Preparation of cyclopentadienylrhodium(I) compounds with a dangling CH2C5H5 unit and their use as starting materials for the synthesis of hetero-bimetallic Rh-Ti and Rh-Zr complexes

Article abstract of DOI:10.1016/S0022-328X(03)00532-1

A series of cyclopentadienylrhodium(I) complexes of the general composition [(η⁵-C₅H₄CH₂ C₅H₅)Rh(L)(L′)] (L=L′=C₂ H₄, C₈H₁₄; L=Pⁱ Pr₃, L′=C₂H₄, CPh₂, C=C=CPh₂; L=SbⁱPr₃, L′=CPh₂) with a dangling CH₂C₅ H₅ unit at the π-bonded five-membered ring has been prepared from the corresponding rhodium(I) precursors and NaC₅H₄CH₂C₅H₅ in THF. The compound [(η⁵-C₅H₄ SiMe₂C₅H₅)Rh(PhC≡CPh) (PⁱPr₃)] has similarly been obtained and characterized by single-crystal X-ray diffraction analysis. Deprotonation of [(η⁵-C₅H₄CH₂ C₅H₅)Rh(L)₂] and [(η ⁵-C₅H₄CH₂C₅ H₅)Rh(L)(L′)] with either ⁿBuLi or NaN(SiMe ₃)₂ affords the corresponding anions which react with [(η⁵-C₅H₅)MCl₃] (M=Ti, Zr) to give hetero-bimetallic Rh-Ti and Rh-Zr complexes with the dianion [(η⁵-C₅H₄)₂ CH₂]^2- as the bridging ligand. Treatment of the dinuclear tetrachloro compound [{CH₂(η⁵-C ₅H₄)₂}{RhCl₂(Pⁱ Pr₃)}{TiCl₂(η⁵-C₅ H₅)}], obtained from the related alkyne complex [{CH₂(η⁵-C₅H₄) ₂}{Rh(PhC≡CPh)(PⁱPr₃)} {TiCl₂(η⁵-C₅H₅)}] and HCl, with methyllithium leads to the formation of the tetramethyl derivative [{CH₂(η⁵-C₅ H₄)₂}{Rh(CH₃)₂(Pⁱ Pr₃)}{Ti(CH₃)₂(η⁵- C₅H₅)}]. On a similar route, the hetero-bimetallic dimethyl compound [{CH₂ (η⁵-C₅H₄)₂} {Rh(=CPh₂)(CO)}{Zr(CH₃)₂(η ⁵-C₅H₅)}] has been prepared.

Full text of DOI:10.1016/S0022-328X(03)00532-1

Journal of Organometallic Chemistry 681 (2003) 70ꢃ81
/
www.elsevier.com/locate/jorganchem
Preparation of cyclopentadienylrhodium(I) compounds with a
dangling CH2C5H5 unit and their use as starting materials for the
synthesis of hetero-bimetallic RhÃ
/
Ti and RhÃ
/
Zr complexes
Bernd Stempfle, Olaf Gevert, Helmut Werner *
Institut fur Anorganische Chemie der Universitat Wurzburg, Am Hubland, D-97074 Wurzburg, Germany
¨ ¨ ¨ ¨
Received 27 January 2003; received in revised form 16 May 2003; accepted 16 May 2003
Dedicated to Professor Bernd Krebs on the occasion of his 65th birthday
Abstract
A series of cyclopentadienylrhodium(I) complexes of the general composition [(h5-C5H4CH2C5H5)Rh(L)(L?)] (Lꢀ
C8H14; Lꢀ C2H4, CPh2, CÄCÄCPh2; Lꢀ CPh2) with a dangling CH2C5H5 unit at the p-bonded five-
Pi Pr3, L?ꢀ SbiPr3, L?ꢀ
membered ring has been prepared from the corresponding rhodium(I) precursors and NaC5H4CH2C5H5 in THF. The compound
[(h5-C5H4SiMe2C5H5)Rh(PhCꢀCPh)(PiPr3)] has similarly been obtained and characterized by single-crystal X-ray diffraction
analysis. Deprotonation of [(h5-C5H4CH2C5H5)Rh(L)2] and [(h5-C5H4CH2C5H5)Rh(L)(L?)] with either nBuLi or NaN(SiMe3)2
affords the corresponding anions which react with [(h5-C5H5)MCl3] (Mꢀ
Ti, Zr) to give hetero-bimetallic RhÃTi and RhÃZr
complexes with the dianion [(h5-C5H4)2CH2]2ꢁ as the bridging ligand. Treatment of the dinuclear tetrachloro compound [{CH2(h5-
/
L?ꢀ/C2H4,
/
/
/
/
/
/
/
/
/
/
C5H4)2}{RhCl2(PiPr3)}{TiCl2(h5-C5H5)}], obtained from the related alkyne complex [{CH2(h5-C5H4)2}{Rh(PhCꢀ
/
CPh)(PiPr3)}{TiCl2(h5-C5H5)}] and HCl, with methyllithium leads to the formation of the tetramethyl derivative [{CH2(h5-
C5H4)2}{Rh(CH3)2(Pi Pr3)}{Ti(CH3)2(h5-C5H5)}]. On a similar route, the hetero-bimetallic dimethyl compound [{CH2(h5-
C5H4)2}{Rh(Ä
CPh2)(CO)}{Zr(CH3)2(h5-C5H5)}] has been prepared.
/
# 2003 Elsevier B.V. All rights reserved.
Keywords: Bis(cyclopentadienyl)methane; Hetero-bimetallic complexes; Rhodium; Titan; Zirkonium
1. Introduction
imido ligands can be connected to the anionic [Rh(h5-
C5H4CH2C5H4)] unit [5]. In continuing these studies, we
recently focussed our effort on the coordination of
[TiX2(h5-C5H5)] and [ZrX2(h5-C5H5)] fragments to the
dangling cyclopentadienyl group of the rhodium-con-
taining anion since we anticipated that due to their
Following our research on compounds of the general
composition [{CH2(h5-C5H4)2}{M(L)2}2] with Mꢀ
/Co
[1], Rh [2] and Ir [3], we became interested in learning
whether complexes of this type with different metal
centers can equally be prepared. After we succeeded
with the preparation of compounds where one metal is
rhodium and the second is cobalt or iridium [4], we
showed that instead of the electron-rich Co or Ir in the
potential cooperative behavior hetero-bimetallic RhÃ
/
Ti
and RhÃZr complexes could be interesting candidates as
/
catalysts or catalyst precursors for olefin polymeriza-
tion.
oxidation ꢂ
Mo in the oxidation state ꢂ
/
I and ꢂ
/
III also the electron-poor Nb and
In this paper, we report the synthesis of a variety of
mononuclear rhodium compounds of the type [(h5-
/
V and ꢂVI with stabilizing
/
C5H4CH2C5H5)Rh(L)2]
and
[(h5-C5H4CH2C5H5)-
Rh(L)(L?)] and illustrate that, after they have been
converted to the corresponding anion, they are useful
starting materials for the formation of hetero-bimetallic
complexes with one d8- or d6- and one d0-metal center.
* Corresponding author. Tel.: ꢂ
888-4623.
E-mail address:
Werner).
/
49-931-888-5270; fax: ꢂ49-931-
/
helmut.werner@mail.uni-wuerzburg.de (H.
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00532-1

B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ
/
81
71
2. Results and discussion
containing the SiMe2C5H5 group as a substituent at
the p-bonded five-membered ring. The preparative
procedure was similar to that used for 5 [4b] and gave
the required product 6 as a yellow solid in 70% isolated
yield (Scheme 2).
Single crystals of 6 could be grown from hexane and
investigated by X-ray diffraction. The result of the
structure analysis is shown in Fig. 1. The molecule has
the expected piano-stool-type structure with bond angles
The sodium salt of the substituted cyclopentadienyl
anion [C5H4CH2C5H5]ꢁ, which has been prepared from
CH2(C5H5)2 and NaNH2 in THF [4a], reacts with the
dimeric rhodium(I) precursors [RhCl(C8H14)2]2,
[RhCl(C2H4)2]2 and [RhCl(C2H4)(PiPr3)]2 to give the
halfsandwich-type complexes 1, 3 and 4 in 57ꢃ74% yield
/
(Scheme 1). In the reaction with the bis(cyclooctene)
derivative, the dinuclear compound 2 has been obtained
as a by-product and separated from 1 by column
chromatography. For the original preparation of 2, the
disodium salt [CH2(C5H4)2]Na2 was used as the sub-
strate [4b]. Similar to 5 [4b], the related compounds 1, 3
and 4 are isolated as yellow or orange oils that are
moderately air-sensitive and readily soluble in all
common organic solvents. They can be stored under
PÃ
from 908. Both the RhÃ
as well as the C(1)ÃC(2)Ã
/
RhÃ
/
C(1) and PÃ
/
RhÃ
C(1) and RhÃ
C(20) and C(2)Ã
/
C(2) that deviate only slightly
C(2) bond lengths
C(1)ÃC(10)
/
/
/
/
/
/
bond angles are nearly identical (see Table 1). A
remarkable feature is that the uncoordinated C5H5
ring occupies a sterically rather unfavorable position
since it lies relatively near to the phenyl group having
C(20) as the ipso-carbon atom. We also note that the
SiMe2 moiety is linked to the sp3-hybridized carbon
atom of the C5H5 ring, analogous as suggested by
Komatsu and Yamazaki [8] for the cobalt complex [(h5-
C5H4SiMe2C5H5)Co(h4-C4Ph4)].
argon at ꢁ78 8C for weeks but slowly decompose at
/
1
room temperature or in solution. The H-NMR spectra
of 1, 3 and 4 display six signals for the olefinic protons
of the dangling C5H5 moiety between d 5.9 and 6.6 ppm,
indicating that two isomers in the approximate ratio of
1:1 are present. We assume that the uncoordinated C5H5
ring is linked either at C(2) or C(3) to the
[CH2C5H4Rh(L)2] or [CH2C5H4Rh(L)(L?)] fragment
and thus a similar situation as that found for 5 exists
[4b]. The assignment for the 13C resonances of the C5H4
carbon atoms follows the rule proposed by Coville and
coworkers [6] that C(1) (ipso-C) is less shielded than
C(2) and C(5) and these are less so than C(3) and C(4).
The chemical shift of the bridging CH2 carbon of the
C5H4CH2C5H5 ligand corresponds to that of CH2Ph2,
which is in full agreement with the increment tables for
disubstituted methane derivatives [7].
Besides the [Rh(olefin)2], [Rh(C2H4)(PiPr3)] and
[Rh(C2Ph2)(PiPr3)] fragments, related units containing
a RhÄ
/
CPh2 or RhÄ
/
CÄ
/
CÄ
/
CPh2 group as a building
block could also be coordinated to the [h5-
C5H4CH2C5H5]ꢁ anion. The results of these studies
are summarized in Scheme 3. The reactions of the
corresponding
NaC5H4CH2C5H5 were carried out in THF between ꢁ
78 8C and room temperature and gave the products 7ꢃ
as blue or violet oils in 64ꢃ77% yields. The metalÃ
rhodium(I)
precursors
with
/
/9
/
/
stibine bond of 9 is rather labile and thus upon passing
a slow stream of CO through a solution of 9 in pentane,
a quantitative conversion to the carbonyl(carbene)
complex 10 takes place. The most typical spectroscopic
features of the carbenerhodium(I) compounds 7, 9 and
After we failed to crystallize compounds 1, 3, 4 and 5,
we prepared for comparison the related complex 6
Scheme 1.

