Isolation of [1]ruthenocenophanes: Synthesis of polyruthenocenylstannanes by ring-opening polymerization

Article abstract of DOI:10.1002/anie.200454022

Strained, ring-tilted [1]ruthenocenophanes 1 have been prepared for the first time. Ring-opening polymerization (ROP) of an example of 1 with a Sn bridge affords a novel, bimetallic, high-molecular-weight polyruthenocenylstannane 2 (R= mesityl).

Full text of DOI:10.1002/anie.200454022

Angewandte
Chemie
Bimetallic Polymers
Isolation of [1]Ruthenocenophanes: Synthesis of
Polyruthenocenylstannanes by Ring-Opening
Polymerization**
Ulf Vogel, Alan J. Lough, and Ian Manners*
Strained [1]ferrocenophanes 1[1] have attracted considerable
attention over the past decade because of their interesting
structures and reactivity and their ability[2] to function as
precursors of high-molecular-weight polyferrocenes through
ring-opening polymerization (ROP). Studies of the unusual
properties of the resulting metallopolymers 2[3] as well as
[*] Dr. U. Vogel, Dr. A. J. Lough, Prof. Dr. I. Manners
Dept. of Chemistry, University of Toronto
80 St. George Street, Toronto, M5S 3H6, Ontario (Canada)
Fax: (+1)416-978-6157
E-mail: imanners@chem.utoronto.ca
[**] We thank the NSERC and the DAAD exchange program for financial
support of this work. U.V. is grateful for a research fellowship
granted by the Deutsche Forschungsgemeinschaft. We also thank
K. T. Kim and S. Fournier for thermal analysis measurements.
Angew. Chem. Int. Ed. 2004, 43, 3321 –3325
DOI: 10.1002/anie.200454022
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3321

Communications
fundamental interest in strained organometallic rings,[4] have
inspired the synthesis and study of a range of new [1]ferro-
cenophanes 1 with either main-group[5] or d- or f-block
elements[6] in the bridge. A feature of these strained
molecules is the presence of a tilting of the cyclopentadienyl
rings which can result in a dihedral angle of up to 328. The
expansion of this chemistry to allow the incorporation of
other metals into analogous strained organometallic mono-
mers is of considerable interest but has been much slower to
develop. Rare examples of strained and potentially polymer-
izable species studied to date include silicon-bridged bis(ben-
zene)chromium complexes,[7] [2]cobaltocenophanes,[8] and
[2]ruthenocenophanes 3 (M = Ru) with a CH2CH2 bridge.[9]
In the latter case, the species were shown to exhibit a
significantly higher ring tilt and degree of strain than their
iron analogues, as a result of the larger size of the ruthenium
atom which forces the Cp rings further apart.[9,10] Herein we
report the first examples of [1]ruthenocenophanes together
with preliminary studies of their ROPbehavior.
Attempts to synthesize silicon-bridged [1]ruthenoceno-
phanes by reaction of the N,N,N’,N’-tetramethylethylenedi-
amine (TMEDA) adduct of dilithiated ruthenocene
Ru(C5H4Li)2·TMEDA (4) with Cl2SiMe2 have been reported
to result in the formation of dimeric and oligomeric spe-
cies.[11,12] Introduction of larger elements such as zirconium or
tin as the bridging atoms might be expected to lead to less-
strained and therefore more-stable [1]ruthenocenophanes.
We attempted to prepare the zirconium-bridged [1]rutheno-
cenophane by the reaction of 4 with [Cl2ZrCp02] (Cp’ =
C5H4tBu) in Et2O at low temperature. Recrystallization of
the crude reaction product from hexanes at À558C afforded 5
as a pale yellow powder in 35% yield (Scheme 1).
Figure 1. Structure of 5 in the solid state, hydrogen atoms are omitted
for clarity. Selected bond lengths [pm] and angles [8]: Ru(1)···Zr(1)
295.04(4), Ru(1)-C(1) 214.6(2), Ru(1)-C(2) 216.9(3), Ru(1)-C(3)
221.3(3), Ru(1)-C(4) 221.0(4), Ru(1)-C(5) 215.5(2), Zr(1)-C(1)
214.6(2), Zr(1)-C(6) 249.5(2), Zr(1)-C(7) 252.9(2), Zr(1)-C(8) 258.5(2),
Zr(1)-C(9) 262.5(2), Zr(1)-C(10) 254.0(2); C(1)-Zr(1)-C(1A) 92.3(1).
