,
CH2@CHA),4.25 and 4.20 (m,2H, ACH2OTi),3.32 (m,
2H, ðCH3Þ2CHA),1.95 (m,2H,CH
2@CHACH2A),
()30 °C) solution gave red microcrystals (1st crop,355
mg). Yield 94%. 1H NMR (C6D6): d 7.04 (d,2H, J ¼ 7:0
Hz,C H3),6.96 (t,1H, J ¼ 7:7 Hz,C H3),5.74 (m,1H,
1.83 (s,15H,C 5Me5),1.52 (m,2H),1.37 (m,2H),1.31
(d,6H, J ¼ 7:0 Hz, ðCH3Þ2CHA),1.26 (d,6H, J ¼ 6:6
Hz, ðCH3Þ2CHA),0.81 (s,3H,Ti AMe) ppm. 13C NMR
(C6D6): d 10.9,23.7,24.0,25.3,26.3,33.2,33.6,43.7,
74.2,114.6,120.5,121.0,123.0,137.0,138.7,158.6 ppm.
6
6
CH2@CHA),5.00 (dd or m,1H,C H2@CHA),4.97 (dd or
m,1H,C H2@CHA),4.56 and 4.36 (m,2H, ACH2OTi),
3.17 (m,2H, ðCH3Þ2CHA),1.92 (m,2H,CH 2@CHA
CH2A),1.81 (s,15H,C 5Me5),1.63 (m,2H),1.31 (m,2H),
1.28 (d,6H, J ¼ 7:0 Hz, ðCH3Þ2CHA),1.20 (d,6H,
J ¼ 7:0 Hz, ðCH3Þ2CHA) ppm. 13C NMR (C6D6): d 11.2,
24.0,24.1,25.1,26.8,32.7,33.7,79.2,114.8,120.2
3.4. Reaction of 1 with 3-buten-1-ol
The basic procedure was the same as that described
above except that 478 mg (1.224 mmol) of 1,and 3-buten-

K. Nomura, Y. Hatanaka / Inorganic Chemistry Communications 6 (2003) 517–522
521
1-ol in place of 5-hexen-1-ol were used. Yellow tan residue
1
Supplementary material
was obtained after the procedure described above. H
NMR (C6D6): d 7.11 (d,2H, J ¼ 7:3 Hz,C 6H3),6.97 (t,
X-ray structure report for CpꢀTiðCF3SO3Þ½OCH2
ðCH2Þ3CH@CH2ŠðOArÞ (3),and 1H and 13C NMR
spectra for 5–6.
1H, J ¼ 7:5 Hz,C H3),5.79 (m,1H,CH 2@CHA),5.03
6
(dd or m,1H,C H2@CHA),4.99 (dd or m,1H,
CH2@CHA),4.30 and 4.25 (m,2H, ACH2OTi),3.30 (m,
2H, ðCH3Þ2CHA),2.27 (m,2H),1.82 (s,15H,C
5Me5),
1.30 (d,6H, J ¼ 7:0 Hz, ðCH3Þ2CHA),1.24 (d,6H,
J ¼ 7:0 Hz, ðCH3Þ2CHA),0.82 (s,3H,Ti AMe) ppm. 13
NMR ðC6D6Þ: d 10.9,11.0,23.9,24.1,26.4,26.6,38.6,
44.4,44.6,74.0,74.1,116.6,120.7,120.9,121.4,123.1,
123.3,135.5,137.3,158.8 ppm.
Acknowledgements
C
The present work is partly supported by Grant-in-
Aid for Scientific Research (B) from the Japan Society
for the Promotion of Science (No. 13555253). The au-
thor would like to express his sincere thanks to Dr. K.
Tsutsumi (NAIST) for showing us to use X-ray crys-
tallography.
3.5. Crystallographic analysis for 3
All measurements were made on a Rigaku RAXIS-
RAPID Imaging Plate diffractometer with graphite
monochromated Mo-Ka radiation. The selected crys-
tal collection parameters are listed in Table 2,and the
structure was solved by direct method and expanded
using Fourier techniques [23]. The non-hydrogen at-
oms were refined anisotropically. Hydrogen atoms
were included but not refined. All calculations were
performed using the teXsan [24] crystallographic
software package of Molecular Structure Corporation.
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Table 2
Crystal and data collection parameters for CpꢀTiðCF3SO3Þ½OCH2
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a
ðCH2Þ3CH@CH2ŠðOArÞð3Þ
Complex
~
ꢁ
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3
Formula; formula weight
Habits; crystal size (mm)
C29H43F3O5STi; 608.61
Red,prism;
0:80 ꢁ 0:50 ꢁ 0:45
Monoclinic
P21/n (No. 14)
8.5325(6); 17.116(2);
22.332(2)
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Crystal system
Space group
ꢀ
ꢀ
ꢀ
a (A); b (A); c (A)
ꢁ
[8] (a) D.W. Stephan,J.C. Stewart,F. Gu erin,R.E.v.H. Spence,W.
3
ꢀ
b (deg); V (A )
Z value
92.825(2); 3257.4(5)
4
1:241 g=cm3
1288.00
243
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(b) D.W. Stephan,J.C. Stewart,S.J. Brown,J.W. Swabey,Q.
Wang,EP881233 A1 (1998).
Dcalcd ðg=cm3Þ
F000
Temp (K)
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ꢀ
k (Mo-Ka) (A)
0.71069
2h range (°)
No. of reflections measured: (Rint
3.0°–55.0°
)
Total: 23172,unique:
7140 (0.100)
7140
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No. of observations
(I > ꢂ10:00dðIÞ)
No. of variables
Residuals: R1; Rw
GOF
352
0.079: 0.192
1.43
(d) R.J. Keaton,K.C. Jayaratne,D.A. Henningsen,L.A. Kot-
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Max (minimum) peak in final diff.
3
0.83 ()0.87)
ꢀ
map (eꢂ/A )
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[14] W.P. Kretschmer,C. Dijkhuis,A. Meetsma,B. Hessen,J.H.
Teuben,Chem. Commun. (2002) 608.
a Diffractometer: Rigaku RAXIS-RAPID Imaging Plate. Structure
solution: direct methods. Refinement: full-matrix least-squares.
P
2
Function minimized:
1=d2ðFo2Þ, p-factor 0.05.
xðFo2 ꢂ Fc2Þ . Least-square weights: w ¼
[15] J. McMeeking,X. Gao,R.E.v.H. Spence,S.J. Brown,D.
Jerermic,USP 6114481 (2000).

522
K. Nomura, Y. Hatanaka / Inorganic Chemistry Communications 6 (2003) 517–522
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(c) G.W. Coates,R.M. Waymouth,J. Am. Chem. Soc. 115 (1993)
91.
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