72
B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ81
/
Scheme 2.
n
with either BuLi or NaN(SiMe3)2 and reacting the in
10 are the two slightly separated signals for the 13C
nuclei of the carbene carbon atom at d 262.0 and 261.8
(for 7), 258.2 and 258.0 (for 9) and 285.7 and 284.9 (for
10) ppm, the two sets being due to the presence of two
isomers as already discussed for compounds 1, 3 and 4.
The 13C-NMR spectrum of 8 also displays two reso-
situ formed anions with [(h5-C5H5)TiCl3] as the sub-
strate. On this route, the RhÃ
/
Ti compounds 11ꢃ14 were
/
obtained in 54ꢃ86% yield (Scheme 4). The composition
/
of the red microcrystalline solids, which for a short
period of time can be handled in air, has been confirmed
both by elemental analysis and spectroscopic techni-
nances for the a-carbon atom of the RhÄ
/
CÄ
/
CÄ/CPh2
chain at d 232.7 and 229.8 ppm, whereas only a single
resonance for the b-C and a single resonance for the g-C
carbon atom is observed. We note that the missing link
ques. The 1H- as well as the 13C-NMR spectra of 11ꢃ
14
/
display two sets of signals for each C5H4 moiety with
chemical shifts comparable to those of the homo-
binuclear compounds [{CH2(h5-C5H4)2}{Rh(L)(L?)}2]
[3] and [{CH2(h5-C5H4)2}{TiCl2(h5-C5H5)}2] [10], re-
spectively. The resonance for the carbene carbon atom
appears in the 13C-NMR spectrum of 14 at d 261.1 ppm
as a doublet of doublets, the chemical shift being nearly
identical to that of the isomers of the precursor 7 (d
262.0 and 261.8 ppm).
between
C5H4CH2C5H5)Rh(Ä
been prepared from the alkynyl(hydrido)rhodium(III)
precursor [RhH(Cꢀ and
CPh)Cl(py)(PiPr3)2]
7
and
8
with the composition [(h5-
CÄ
CHPh)(PiPr3)] has previously
/
/
/
NaC5H4CH2C5H5 in 76% yield [4b]. The counterpart
of 8 with an unsubstituted cyclopentadienyl ring is also
known [9].
To use the mononuclear cyclopentadienylrhodium(I)
compounds with the dangling CH2C5H5 unit as starting
materials for the synthesis of hetero-bimetallic com-
plexes, the corresponding anions had to be generated.
This was done by treating the precursors 1, 3, 5 and 7
Upon treatment with HCl, compound 13 can be
converted to the Rh(III)Ã/Ti(IV) derivative 15 in nearly
quantitative yield (Scheme 5). If we take our experience
with the protonation of electron-rich cyclopentadienyl
complexes of Group 9 into consideration [11], we
Fig. 1. Molecular structure of compound 6; anisotropic displacement parameters are depicted at the 50% probability level. Hydrogen atoms are
omitted for clarity.

B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ
/
81
73
Table 1
Selected bond distances (A) and bond angles (8) with estimated S.D. for compound 6
˚
˚
Bond distances (A)
RhÃ
RhÃ
RhÃ
/
P
2.242(3)
2.06(1)
2.07(1)
1.27(1)
1.44(1)
C(2)Ã
/
C(20)
1.43(1)
1.87(1)
1.89(1)
1.86(1)
1.90(1)
C(40)Ã
C(41)Ã
C(42)Ã
C(43)Ã
C(44)Ã
/
C(41)
C(42)
C(43)
C(44)
C(40)
1.48(2)
1.32(2)
1.43(2)
1.33(2)
1.48(2)
/C(1)
SiÃ
SiÃ
SiÃ
SiÃ
/
C(30)
C(35)
C(36)
C(40)
/
/C(2)
/
/
C(1)Ã
/C(2)
/
/
C(1)Ã
/C(10)
/
/
Bond angles (8)
C(1)Ã
C(2)Ã
C(2)Ã
C(1)Ã
C(30)Ã
C(30)Ã
C(30)Ã
C(35)Ã
/
RhÃ
/
P
93.5(3)
93.6(3)
150(1)
150(1)
112.1(5)
SiÃ
SiÃ
C(40)Ã
C(41)Ã
C(41)Ã
C(42)Ã
C(43)Ã
/
C(40)Ã
C(40)Ã
/
C(41)
C(44)
109.3(9)
110.6(9)
110(1)
/
RhÃ
/P
/
/
/
C(1)Ã
/C(10)
/
C(41)Ã
C(40)Ã
C(42)Ã
C(43)Ã
C(44)Ã
/
C(42)
C(44)
C(43)
C(44)
C(40)
/
C(2)Ã
/C(20)
/
/
101(1)
110(1)
108(1)
111(1)
/
SiÃ
SiÃ
SiÃ
SiÃ
/
C(40)
C(35)
C(36)
C(36)
/
/
/
/
108.9(5)
108.7(5)
110.5(6)
/
/
/
/
/
/
/
/
assume that in the initial step of the reaction an attack
of HCl at the rhodium center takes place which is
followed by a migratory insertion of the alkyne ligand
ppm. The corresponding resonances for the 13C nuclei
appear in the 13C-NMR spectrum at d ꢁ
15.0 ppm (dd)
/
and d 45.8 ppm (s), respectively. Regarding the reactiv-
ity of 16, we observed that the compound reacts
photochemically with CO to presumably give the
hetero-bimetallic dicarbonyl complex [{CH2(h5-
C5H4)2}{Rh(CH3)2(PiPr3)}{Ti(CO)2(h5-C5H5)}]. This
molecule, however, is extremely air- and light-sensitive
and thus we failed to characterize the compound by a
correct elemental analysis.
into the generated RhÃ
intermediate would then react with a second molecule
of HCl by cleavage of the RhꢁCPhÄCHPh bond and
elimination of stilbene [12].
/H bond. The vinylrhodium
/
/
The chloro ligands of the hetero-bimetallic compound
15 can easily be substituted by methyl groups if the
starting material is treated with an excess of methyl-
lithium. Due to some unknown side reactions and the
sensitivity of the product toward heat and light, the
isolated yield of 16 was only 38%. The presence of two
methyl units at rhodium and of two at titanium is
confirmed by the 1H-NMR spectrum of 16, which shows
The synthesis of the RhÃ
(Scheme 6) proceeded analogous to that of the RhÃ
/
Zr complexes 17ꢃ
/
19
Ti
/
counterparts. The yield of the hetero-bimetallic pro-
ducts, which are oily or low-melting substances, is good
to excellent. Attempts to replace the chloro for hydrido
ligands in 18 and 19, using either NaBH4 or LiAlH4 as
hydride source, remained unsuccessful. We note that a
for the RhÃ
ppm and for the TiÃ
/
CH3 protons a doublet of doublets at d 0.70
/CH3 protons a singlet at d 0.01
Scheme 3.