larger size of the ruthenium atom in comparison to the iron
atom, 5 shows more strain than the corresponding iron
compound 1 (ERn = ZrCp02). The tilt angle a for 5 is 10.48,
which is significantly greater than for the analogous iron
compound (68),[6a] but the increase in tilt is not as high as
expected when compared with 3[10]. Another feature indicat-
ing the strain in 5 is the Cpcentroid-Ru-Cpcentroid angle q which is
1758 as opposed to 177.38 in 1 (ERn = ZrCp0 ). The angle b
2 À
between the planes of the Cp rings and the Zr C(1) bond is
418, which is slightly larger than in 1 (ERn = ZrCp02, 40.18).[6a]
The constrained geometry in 5 forces the Ru atom and the Zr
À
atom into close contact. The Ru Zr distance is 295.04(4) pm,
À
close to distances found for Ru Zr single bonds ([Cp2Zr{Ru-
[14]
À
(CO)2Cp}2]: Zr Ru = 293.8(1), 294.9(1) pm;
[Cp2Zr{Ru-
The electronic
[15]
À
(CO)2Cp}OtBu]: Zr Ru = 291.0(1) pm).
nature of this interaction is currently under theoretical
investigation.
To determine if 5 can be polymerized thermally, a DSC
(differential scanning calorimetry) experiment was carried
out. It showed a melt endotherm at 1888C; a ROPexotherm
could not be detected. On heating the monomer to 2008C in a
sealed tube for 4 days, only unconverted starting material was
recovered. Compound 5 is also unreactive towards anionic
initiators such as MeLi.
Scheme 1. Synthesis of 4 and 5.
The identity of 5 was confirmed by 1H NMR and
13C NMR spectroscopy, and by mass spectrometry. The
1H NMR spectrum indicates a ring-strained structure with a
set of two pseudotriplets at d = 4.52 and 4.86 ppm, which we
assigned to the a and b H atoms of the Cp ring bound to
ruthenium. The 13C NMR spectrum shows an unusual down-
field shift for the signal of the ipso-C atom of the ruthenocene
Cp ring at d = 162.5 ppm. The same is observed for the
analogous iron compound 1 (ERn = ZrCp02),[6a] in which the
corresponding shift is d = 159.0 ppm. For strained [1]ferroce-
nophanes the signals for the ipso-Cp carbon atoms are usually
shifted upfield relative to those for unstrained compounds.
To probe the structure of 5, an X-ray crystal structure
determination of a single crystal grown from hexanes at
À308C was conducted (Figure 1).[13] As expected from the
Tin-bridged [1]ferrocenophanes can be isolated with
bulky substituents and are sufficiently strained to undergo
[5b]
ROP. To synthesize a tin-bridged [1]ruthenocenophane, 4
was treated with Cl2SnMes2 at low temperature in Et2O. A
1H NMR spectrum of the crude reaction mixture showed
broad peaks owing to the formation of presumably oligomeric
material. However, signals attributable to the tin-bridged
[1]ruthenocenophane 6 could also be detected in the mixture.
When the reaction was carried out in THF instead of Et2O, 6
was formed as the main product. Extraction of the crude
reaction mixture with hexanes and repeated recrystallizations
from Et2O led to the isolation of 6 in 13% yield (Scheme 2).[16]
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Chemie
shoulder in the same wavelength region. This behavior is also
observed for [1]ruthenocenophanes.
To determine the solid-state structure of 6 an X-ray
diffraction study was carried out on single crystals grown from
nBu2O (Figure 3).[13] Complex 6 is isostructural with 1 (ERn =
Scheme 2. Synthesis of 6 (Mes= 2,4,6-trimethylphenyl).