74
B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ
/
81
Scheme 4.
relative of 17 with two CO instead of two ethene ligands
and an indenyl instead of a cyclopentadienyl ring at
rhodium is known and has been prepared stepwise from
[(h5-C5H5)ZrCl3(dme)], [Me2C(C5H4)(C9H6)]Li2 and
[RhCl(CO)2]2 as starting materials [13].
in toluene as solvent to give in 1 h 9.7 g of polyethylene
(PE). The activity (g PE per g(12) h) at a pressure of 1
bar is 3490, which is comparable to that with [(h5-
C5H5)2TiCl2] and MAO as the catalytic system [14]. We
are currently investigating, whether there is a difference
in the tacticity of polypropylene if 12 or 17 and MAO
Similarly, as described for the preparation of 15, the
Rh(C2Ph2) unit of 18 could be converted to a RhCl2
moiety by treatment with HCl. The so-formed tetra-
chloro complex 20 was obtained as a red oil in 91%
yield. While attempts to prepare the analogous carbo-
nyl(dichloro)rhodium compound [{CH2(h5-C5H4)2}-
{Rh(CO)Cl2}{ZrCl2(h5-C5H5)}] from 19 and HCl
failed, the carbene(carbonyl) complex 19 afforded
upon reaction with methyllithium the Zr(CH3)2 deriva-
tive 21 in moderate yield (Scheme 7). Our hope that by
careful warming or by low-temperature UV irradiation
of 21 one of the methyl groups could be transformed
from zirconium to rhodium, thereby generating an acyl
or alkyl ligand at the electron-rich metal center and
instead of [(h5-C5H5)2MCl2] (Mꢀ
/
Ti, Zr) and MAO are
used as catalysts for the polymerization of propylene,
and we will report about the results of these studies in
due course.
3. Experimental
All experiments were carried out under an atmosphere
of argon by Schlenk techniques. The starting materials
NaC5H4CH2C5H5 [4a], Me2Si(C5H5)2 [15], [RhCl-
(C8H14)2]2 [16], [RhCl(C2H4)2]2 [17], [RhCl(C2H4)-
(PiPr3)]2 [18], trans-[RhCl(PhCꢀ
trans-[RhCl(Ä P, Sb) [19], trans-
CPh2)(EiPr3)2] (Eꢀ
[RhCl(ÄCÄCÄ
/
CPh)(PiPr3)2] [12],
equally a metalÃ
/
metal bond, was not fulfilled.
/
/
/
/
/
CPh2)(PiPr3)2] [20], [(h5-C5H5)TiCl3]
The results of some preliminary experiments regard-
ing the catalytic potential of the apparently most
suitable hetero-bimetallic complex 12 can be summar-
ized as follows. With 0.058 mmol of 12 and an excess of
[21] and [(h5-C5H5)ZrCl3] [22] were prepared as de-
scribed in the literature. NMR spectra were recorded at
room temperature (r.t.) on Bruker AC 200 and Bruker
MAO as co-catalyst (ratio 12:MAOꢀ/260), C2H4 reacts
AMX 400 instruments, and IR spectra on a Perkinꢃ
/
Scheme 5.

B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ
/
81
75
Scheme 6.
Elmer 1420 or an IFS 25 FT-IR infrared spectrometer.
Melting points were determined by DTA. Abbreviations
used: s, singlet; d, doublet; sept, septet; m, multiplet; br,
broadened signal.
2), the solvent was removed and the remaining yellow oil
was dried in vacuo; yield 174 mg (57%). Anal. Found: C,
70.07; H, 8.71. Calc. for C27H39Rh: C, 69.52; H, 8.43%.
1H-NMR (CDCl3, 200 MHz): d 6.56, 6.40, 6.35, 6.24,
6.14, 5.99 (all m, 3H, olefinic protons of C5H5), 4.92,
4.41 (both m, 2H each, C5H4Rh), 3.50, 3.43 (both m,
3.1. Preparation of [(h5-C5H4CH2C5H5)Rh(C8H14)2]
(1) and [{CH2(h5-C5H4)2}{Rh(C8H14)2}2] (2)
2H, CH2), 2.85 (m, 2H, CH2 of C5H5), 2.30 (m, 4H, Ä
/
CH of C8H14), 1.58, 1.28 (both m, 24H, CH2 of C8H14)
ppm. 13C-NMR (CDCl3, 50.3 MHz): d 148.3, 146.3
(both s, carbon atom of C5H5 connected with CH2),
A
suspension of 109 mg (0.66 mmol) of
NaC5H4CH2C5H5 in 15 ml of THF was cooled to
78 8C and then treated under continuous stirring with
135.5, 134.4, 133.1, 128.3, 127.6 (all s, Ä
108.3, 107.4 (both s, ipso-C of C5H4Rh), 91.0, 90.1 (both
d, J(Rh,C)ꢀ3.7 Hz, C(2,5) of C5H4Rh), 88.2 (m, C(3,4)
of C5H4Rh), 65.1, 64.2 (both m, ÄCH of C8H14), 43.6,
/
CH of C5H5),
ꢁ
/
a solution of 251 mg (0.35 mmol) of [RhCl(C8H14)2]2 in
10 ml of THF. After the reaction mixture was warmed
to r.t., it was stirred for 2 h. The solvent was evaporated
in vacuo, and the residue was extracted three times with
5 ml of hexane each. The combined extracts were
concentrated to ca. 1 ml and the solution was chroma-
tographed on Al2O3 (neutral, activity grade III, length
of column 10 cm). With hexane two fractions were
eluted of which the first contained the mononuclear
complex 1. It was brought to dryness in vacuo, the
residue was dissolved in 3 ml of hexane and the solution
was again chromatographed on Al2O3. From the major
fraction (the minor fraction contained small amounts of
/
/
41.9 (both s, CH2 of C5H5), 33.4, 33.0, 27.0 (all s, CH2 of
C8H14), 27.1, 25.3 (both s, CH2) ppm. The solvent of the
second fraction containing the dinuclear compound 2
was also evaporated in vacuo to give a light red oil; yield
61 mg (24%). Anal. Found: C, 65.75; H, 8.77. Calc. for
1
C43H66Rh2: C, 65.47; H, 8.43%. H-NMR (CDCl3, 200
MHz): d 4.93 (br s, 4H, H(2,5) of C5H4Rh), 4.42 (br s,
4H, H(3,4) of C5H4Rh), 3.46 (br s, 2H, CH2), 2.32 (m,
8H, Ä
/
CH of C8H14), 1.58, 1.30 (both m, 48H, CH2 of
C8H14) ppm.
Scheme 7.

76
B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ81
/
3.2. Preparation of [(h5-C5H4CH2C5H5)Rh(C2H4)2]
(3)
81.0 MHz): d 71.8, 71.7 (both d, J(Rh,P)ꢀ
ppm.
/200.5 Hz)
A
suspension of 179 mg (1.08 mmol) of
3.4. Preparation of [(h5-C5H4SiMe2C5H5)Rh(PhCꢀ
CPh)(PiPr3)] (6)
/
NaC5H4CH2C5H5 in 25 ml of THF was cooled to ꢁ
/
78 8C and then treated under continuous stirring with a
solution of 214 mg (0.55 mmol) of [RhCl(C2H4)2]2 in 10
ml of THF. After the reaction mixture was warmed to
r.t., it was stirred for 3 h. The solvent was evaporated in
vacuo and the residue was extracted three times with 5
ml of hexane each. The combined extracts were con-
centrated to ca. 1 ml and the solution was chromato-
graphed on Al2O3 (neutral, activity grade III, length of
column 10 cm). With hexane, a bright yellow fraction
was eluted from which after removal of the solvent a
yellow oil was isolated; yield 241 mg (74%). Anal.
Found: C, 59.73; H, 6.49. Calc. for C15H19Rh: C,
A suspension of 8 mg (0.20 mmol) of NaNH2 in 3 ml
of THF was cooled to ꢁ78 8C and then treated under
continuous stirring with a solution of 38 mg (0.20 mmol)
of Me2Si(C5H5)2 in 3 ml of THF. After the reaction
mixture was warmed to r.t., it was irradiated in an
ultrasound bath for 10 min. The milky suspension was
/
again cooled to ꢁ78 8C and slowly evacuated to remove
/
NH3. While the low temperature was maintained, the
suspension was treated with a solution of 115 mg (0.20
mmol) of trans-[RhCl(PhCꢀ
CPh)(PiPr3)2] in 5 ml of
/
THF. The reaction mixture was warmed to r.t. and
stirred for 3 h. The solvent was evaporated in vacuo and
the residue was extracted three times with 5 ml of
pentane each. The combined extracts were concentrated
to ca. 2 ml in vacuo and the solution was chromato-
graphed on Al2O3 (neutral, activity grade III, length of
column 10 cm). With hexane, first an off-white fraction
was eluted which was withdrawn. Continuous elution
with hexane gave a yellow fraction which was concen-
trated to ca. 1 ml in vacuo. After the solution was stored
1
59.61; H, 6.34%. H-NMR (CDCl3, 200 MHz): d 6.52,
6.42, 6.33, 6.21, 6.14, 5.97 (all m, 3H, olefinic protons of
C5H5), 5.22 (m, 2H, H(2,5) of C5H4Rh), 5.01 (m, 2H,
H(3,4) of C5H4Rh), 2.93, 2.90 (both s, 2H, CH2), 2.83
(m, 2H, CH2 of C5H5), 2.65, 1.21 (both m, 8H, C2H4)
ppm. 13C-NMR (CDCl3, 50.3 MHz): d 147.8, 146.2 (s,
carbon atom of C5H5 connected with CH2), 133.4,
133.0, 132.4, 131.4, 128.4, 128.0 (all s, Ä
110.7, 110.6 (both d, J(Rh,C)ꢀ3.0 Hz, ipso-C of
C5H4Rh), 88.6, 88.1 (both d, J(Rh,C)ꢀ3.8 Hz, C(2,5)
/CH of C5H5),
/
/
at ꢁ
separated from the mother liquor, washed with small
quantities of pentane (ꢁ20 8C) and dried; yield 88 mg
(70%). Anal. Found: C, 67.32; H, 7.68. Calc. for
/
78 8C, yellow crystals precipitated which were
of C5H4Rh), 87.0 (m, C(3,4) of C5H4Rh), 43.3, 41.3
(both s, CH2 of C5H5), 38.2 (m, C2H4), 26.5, 25.6 (both
s, CH2) ppm.
/
C35H46PRhSi: C, 66.86; H, 7.38%. IR (hexane): n(Cꢀ
/
3.3. Preparation of [(h5-
C) 1830 cmꢁ1. 1H-NMR (C6D6, 200 MHz): d 8.05, 7.12
(both m, 10H, C6H5), 6.32, 6.15 (both m, 4H, olefinic
protons of C5H5), 5.05, 4.95 (both m, 2H each,
C5H4Rh), 2.85 (m, 1H, SiCH of C5H5), 1.45 (m, 3H,
C5H4CH2C5H5)Rh(C2H4)(PiPr3)] (4)
This compound was prepared analogous as described
for 3 from 164 mg (0.99 mmol) of NaC5H4CH2C5H5
and 291 mg (0.45 mmol) of [RhCl(C2H4)(PiPr3)]2. After
column chromatography and evaporation of the sol-
vent, an orange oil was isolated; yield 133 mg (68%).
Anal. Found: C, 60.49; H, 8.32. Calc. for C22H36PRh:
C, 60.85; H, 8.36%. 1H-NMR (C6D6, 200 MHz): d 6.42,
6.29, 6.21, 6.11, 6.00, 5.90 (all m, 3H, olefinic protons of
C5H5), 5.14, 5.08 (both m, 2H, H(2,5) of C5H4Rh), 5.00
(m, 2H, H(3,4) of C5H4Rh), 3.16, 3.11 (both m, 2H,
CH2), 2.83, 2.78 (both m, 2H, CH2 of C5H5), 2.33, 1.68
(both m, 2H each, C2H4), 1.46 (m, 3H, PCHCH3), 1.00,
PCHCH3), 1.07, 0.98 (both dd, J(P,H)ꢀ
J(H,H)ꢀ7.1 Hz, 18H, PCHCH3), 0.30 (s, 6H, SiCH3)
ppm. 31P-NMR (C6D6, 81.0 MHz):
57.0 (d,
J(Rh,P)ꢀ244.0 Hz) ppm.
/
13.2 Hz,
/
d
/
3.5. Preparation of [(h5-C5H4CH2C5H5)Rh
(Ä
CPh2)(PiPr3)] (7)
/
This compound was prepared analogous as described
for 3 from 34 mg (0.21 mmol) of NaC5H4CH2C5H5 and
127 mg (0.21 mmol) of trans-[RhCl(Ä
/
CPh2)(PiPr3)2].
0.96 (both dd, J(P,H)ꢀ
/
13.2 Hz, J(H,H)ꢀ
/
7.0 Hz, 18H,
PCHCH3) ppm. 13C-NMR (C6D6, 50.3 MHz): d 148.9,
146.5 (both s, carbon atoms of C5H5 connected with
After column chromatography and evaporation of the
solvent, a deep blue oil was isolated; yield 77 mg (65%).
Anal. Found: C, 68.85; H, 7.22. Calc. for C33H42PRh:
1
CH2), 135.4, 133.3, 132.6, 130.9, 128.4, 127.5 (all s, Ä
of C5H5), 103.4, 102.7 (both dd, J(Rh,C)ꢀ8.0 Hz,
J(P,C)ꢀ3.0 Hz, ipso-C of C5H4Rh), 86.4, 85.7 (both m,
C(2,5) of C5H4Rh), 84.1 (m, C(3,4) of C5H4Rh), 43.4,
41.3 (both s, CH2 of C5H5), 38.2 (d, J(Rh,C)ꢀ13.4 Hz,
C2H4), 28.6 (br s, CH2), 25.0 (d, J(P,C)ꢀ19.5 Hz,
PCHCH3), 19.8 (s, PCHCH3) ppm. 31P-NMR (C6D6,
/CH
C, 69.21; H, 7.39%. H-NMR (C6D6, 200 MHz): d 7.44
/
(m, 4H, C6H5), 7.07 (m, 6H, C6H5), 6.49, 6.41, 6.30.
6.22, 6.12, 5.97 (all m, 3H, olefinic protons of C5H5),
5.02, 4.91 (both m, 2H each, C5H4Rh), 2.98 (br s, 2H,
CH2), 2.91 (m, 2H, CH2 of C5H5), 1.41 (m, 3H,
/
/
/
PCHCH3), 1.01, 0.94 (both dd, J(P,H)ꢀ
/
13.0 Hz,
7.0 Hz, 18H, PCHCH3) ppm. 13C-NMR
J(H,H)ꢀ
/

B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ
/
81
77
(C6D6, 50.3 MHz): d 262.0, 261.8 (both dd, J(Rh,C)ꢀ
/
3.7. Preparation of [(h5-C5H4CH2C5H5)Rh
(Ä
CPh2)(SbiPr3)] (9)
51.1 Hz, J(P,C)ꢀ CPh2), 150.6, 148.7
/
18.0 Hz, RhÄ
/
/
(both s, ipso-C of C6H5), 147.2, 146.4 (both s, carbon
atom of C5H5 connected with CH2), 135.1, 135.0, 133.7,
This compound was prepared analogous as described
for 3 from 66 mg (0.40 mmol) of NaC5H4CH2C5H5 and
131.9, 131.1, 130.1, 129.1, 128.1 (all s, C6H5 and Ä
C5H5), 103.2, 101.1 (both dd, J(Rh,C)ꢀ5.7 Hz,
J(P,C)ꢀ2.7 Hz, ipso-C of C5H4Rh), 85.9 (dd,
J(Rh,C)ꢀJ(P,C)ꢀ2.8 Hz, C(2,5) of C5H4Rh), 80.6
(m, C(3,4) of C5H4Rh), 43.3, 41.5 (both s, CH2 of
C5H5), 30.5, 30.2 (both s, CH2), 26.5 (d, J(P,C)ꢀ18.0
Hz, PCHCH3), 20.4 (s, PCHCH3) ppm. 31P-NMR
(C6D6, 81.0 MHz): d 58.1, 58.0 (both d, J(Rh,P)ꢀ
242.8 Hz) ppm.
/
CH of
/
320 mg (0.40 mmol) of trans-[RhCl(Ä
/
CPh2)(SbiPr3)2].
/
After column chromatography and evaporation of the
solvent, a deep blue oil was isolated; yield 206 mg (77%).
Anal. Found: C, 59.93; H, 6.49. Calc. for C33H42RhSb:
/
/
1
/
C, 59.75; H, 6.38%. H-NMR (C6D6, 200 MHz): d 7.70
(m, 4H, C6H5), 7.04 (m, 6H, C6H5), 6.52, 6.40, 5.34,
6.26, 6.10, 5.92 (all m, 3H, olefinic protons of C5H5),
5.14, 4.98 (both m, 2H each, C5H4Rh), 3.02 (br s, 2H,
CH2), 2.91 (m, 2H, CH2 of C5H5), 1.33 (sept, 3H,
/
J(H,H)ꢀ
7.0 Hz, SbCHCH3) ppm. 13C-NMR (C6D6, 50.3 MHz):
d 258.2, 258.0 (both d, J(Rh,C)ꢀ46.9 Hz, RhÄCPh2),
/
6.9 Hz, SbCHCH3), 1.08 (d, 18H, J(H,H)ꢀ
/
3.6. Preparation of [{h5-C5H4CH2C5H5}Rh(Ä
CPh2)(PiPr3)] (8)
/
CÄ
/
CÄ
/
/
/
166.6, 160.0 (both s, ipso-C of C6H5), 148.1, 147.4 (both
s, carbon atom of C5H5 connected with CH2), 135.1,
135.0, 133.7, 131.9, 131.1, 130.1, 129.1, 128.1 (all s, C6H5
A solution of 224 mg (0.34 mmol) of trans-[RhCl(Ä
/
CÄCÄ
/
/
CPh2)(PiPr3)2] in 25 ml THF was cooled to ꢁ
/
78 8C and then treated under continuous stirring with
a solution of 75 mg (0.45 mmol) of NaC5H4CH2C5H5 in
15 ml of THF. After the reaction mixture was warmed
to r.t., it was stirred for 3 h. The solvent was evaporated
in vacuo and the residue was extracted three times with
10 ml of hexane each. To the combined extracts, 0.5 ml
of CH3I was added and after stirring for 30 min, the
solution was filtered. The filtrate was concentrated in
vacuo to ca. 1 ml and the solution was chromatographed
on Al2O3 (neutral, activity grade V, length of column 8
cm). With hexane, a violet fraction was eluted which was
purified by a repeated chromatography. After evapora-
tion of the solvent, a violet oil was obtained; yield 95 mg
(64%). Anal. Found: C, 70.38; H, 6.99. Calc. for
and Ä
Hz, ipso-C of C5H4Rh), 84.4, 84.3 (both d, J(Rh,C)ꢀ
3.8 Hz, C(2,5) of C5H4Rh), 80.7 (d, J(Rh,C)ꢀ2.2 Hz,
/
CH of C5H5), 102.5, 101.6 (both d, J(Rh,C)ꢀ5.7
/
/
/
C(3,4) of C5H4Rh), 43.4, 41.3 (both s, CH2 of C5H5),
31.6, 30.9 (both s, CH2), 22.0 (s, SbCHCH3), 18.4 (d,
J(Rh,C)ꢀ3.1 Hz, SbCHCH3) ppm.
/
3.8. Preparation of [(h5-C5H4CH2C5H5)Rh
(ÄCPh2)(CO)] (10)
/
A slow stream of CO was passed through a solution
of 206 mg (0.31 mmol) of 9 in 20 ml of pentane. After
the gas flow was stopped, the solution was stirred for 1 h
at r.t., which led to a change of color from blue to deep
red. The solvent was evaporated in vacuo, the residue
was dissolved in 2 ml of hexane and the solution was
chromatographed on Al2O3 (neutral, activity grade III,
length of column 10 cm). With hexane, a red fraction
was eluted from which a red oil was isolated; yield 130
mg (95%). Anal. Found: C, 68.10; H, 4.83. Calc. for
C25H21ORh: C, 68.19; H, 4.81%. IR (hexane): n(CO)
1980 cmꢁ1. 1H-NMR (C6D6, 200 MHz): d 7.43 (m, 4H,
C6H5), 6.99 (m, 6H, C6H5), 6.51, 6.46, 6.33, 6.25, 6.07,
5.88 (all m, 3H, olefinic protons of C5H5), 5.22, 4.90
(both m, 2H each, C5H4Rh), 3.15, 3.04 (both s, 2H,
CH2), 2.76, 2.69 (both s, 2H, CH2 of C5H5) ppm. 13C-
NMR (C6D6, 50.3 MHz): d 285.7, 284.9 (both d,
C35H42PRh: C, 70.46; H, 7.10%. IR (hexane): n(CÄ
/
CÄ
/
C) 1934 cmꢁ1. H-NMR (C6D6, 200 MHz): d 7.92 (m,
4H, C6H5), 7.19 (m, 6H, C6H5), 6.49, 6.42, 6.27, 6.19,
6.08, 5.92 (all m, 3H, olefinic protons of C5H5), 5.17,
4.89 (both m, 4H, C5H4Rh), 3.10 (br s, 2H, CH2), 2.79,
2.75 (both s, 2H, CH2 of C5H5), 2.13 (m, 3H, PCHCH3),
1
0.97 (dd, J(P,H)ꢀ
PCHCH3) ppm. 13C-NMR (C6D6, 50.3 MHz): d
232.7, 229.8 (both dd, J(Rh,C)ꢀ68.3 Hz, J(P,C)ꢀ
28.0 Hz, RhÄC), 202.6 (dd, J(Rh,C)ꢀ16.3 Hz,
J(P,C)ꢀ7.0 Hz, RhÄCÄC), 149.6, 148.9 (both s, ipso-
/
13.2 Hz, J(H,H)ꢀ
/
7.1 Hz, 18H,
/
/
/
/
/
/
/
C of C6H5), 146.2, 146.0 (both s, carbon atom of C5H5
connected with CH2), 135.0, 134.7, 133.0, 131.9, 130.8,
130.3, 128.1, 127.0 (all s, C6H5 and Ä
(dd, J(Rh,C)ꢀ2.1 Hz, J(P,C)ꢀ4.9 Hz, RhÄ
104.7, 103.7 (both dd, J(Rh,C)ꢀ4.8 Hz, J(P,C)ꢀ
Hz, ipso-C of C5H4Rh), 84.9 (dd, J(Rh,C)ꢀJ(P,C)ꢀ
/
CH of C5H5), 120.9
CÄCÄC),
2.8
/
/
/
/
/
J(Rh,C)ꢀ
/
47.8 Hz, RhÄ
/
CPh2), 192.9, 192.4 (both d,
/
/
J(Rh,C)ꢀ
/
100.4 Hz, CO), 165.0, 161.3 (both s, ipso-C
/
/
of C6H5), 146.5, 145.0 (both s, carbon atom of C5H5
connected with CH2), 134.8, 133.7, 131.9, 130.8, 128.8,
3.8 Hz, C(2,5) of C5H4Rh), 81.7 (m, C(3,4) of C5H4Rh),
43.2, 41.8 (both s, CH2 of C5H5), 31.1, 30.9 (both s,
127.1, 126.8, 125.3 (all s, C6H5 and Ä
105.4, 104.3 (both d, J(Rh,C)ꢀ4.8 Hz, ipso-C of
C5H4Rh), 90.2, 90.1 (both d, J(Rh,C)ꢀ3.5 Hz, C(2,5)
of C5H4Rh), 88.7 (d, J(Rh,C)ꢀ3.0 Hz, C(3.4) of
/CH of C5H5),
CH2), 26.8 (d, J(P,C)ꢀ
PCHCH3) ppm. 31P-NMR (C6D6, 81.0 MHz): d 69.0,
68.9 (both d, J(Rh,P)ꢀ199.2 Hz) ppm.
/
22.1 Hz, PCHCH3), 19.8 (s,
/
/
/
/