The identity of 6 was confirmed by NMR and UV/Vis
spectroscopy and mass spectrometry. Signals attributable to
the a and b H atoms of the Cp ring are detected in the
1H NMR spectrum at d = 5.03 and 4.30 ppm, respectively. At
d = 0.73 ppm the separation of these signals (DdCp) is larger
than in the analogous iron compound 1 (ERn = SnMes2), for
which DdCp is 0.13 ppm.[5b] This increasing separation has been
attributed to an increased tilt angle a in several other cases,
but in this study we could not confirm this trend. On the
contrary, we found that in some cases DdCp decreases with
increasing a: The [2]ruthenocenophane 3 (M = Ru, a =
29.6(5)8) shows a separation of 0.38 ppm for the hydrogen
atoms of the Cp ring,[12] whereas for the analogous [2]ferro-
cenophane 3 (M = Fe, a = 21.6(5)8)[17] this value increases to
Figure 3. Structure of 6 in the solid state. Only one of the three inde-
pendent molecules in the unit cell is depicted, hydrogen atoms are
omitted for clarity. Selected bond lengths [pm] and angles [8]:
Ru(1)···Sn(1) 299.63(7), Ru(1)-C(1) 213.0(6), Ru(1)-C(2) 215.0(7),
Ru(1)-C(3) 221.3(8), Ru(1)-C(4) 221.4(7), Ru(1)-C(5) 215.2(6), Ru(1)-
C(6) 215.5(6), Ru(1)-C(7) 215.4(7), Ru(1)-C(8) 221.5(7), Ru(1)-C(9)
220.8(8), Ru(1)-C(10) 214.6(7), Sn(1)-C(1) 219.7(6), Sn(1)-C(6)
218.1(6), Sn(1)-C(11) 217.0(6), Sn(1)-C(20) 217.4(6), C(1)-Sn(1)-C(6)
91.2(2), C(11)-Sn(1)-C(20) 116.7(2).
d = 0.88 ppm.[12] The same can be observed for 5 (5: DdCp
=
0.34 ppm; 1 (ERn = ZrCp20 ): DdCp = 0.37 ppm). The shift of the
13C NMR signal for the Cp ipso-carbon atom of 6 (d =
31.8 ppm) seems to follow the usual trend: The signal is
shifted upfield relative to that for the corresponding iron
complex 1 (ERn = SnMes2, d = 38.2 ppm).
Also indicating the strain in 6 is the UV/Vis spectrum in
CH2Cl2 (Figure 2) which shows a band at 363 nm (emax
=
SnMes2) and crystallizes in the space group P21/c with three
independent molecules (designated 6I, 6II, 6III) in the asym-
metric unit. The three molecules mainly differ in the rotation
À
of the mesityl groups around the Sn C bond. The tilt angles a
are 20.9(3), 20.2(3), and 20.8(4)8, which are significantly
higher than in 1 (ERn = SnMes2, a = 15.3(2), 14.5(2), and
15.7(3)8).[5b] The b angles (6I 34.7, 35.5; 6II 35.7, 35.6; 6III 35.6,
35.38) are comparable to 1 (ERn = SnMes2, a = 35.3(2)). As
expected, the angle q between the Cp-ring centroids and the
central Ru atom in 6 (q = 164.3, 164.9, and 164.58) is smaller
than in the analogous iron compound 1 (ERn = SnMes2, q =
167.5(2), 168.0(2), and 167.3(2)8) and therefore also indicates
À
À
the higher strain in 6. The average Sn C bond lengths (Sn
À
C
Mes: 216.9(7) pm; Sn CCp: 219.3(7) pm) are consistent with
values typically found for such bonds. As in the case of 5, the
Ru and the bridging Sn atom are forced into close contact
À
with the distance Ru Sn being 299.63(7), 299.36(7), and
299.26(8) pm. These distances are longer than the values
[20]
Figure 2. UV/Vis spectra of ruthenocene (c), 5 (g), and 6 (a)
in CH2Cl2.
À
normally found for Ru Sn single bonds, but shorter than
À
the long distances in [Ru6C(CO)16SnCl3]2 in which a five-
coordinate tin atom asymmetrically bridges two ruthenium
436 LmolÀ1 cmÀ1). For comparison, ruthenocene shows an
absorption band at 322 nm, which can be resolved into two
atoms
(Ru Sn = 314.0(2),
258.1(3),
310.2(2),
and
À
258.3(3) pm).[21] Based on these findings an interaction
between the two elements cannot be ruled out.