78
B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ81
/
C5H4Rh), 43.5, 41.3 (both s, CH2 of C5H5), 30.9 (br s,
CH2) ppm.
ml in vacuo and the solution layered with 15 ml of
pentane. After storing the mixture at ꢁ78 8C, red
/
crystals precipitated which were filtered, washed twice
with 5 ml of pentane each and dried; yield 159 mg (66%).
Anal. Found: C, 49.91; H, 4.86; Rh, 20.87; Ti, 9.33.
Calc. for C20H23Cl2RhTi: C, 49.52; H, 4.78; Rh, 21.21;
3.9. Preparation of [{CH2(h5-
C5H4)2}{Rh(C8H14)2}{TiCl2(h5-C5H5)}] (11)
1
A solution of 176 mg (0.38 mmol) of 1 in 15 ml of
Ti, 9.87%. H-NMR (CDCl3, 200 MHz): d 6.55 (s, 5H,
hexane was cooled to ꢁ
/
78 8C and then treated with 0.20
C5H5), 6.42, 6.39 (both vt, Nꢀ2.1 Hz, 2H each,
/
ml (0.40 mmol) of a 2.0-M solution of n-butyllithium in
hexane. After the reaction mixture was warmed to r.t., it
was stirred for 20 min. The solvent was removed in
vacuo, the residue was washed twice with 5 ml of hexane
each and then dissolved in 15 ml of THF. The solution
containing the lithium salt of the anion of 1 was cooled
C5H4Ti), 5.27, 4.99 (both m, 4H, C5H4Rh), 3.82 (s,
2H, CH2), 2.72, 1.25 (both br s, C2H4) ppm. 13C-NMR
(CDCl3, 50.3 MHz): d 136.4 (s, ipso-C of C5H4Ti), 122.9
(s, C(2,5) of C5H4Ti), 117.1 (s, C(3,4) of C5H4Ti), 119.9
(s, C5H5Ti), 111.2 (m, ipso-C of C5H4Rh), 89.0 (d,
J(Rh,C)ꢀ
/
3.0 Hz, C(2,5) of C5H4Rh), 87.0 (d,
3.6 Hz, C(3,4) of C5H4Ti), 39.2 (m, C2H4),
to ꢁ
/
78 8C and added dropwise to a solution of 86 mg
J(Rh,C)ꢀ
/
(0.39 mmol) of [(h5-C5H5)TiCl3] in 15 ml of THF. The
reaction was warmed slowly (ca. 2 h) to r.t. and stirred
for 2 h. The solvent was evaporated in vacuo and the
residue was extracted three times with 10 ml of toluene
each. The combined extracts were concentrated to ca. 2
ml in vacuo and the solution layered with 15 ml of
29.9 (s, CH2) ppm.
3.11. Preparation of [{CH2(h5-C5H4)2}{Rh(PhCꢀ
CPh)(PiPr3)}{TiCl2(h5-C5H5)}] (13)
/
This compound was prepared analogous as described
for 11 from 224 mg (0.38 mmol) of [(h5-
pentane. After storing the mixture at ꢁ
/
78 8C, red
crystals precipitated which were filtered, washed twice
with 5 ml of pentane each and dried; yield 133 mg (54%).
Anal. Found: C, 59.59; H, 6.60. Calc. for
C32H43Cl2RhTi: C, 59.18; H, 6.67%. 1H-NMR
(CDCl3, 400 MHz): d 6.58 (s, 5H, C5H5Ti), 6.43, 6.31
C5H4CH2C5H4Li)Rh(PhCꢀ
/
CPh)(PiPr3)]
(prepared
from 5 and an equimolar amount of n-butyllithium)
and 83 mg (0.38 mmol) of [(h5-C5H5)TiCl3] in 30 ml of
THF. After recrystallization from toluene/hexane, a
light red solid was isolated; yield 251 mg (86%). Anal.
Found: C, 60.08; H, 5.99; Rh, 13.11. Calc. for
(both vt, Nꢀ/2.1 Hz, 2H each, C5H4Ti), 4.95 (m, 4H,
H(2,5) of C5H4Rh), 4.45 (m, 4H, H(3,4) of C5H4Rh),
C39H46Cl2PRhTi: C, 61.04; H, 6.04; Rh, 13.41%. IR
1
3.03 (br s, 2H, CH2), 2.31 (m, 4H, Ä
/
CH of C8H14), 1.60,
(toluene): n(Cꢀ
/
C) 1832 cmꢁ1. H-NMR (C6D6, 200
1.29 (both m, 24H, CH2 of C8H14) ppm. 13C-NMR
(CDCl3, 100.6 MHz): d 136.8 (s, ipso-C of C5H4Ti),
121.9 (s, C(2,5) of C5H4Ti), 119.8 (s, C5H5Ti), 117.9 (s,
MHz): d 8.10, 7.08 (both m, 10H, C6H5), 6.54 (s, 5H,
C5H5Ti), 6.48, 6.36 (both m, 2H each, C5H4Ti), 5.52,
5.25 (both m, 2H each, C5H4Rh), 3.38 (s, 2H, CH2), 1.61
C(3,4) of C5H4Ti), 108.0 (d, J(Rh,C)ꢀ
/
3.2 Hz, ipso-C of
3.8 Hz, C(2,5) of
(m, 3H, PCHCH3), 0.90 (dd, J(P,H)ꢀ
/
12.9 Hz,
7.1 Hz, 18H, PCHCH3) ppm. 13C-NMR
C5H4Rh), 90.1 (d, J(Rh,C)ꢀ
/
J(H,H)ꢀ
/
C5H4Rh), 88.2 (d, J(Rh,C)ꢀ
/
3.4 Hz, C(3,4) of
(C6D6, 50.3 MHz): d 136.7 (s, ipso-C of C5H4Ti),
133.7 (s, ipso-C of C6H5), 132.0, 128.2, 126.0 (all s,
C6H5), 121.9 (s, C(2,5) of C5H4Ti), 117.3 (s, C(3,4) of
C5H4Rh), 64.7 (m, Ä
/
CH of C8H14), 33.4, 32.1, 31.2,
27.1 (all s, m-CH2 and CH2 of C8H14).
C5H4Ti), 119.9 (s, C5H5Ti), 104.6 (dd, J(Rh,C)ꢀ
Hz, J(P,C)ꢀ3.6 Hz, ipso-C of C5H4Rh), 96.1, 95.9
(both dd, J(Rh,C)ꢀ18.3 Hz, J(P,C)ꢀ4.9 Hz, CꢀC),
87.9 (m, C(2,5) of C5H4Rh), 82.9 (m, C(3,4) of
C5H4Rh), 30.2 (s, CH2), 26.1 (d, J(P,C)ꢀ21.6 Hz,
PCHCH3), 19.9 (s, PCHCH3) ppm. 31P-NMR (C6D6,
81.0 MHz): d 73.1 (d, J(Rh,P)ꢀ200.5 Hz) ppm.
/12.0
3.10. Preparation of [{CH2(h5-
C5H4)2}{Rh(C2H4)2}{TiCl2(h5-C5H5)}] (12)
/
/
/
/
A solution of 149 mg (0.49 mmol) of 3 in 15 ml of
/
hexane was cooled to ꢁ78 8C and then treated with 0.20
/
ml (0.50 mmol) of a 2.5-M solution of n-butyllithium in
hexane. After the reaction mixture was warmed to r.t., it
was stirred for 1 h. The solvent was removed in vacuo,
the residue was washed twice with 5 ml of hexane each
and then dissolved in 15 ml of THF. The solution
containing the lithium salt of the anion of 3 was cooled
/
3.12. Preparation of [{CH2(h5-C5H4)2}{Rh
(Ä
CPh2)(PiPr3)}{TiCl2(h5-C5H5)}] (14)
/
A solution of 158 mg (0.28 mmol) of 7 in 20 ml ether
was cooled to ꢁ78 8C and then treated with a solution
to ꢁ
/
78 8C and added dropwise to a solution of 110 mg
/
(0.50 mmol) of [(h5-C5H5)TiCl3] in 10 ml of THF. The
reaction was warmed slowly (ca. 2 h) to r.t. and stirred
for 3 h. The solvent was evaporated in vacuo and the
residue was extracted three times with 10 ml of toluene
each. The combined extracts were concentrated to ca. 2
of 51 mg (0.28 mmol) of NaN(SiMe3)2 in 10 ml of ether.
After the reaction mixture was slowly warmed to r.t., it
was stirred for 30 min. The solvent was removed in
vacuo, the residue was washed twice with 5 ml of
pentane each and then dissolved in 15 ml of THF. The

B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ
/
81
79
solution containing the sodium salt of anion of 6 was
24.5 (d, J(P,C)ꢀ
ppm. 31P-NMR (C6D6, 162.0 MHz): d 57.9 (d,
J(Rh,P)ꢀ133.0 Hz) ppm.
/
22.4 Hz, PCHCH3), 20.6 (s, PCHCH3)
cooled to ꢁ78 8C and added dropwise to a solution of
/
62 mg (0.28 mmol) of [(h5-C5H5)TiCl3] in 15 ml of THF.
The reaction was warmed slowly (ca. 4 h) to r.t. and
stirred for 6 h. The solvent was evaporated in vacuo and
the residue was extracted three times with 10 ml of
toluene each. The combined extracts were concentrated
to ca. 2 ml in vacuo and the solution layered with 10 ml
/
3.14. Preparation of [{CH2(h5-
C5H4)2}{Rh(CH3)2(PiPr3)}{Ti(CH3)2(h5-C5H5)}]
(16)
of pentane. After storing the mixture at ꢁ
/
78 8C, dark
A solution of 284 mg (0.43 mmol) of 15 in 20 ml THF
red crystals precipitated which were filtered, washed
twice with 5 ml of pentane each and dried; yield 132 mg
(63%). Anal. Found: C, 60.09; H, 6.21. Calc. for
C38H46Cl2PRhTi: C, 60.44; H, 6.09%. 1H-NMR
(C6D6, 400 MHz): d 7.43 (m, 4H, C6H5), 7.04 (m, 6H,
C6H5), 6.49 (s, 5H, C5H5Ti), 6.42, 6.18 (both m, 2H
each, C5H4Ti), 5.12, 4.94 (both m, 2H each, C5H4Rh),
3.74 (s, 2H, CH2), 1.40 (m, 3H, PCHCH3), 0.99 (dd,
was cooled to ꢁ78 8C and then treated with 0.95 ml
/
(1.75 mmol) of a 1.85-M solution of methyllithium in
hexane. The reaction mixture was slowly warmed to
0 8C, stirred for 3 h and then warmed to r.t. A small
amount of water (ca. 0.2 ml) was added to remove the
excess of CH3Li. The solvent was evaporated in vacuo
and the residue was extracted three times with 10 ml of
hexane each. The combined extracts were concentrated
J(P,H)ꢀ
ppm. 13C-NMR (C6D6, 100.6 MHz): d 261.1 (dd,
J(Rh,C)ꢀ51.4 Hz, J(P,C)ꢀ18.0 Hz, RhÄCPh2),
150.6, 148.7 (both s, ipso-C of C6H5), 136.5 (s, ipso-C
of C5H4Ti), 131.4, 131.0, 130.2, 129.0, 128.1, 126.3 (all s,
C6H5), 122.3 (s, C(2,5) of C5H4Ti), 117.9 (s, C(3,4) of
/
13.0 Hz, J(H,H)ꢀ
/
7.0 Hz, 18H, PCHCH3)
to ca. 2 ml in vacuo and the solution stored at ꢁ78 8C
/
for 24 h. Orange crystals precipitated which were
filtered, washed twice with 2 ml of pentane each (0 8C)
and dried; yield 94 mg (38%). Anal. Found: C, 59.73; H,
/
/
/
1
8.22. Calc. for C29H48PRhTi: C, 60.25; H, 8.30%. H-
NMR (C6D6, 400 MHz): d 5.74 (s, 5H, C5H5Ti), 5.68,
5.59 (both m, 4H, C5H4Ti), 5.14, 4.93 (both m, 2H each,
C5H4Rh), 3.32 (br s, 2H, CH2), 1.99 (m, 3H, PCHCH3),
C5H4Ti), 119.9 (s, C5H5Ti), 102.9 (dd, J(Rh,C)ꢀ
Hz, J(P,C)ꢀ2.7 Hz, ipso-C of C5H4Rh), 85.9 (dd,
J(Rh,C)ꢀJ(P,C)ꢀ2.8 Hz, C(2,5) of C5H4Rh), 80.6 (m,
C(3,4) of C5H4Rh), 30.8 (s, CH2), 26.5 (d, J(P,C)ꢀ18.0
Hz, PCHCH3), 20.4 (s, PCHCH3) ppm. 31P-NMR
(C6D6, 81.0 MHz): d 58.0 (d, J(Rh,P)ꢀ242.8 Hz) ppm.
/5.8
/
/
/
1.02 (dd, J(P,H)ꢀ
/
13.0 Hz, J(H,H)ꢀ
/
7.0 Hz, 18H,
/
PCHCH3), 0.70 (dd, J(Rh,H)ꢀ
/
2.6 Hz, J(P,H)ꢀ3.5
/
Hz, 6H, RhCH3), 0.01 (s, 6H, TiCH3) ppm. 13C-NMR
(C6D6, 100.6 MHz): d 134.2 (s, ipso-C of C5H4Ti), 122.8
(s, C(2,5) of C5H4Ti), 118.8 (s, C5H5Ti), 114.7 (s, C(3,4)
/
3.13. Preparation of [{CH2(h5-
C5H4)2}{RhCl2(PiPr3)}{TiCl2(h5-C5H5)}] (15)
of C5H4Ti), 108.1 (d, J(Rh,C)ꢀ
C5H4Rh), 89.7 (d, J(Rh,C)ꢀ3.4 Hz, C5H4Rh), 88.5
(m, C5H4Rh), 45.8 (s, TiCH3), 29.0 (s, CH2), 25.3 (d,
J(P,C)ꢀ20.0 Hz, PCHCH3), 20.0 (s, PCHCH3), ꢁ15.0
(dd, J(Rh,C)ꢀ29.8 Hz, J(P,C)ꢀ13.6 Hz, RhCH3)
ppm. 31P-NMR (C6D6, 162.0 MHz): d 62.7 (d,
J(Rh,P)ꢀ169.8 Hz) ppm.
/3.8 Hz, ipso-C of
/
A slow stream of dry HCl was passed at ꢁ
/
78 8C for
/
/
10 s through a solution of 167 mg (0.22 mmol) of 13 in
20 ml THF. The solution was then slowly warmed to
room temperature and stirred for 30 min. The solvent
was evaporated in vacuo and the residue extracted three
times with 5 ml of CHCl3 each. The combined extracts
were concentrated to ca. 2 ml in vacuo and the solution
was layered with 6 ml of pentane. After the mixture was
/
/
/
3.15. Preparation of [{CH2(h5-
C5H4)2}{Rh(C2H4)2}{ZrCl2(h5-C5H5)}] (17)
stored at ꢁ
/
78 8C for 24 h, a dark red solid precipitated
A solution of 180 mg (0.60 mmol) of 3 in 15 ml of
which was washed twice with small amounts of pentane
and dried; yield 129 mg (89%). Anal. Found: C, 45.17;
H, 5.55; Rh, 15.29; Ti, 7.01. Calc. for C25H36Cl4PRhTi:
C, 45.48; H, 5.50; Rh, 15.59; Ti, 7.20%. 1H-NMR
(C6D6, 400 MHz): d 6.55 (s, 5H, C5H5Ti), 6.41, 6.28
(both m, 2H each, C5H4Ti), 5.58, 5.36 (both m, 2H each,
C5H4Rh), 3.79 (br s, 2H, CH2), 2.88 (m, 3H, PCHCH3),
ether was cooled to ꢁ78 8C and then treated with a
/
solution of 109 mg (0.60 mmol) of NaN(SiMe3)2 in 10
ml of ether. After the reaction mixture was warmed to
r.t., it was stirred for 30 min. The solvent was removed
in vacuo, the residue was washed twice with 5 ml of
pentane each and then dissolved in 15 ml of THF. The
solution containing the sodium salt of anion of 3 was
1.25 (dd, J(P,H)ꢀ
/
13.8 Hz, J(H,H)ꢀ
/
7.2 Hz, 18H,
cooled to ꢁ78 8C and added dropwise to a solution of
/
PCHCH3) ppm. 13C-NMR (C6D6, 100.6 MHz): d
137.0 (s, ipso-C von C5H4Ti), 122.6 (s, C(2,5) of
C5H4Ti), 118.2 (s, C(3,4) of C5H4Ti), 121.2 (s,
160 mg (0.60 mmol) of [(h5-C5H5)ZrCl3] in 10 ml of
THF. The reaction was warmed slowly (ca. 3 h) to r.t.,
stirred for 8 h and then worked up as described for 12.
An orange microcrystalline solid was isolated; yield 231
mg (73%). Anal. Found: C, 46.29; H, 4.22. Calc. for
C5H5Ti), 90.3 (dd, J(Rh,C)ꢀ
Hz, ipso-C of C5H4Rh), 86.0 (br s, C5H4Rh), 82.5 (dd,
J(Rh,C)ꢀJ(P,C)ꢀ3.8 Hz, C5H4Rh), 32.7 (br s, CH2),
/
12.2 Hz, J(P,C)ꢀ3.8
/
1
/
/
C21H23Cl2RhZr: C, 46.67; H, 4.29%. H-NMR (C6D6,

80
B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ81
/
400 MHz): d 6.41 (s, 5H, C5H5), 6.31, 6.20 (both m, 2H
each, C5H4Zr), 5.22, 5.03 (both m, 2H each, C5H4Rh),
3.72 (s, 2H, CH2), 2.61, 1.30 (both m, 4H each, C2H4)
ppm. 13C-NMR (C6D6, 100.6 MHz): d 132.2 (s, ipso-C
of C5H4Zr), 117.9 (s, C(2,5) of C5H4Zr), 116.2 (s,
C5H5Zr), 113.8 (s, C(3,4) of C5H4Zr), 111.2 (d,
mmol) of NaN(SiMe3)2 and 81 mg (0.31 mmol) of [(h5-
C5H5)ZrCl3]. After extraction of the crude product with
pentane (three times with 20 ml each), a yellow oil was
obtained; yield 140 mg (81%). Anal. Found: C, 53.88; H,
3.79. Calc. for C30H25Cl2ORhZr: C, 54.06; H, 3.78%. IR
(CH2Cl2): n(CO) 1971 cmꢁ1 1H-NMR (C6D6, 400
.
J(Rh,C)ꢀ
J(Rh,C)ꢀ
J(Rh,C)ꢀ
31.0 (s, CH2).
/
2.6 Hz, ipso-C of C5H4Rh), 88.9 (d,
3.2 Hz, C(2,5) of C5H4Rh), 86.2 (d,
3.6 Hz, C(3,4) of C5H4Rh), 38.2 (m, C2H4),
MHz): d 7.41 (m, 4H, C6H5), 7.02 (m, 6H, C6H5),
6.49 (s, 5H, C5H5), 6.41, 6.23 (both m, 2H each,
C5H4Zr), 5.22, 4.90 (both m, 2H each, C5H4Rh), 3.89
(s, 2H, CH2) ppm. 13C-NMR (C6D6, 100.6 MHz): d
/
/
284.9 (d, J(Rh,C)ꢀ
/
48.6 Hz, RhÄ
/
CPh2), 192.2 (d,
3.16. Preparation of [{CH2(h5-C5H4)2}{Rh(PhCꢀ
CPh)(PiPr3)}{ZrCl2(h5-C5H5)}] (18)
/
J(Rh,C)ꢀ100.8 Hz, CO), 165.1, 160.4 (both s, ipso-C
/
of C6H5), 134.0 (s, ipso-C of C5H4Zr), 128.8, 128.3,
127.7, 127.0, 126.6, 125.4 (all s, C6H5), 117.3 (s, C(2,5) of
C5H4Zr), 115.4 (s, C5H5), 113.2 (s, C(3,4) of C5H4Zr),
A solution of 365 mg (0.62 mmol) of 5 in 15 ml of
ether was cooled to ꢁ
/
78 8C and then treated with a
104.7 (d, J(Rh,C)ꢀ4.8 Hz, ipso-C of C5H4Rh), 90.0 (d,
/
solution of 114 mg (0.62 mmol) of NaN(SiMe3)2 in 10
ml of ether. After the reaction mixture was warmed to
r.t., it was stirred for 30 min. The solvent was removed
in vacuo, the residue was washed twice with 5 ml of
pentane each and then dissolved in 15 ml of THF. The
solution containing the sodium salt of anion of 5 was
J(Rh,C)ꢀ
J(Rh,C)ꢀ
ppm.
/
3.6 Hz, C(2,5) of C5H4Rh), 88.7 (d,
3.0 Hz, C(3,4) of C5H4Rh), 32.0 (s, CH2)
/
3.18. Preparation of [{CH2(h5-
C5H4)2}{RhCl2(PiPr3)}{ZrCl2(h5-C5H5)}] (20)
cooled to ꢁ78 8C and added dropwise to a solution of
/
165 mg (0.62 mmol) of [(h5-C5H5)ZrCl3] in 15 ml of
THF. The reaction was warmed slowly (ca. 3 h) to r.t.
and then stirred for 8 h. The solvent was evaporated in
vacuo and the residue extracted three times with 10 ml
of CH2Cl2 each. The combined extracts were concen-
trated to ca. 1 ml in vacuo and the solution was layered
A slow stream of dry HCl was passed for 30 s through
a solution of 260 mg (0.32 mmol) of 18 in 20 ml of
CHCl3. The solution was stirred for 1 h at r.t., and then
the solvent was evaporated in vacuo. The residue was
dissolved in 20 ml of CH2Cl2 and the extract was
filtered. The filtrate was brought to dryness in vacuo
and the remaining red oil washed three times with 10 ml
of pentane each; yield 205 mg (91%). Anal. Found: C,
42.89; H, 4.99. Calc. for C26H36Cl4PRhZr: C, 43.65; H,
5.07%. 1H-NMR (C6D6, 400 MHz): d 6.48 (s, 5H,
C5H5), 6.33, 6.20 (both m, 2H each, C5H4Zr), 5.62, 5.41
(both m, 2H each, C5H4Rh), 3.92 (br s, 2H, CH2), 2.85
with 15 ml of pentane. After cooling to ꢁ78 8C, a
/
brownish-yellow solid precipitated which upon warming
to r.t. became an oil; yield 327 mg (65%). Anal. Found:
C, 57.49; H, 5.66. Calc. for C39H46Cl2PRhZr: C, 57.76;
H, 5.72%. IR (CH2Cl2): n(Cꢀ
C) 1826 cmꢁ1. 1H-NMR
/
(C6D6, 200 MHz): d 8.20 (m, 4H, C6H5), 7.19 (m, 6H,
C6H5), 6.50 (s, 5H, C5H5Zr), 6.34, 6.20 (both m, 2H
each, C5H4Zr), 5.42, 5.21 (both m, 2H each, C5H4Rh),
3.78 (s, 2H, CH2), 1.60 (m, 3H, PCHCH3), 0.90 (dd,
(m, 3H, PCHCH3), 1.35 (dd, J(P,H)ꢀ
/
14.0 Hz,
7.2 Hz, 18H, PCHCH3) ppm. 13C-NMR
J(H,H)ꢀ
/
(C6D6, 100.6 MHz): d 133.7 (s, ipso-C of C5H4Zr),
116.9 (s, C(2,5) of C5H4Zr), 116.0 (s, C5H5), 113.2 (s,
C(3,4) of C5H4Zr), 104.7 (m, ipso-C of C5H4Rh), 86.8
(m, C(2,5) of C5H4Rh), 80.8 (m, C(3,4) of C5H4Rh),
J(P,H)ꢀ
/
12.9 Hz, J(H,H)ꢀ7.2 Hz, 18H, PCHCH3)
/
ppm. 13C-NMR (C6D6, 50.3 MHz): d 133.7 (s, ipso-C of
C6H5), 132.8 (s, ipso-C of C5H4Zr), 131.5, 128.1, 125.5
(all s, C6H5), 117.9 (s, C(2,5) of C5H4Zr), 116.6 (s,
C5H5Zr), 113.8 (s, C(3,4) of C5H4Zr), 105.2 (dd,
32.1 (s, CH2), 25.6 (d, J(P,C)ꢀ
(s, PCHCH3) ppm. 31P-NMR (CDCl3, 162.0 MHz): d
58.5 (d, J(Rh,P)ꢀ134.7 Hz) ppm.
/20.9 Hz, PCHCH3), 20.2
J(Rh,C)ꢀ
C5H4Rh), 96.2, 96.0 (both dd, J(Rh,C)ꢀ
J(P,C)ꢀ5.3 Hz, CꢀC), 87.7 (dd, J(Rh,C)ꢀ
2.6 Hz, C(2,5) of C5H4Rh), 82.6 (d, J(Rh,C)ꢀ
C(3,4) of C5H4Rh), 31.0 (s, CH2), 26.1 (d, J(P,C)ꢀ
Hz, PCHCH3), 19.9 (s, PCHCH3) ppm. 31P-NMR
(C6D6, 81.0 MHz): d 71.6 (d, J(Rh,P)ꢀ200.2 Hz) ppm.
/
11.7 Hz, J(P,C)ꢀ
/
2.4 Hz, ipso-C of
17.5 Hz,
J(P,C)ꢀ
4.0 Hz,
21.0
/
/
/
/
/
/
3.19. Preparation of [{CH2(h5-C5H4)2}{Rh
(Ä
CPh2)(CO)}{Zr(CH3)2(h5-C5H5)}] (21)
/
/
/
A solution of 180 mg (0.27 mmol) of 19 in 15 ml THF
was cooled to ꢁ78 8C and then treated with 0.20 ml
/
/
(0.30 mmol) of a 1.5-M solution of methyllithium in
hexane. The reaction mixture was slowly warmed to
0 8C, stirred for 3 h and then warmed to r.t. A small
amount of water (ca. 0.1 ml) was added to remove the
excess of CH3Li. The solvent was evaporated in vacuo
and the residue was extracted three times with 15 ml of
3.17. Preparation of [{CH2(h5-C5H4)2}{Rh
(Ä
CPh2)(CO)}{ZrCl2(h5-C5H5)}] (19)
/
This compound was prepared analogous as described
for 17 from 115 mg (0.26 mmol) of 10, 55 mg (0.30

B. Stempfle et al. / Journal of Organometallic Chemistry 681 (2003) 70ꢃ
/
81
81
hexane each. The combined extracts were concentrated
to ca. 2 ml in vacuo and the solution stored at ꢁ78 8C
Acknowledgements
/
for 3 days. Deep red crystals precipitated which upon
warming to r.t. became an oil; yield 76 mg (49%). Anal.
Found: C, 60.88; H, 4.57. Calc. for C32H31ORhZr: C,
We thank the Deutsche Forschungsgemeinschaft and
the Fonds der Chemischen Industrie for financial
support. Moreover, we acknowledge support by Mrs.
R. Schedl and Mr. C.P. Kneis (elemental analysis and
1
61.44; H, 4.96%. IR (hexane): n(CO) 1964 cmꢁ1. H-
NMR (C6D6, 400 MHz): d 7.44 (m, 4H, C6H5), 7.07 (m,
6H, C6H5), 6.52 (s, 5H, C5H5), 6.38, 6.18 (both m, 2H
each, C5H4Zr), 5.09, 4.79 (both m, 2H each, C5H4Rh),
DTA), and Mrs. M.L. Schafer and Dr. W. Buchner
¨
(NMR spectra).
3.67 (s, 2H, CH2), ꢁ
NMR (C6D6, 100.6 MHz): d 287.8 (d, J(Rh,C)ꢀ
Hz, RhÄCPh2), 189.8 (d, J(Rh,C)ꢀ98.8 Hz, CO),
/
0.29 (s, 3H, ZrCH3) ppm. 13C-
45.5
/
/
/
References
165.2, 160.5 (both s, ipso-C of C6H5), 129.9 (s, ipso-C
of C5H4Zr), 128.9, 128.2, 127.6, 127.0, 126.4, 125.4 (all s,
C6H5), 116.4 (s, C(2,5) of C5H4Zr), 114.2 (s, C5H5),
[1] (a) H. Werner, F. Lippert, T. Bohley, J. Organomet. Chem. 369
(1989) C27;
113.1 (s, C(3,4) of C5H4Zr), 105.0 (d, J(Rh,C)ꢀ
ipso-C of C5H4Rh), 90.1 (d, J(Rh,C)ꢀ3.6 Hz, C(2,5) of
C5H4Rh), 88.7 (d, J(Rh,C)ꢀ3.0 Hz, C(3,4) of
/
4.9 Hz,
(b) H. Werner, F. Lippert, T. Bohley, Z. Anorg, Allg. Chem. 620
(1994) 2053;
(c) F. Lippert, Dissertation, Universitat Wurzburg, 1989.
/
¨
¨
/
[2] (a) H. Werner, H.J. Scholz, R. Zolk, Chem. Ber. 118 (1985) 4531;
(b) H. Werner, M. Treiber, A. Nessel, F. Lippert, P. Betz, C.
Kruger, Chem. Ber. 125 (1992) 337;
C5H4Rh), 32.2 (s, ZrCH3), 31.4 (s, CH2) ppm.
¨
3.20. Crystal structure analysis of 6
(c) M. Treiber, Dissertation, Universitat Wurzburg, 1989.
¨
¨
[3] (a) A. Nessel, O. Nurnberg, J. Wolf, H. Werner, Angew. Chem.
¨
103 (1991) 999;
(b) A. Nessel, O. Nurnberg, J. Wolf, H. Werner, Angew. Chem.
¨
Int. Ed. Engl. 30 (1991) 1006;
(c) H. Werner, J. Wolf, A. Nessel, A. Fries, B. Stempfle, O.
Crystals were obtained from hexane at ꢁ
Crystal structure determination of 6: C35H46PRhSi,
Mrꢀ628.69; tetragonal, space group P4/n (No. 85),
Zꢀ8, aꢀ
/
78 8C.
/
˚
˚
/
/
bꢀ
1.218 g cmꢁ3, lꢀ
Ka)ꢀ
0.594 mmꢁ1. Crystal size 0.10ꢄ
0.23 mm3; 2Umax
508; 5557 reflections were measured,
5320 of these were independent (Rint 0.0664) and
employed in the structure refinement (352 parameters).
The R values are R1ꢀ0.0559 and wR2ꢀ0.1415 [I ꢁ
2s(I)] and R1ꢀ0.1961 and wR2ꢀ0.1932 (all data);
reflex/parameter ratioꢀ15.1; min./max. residual elec-
tron density: 0.975/ꢁ
352 e Aꢁ3. Data were collected on
/
26.020(5) A, cꢀ
/
10.125(5) A, Vꢀ
/
6855(4)
293(2) K,
0.23ꢄ
Nurnberg, Can. J. Chem. 73 (1995) 1050.
¨
[4] (a) H. Werner, D. Schneider, M. Schulz, Chem. Ber. 125 (1992)
1017;
3
˚
˚
A , Dcalc
m(Moꢃ
ꢀ
/
/
0.71073 A, Tꢀ
/
/
/
/
/
(b) D. Schneider, H. Werner, Organometallics 12 (1993) 4420.
[5] B. Stempfle, S. Schmidt, J. Sundermeyer, H. Werner, Chem. Ber.
128 (1995) 877.
ꢀ
/
ꢀ
/
[6] L. Carlton, P. Johnston, N.J. Coville, J. Organomet. Chem. 339
(1988) 339.
/
/
/
[7] E. Breitmaier, W. Voelter, Carbon-13 NMR Spectroscopy, VCH,
Weinheim, 1987.
[8] H. Komatsu, H. Yamazaki, J. Organomet. Chem. 634 (2001) 109.
/
/
/
˚
/
[9] H. Werner, R. Wiedemann, M. Laubender, B. Windmuller, P.
¨
a Enraf-Nonius CAD 4 diffractometer. A semi-empiri-
cal absorption correction was applied. The structure was
solved by direct methods (SHELXS-86) [23] and refined
against F2 by least-squares (SHELXL-93) [24]. All non-
hydrogen atoms were refined anisotropically. The posi-
Steinert, O. Gevert, J. Wolf, J. Am. Chem. Soc. 124 (2002) 6966.
[10] B. Stempfle, H. Werner, Gazz. Chim. Ital. 125 (1995) 287.
[11] (a) H. Werner, Angew. Chem. 95 (1983) 932;
(b) H. Werner, Angew. Chem. Int. Ed. Engl. 22 (1983) 927.
[12] H. Werner, J. Wolf, U. Schubert, K. Ackermann, J. Organomet.
Chem. 317 (1986) 327.
tions of all hydrogen atoms were calculated according to
˚
H, 0.95 A) and used only in
structure factor calculations.
[13] G.M. Diamond, M.L.H. Green, N.A. Popham, A.N. Chernega, J.
Chem. Soc. Chem. Commun. (1994) 727.
ideal geometry (distance CÃ
/
[14] K.H. Reichert, Transition metal-catalyzed polymerizations, in:
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4. Supplementary material
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[17] R. Cramer, Inorg. Synth. 15 (1974) 1501.
Crystallographic data (excluding structure factors) for
the structural analysis have been deposited with the
Cambridge Crystallographic Data Centre, CCDC No.
201883 for compound 6. Copies of this information may
be obtained free of charge on application to the
Director, CCDC, 12 Union Road, Cambridge, CB2
[18] H. Werner, R. Feser, J. Organomet. Chem. 232 (1982) 351.
[19] H. Werner, P. Schwab, E. Bleuel, N. Mahr, P. Steinert, J. Wolf,
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(1982) 1277.
1EZ, UK (Fax: ꢂ44-1223-336033; e-mail: depos-
/
[23] G.M. Sheldrick, Acta. Crystallogr. Sect. A 46 (1990) 467.
[24] G.M. Sheldrick, Program for crystal structure refinement, Uni-
versity of Gottingen, Gottingen, 1993.
it@ccdc.cam.ac.uk or www: http://www.ccdc.cam.a-
c.uk).
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