bands when measured at 77 K (339 nm, emax
=
120 LmolÀ1 cmÀ1 and 308 nm, emax = 160 LmolÀ1 cmÀ1). These
A DSC study of 6 showed no melt transition, but a ROP
exotherm was detected at 1818C. On heating 6 in a sealed
tube at 2008C for 4.5 h, the polymeric material 7 was obtained
after precipitation from THF into methanol (Scheme 3). The
structure of 7 was confirmed by NMR spectroscopy. The
1H NMR spectrum of 7 shows peaks for the H atoms of the Cp
1
1
1
1
bands have been assigned to the A1g! E1g and A1g! E2g
transitions, respectively.[18] For strained ferrocenophanes it
has been shown that the longer wavelength band is red-shifted
and the absorption coefficient of this band increases with the
amount of ring tilt.[5,19] Compound 5 only shows a weak
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2.4 Hz, 4H; Cp), 4.30 (t, 3J(H,H) = 2.4 Hz, 4H; Cp), 2.75 (s, 4J(117/
119Sn,1H) = 6.9 Hz, 12H; o-CH3), 2.14 ppm (s, 6H; p-CH3); 13C NMR
(100.5 MHz, C6D6, 258C): d = 145.7 (s, 2J(117/119Sn,13C) = 42 Hz; o-
Mes), 139.6 (s, 4J(117/119Sn,13C) = 11 Hz; p-Mes), 136.8 (s,
1J(119Sn,13C) = 406 Hz, 1J(117Sn,13C) = 392 Hz; ipso-Mes), 129.4 (s,
3J(119Sn,13C) = 50 Hz, 3J(117Sn,13C) = 48 Hz; m-Mes), 79.8 (s, 3J
2
(
117/119Sn,13C) = 34 Hz, Cp), 77.9 (s, J(117/119Sn,13C) = 49 Hz; Cp), 31.8
Scheme 3. Ring-opening polymerization of 6.
(s, 1J(119Sn,13C) = 398 Hz, 1J(117Sn,13C) = 380 Hz; ipso Cp), 25.6 (s,
3J(119Sn,13C) = 42 Hz, 3J(117Sn,13C) = 40 Hz; o-CH3), 21.4 ppm (s,
5J(117/119Sn,13C) = 7 Hz; p-CH3); 119Sn NMR (111.8 MHz, C6D6,
258C) d = À112.5 ppm; MS: m/z:(%) 586 (6) [M+], 467 (23)
[M+ÀMes], 349 (100) [M+À2Mes + H], 232 (48) [RuCp2+]; UV/Vis
(CH2Cl2): lmax (e) = 363 nm (436 LmolÀ1 cmÀ1); elemental analysis:
calcd for C28H30RuSn (%): C 57.36, H 5.16; found: C 57.21, H 5.51.
7: 6 (130 mg, 0.22 mmol) was sealed in an evacuated tube and
heated to 2008C for 4.5 h. The crude polymer was purified by
repeated precipitation from THF into methanol to yield 7 as a white
powder, which was dried in vacuo (59 mg, 45%). 1H NMR (300 MHz,
C6D6, 258C): d = 6.72 (s, 4H; m-H), 4.71 (s, 4H; Cp), 4.65 (s, 4H; Cp),
2.37 (s, 12H; o-CH3), 2.12 ppm (s, 6H; p-CH3); 13C NMR (100.5 MHz,
ring as well as the mesityl ligands, which are typically broad as
expected for a polymer. The most prominent feature of the
13C NMR spectrum of 7 is the signal for the Cp ipso-carbon
atom at d = 76.9 ppm, which shows a significant downfield
shift relative to that of the monomer 6 (d = 31.8 ppm). GPC
analysis in THF versus polystyrene standards showed the
material to be of high molecular weight with a relatively
broad molecular-weight distribution (Mn = 2.7·105, Mw/Mn =
2.28). The polymer 7 is stable to air, moderately soluble in
organic solvents such as toluene, CH2Cl2 and THF, and
insoluble in hexanes and methanol. DSC analysis showed a
glass transition temperature (Tg) of 2218C. Thermogravimet-
ric analysis of 7 showed decomposition starting at 2708C. The
ceramic yield at 9008C was 32%.
Further studies of the reactivity of 5 and 6 are in progress.
Current work is also focused on the synthesis of other
examples of [1]ruthenocenophanes with different bridging
elements and the study of the properties of the resulting ring-
opened polymers, which should differ substantially from those
based on ferrocene.
2
C6D6, 258C): d = 144.5 (s, J(117/119Sn,13C) = 33 Hz; o-Mes), 141.6 (s;
ipso-Mes) 138.2 (s; p-Mes), 129.0 (s; m-Mes), 77.9 (s; Cp), 76.9 (s;
ipso-Cp), 75.2 (s, J(117/119Sn,13C) = 36 Hz; Cp), 26.9 (s, 3J
(
117/119Sn,13C) = 32 Hz; o-CH3), 21.5 ppm (s; p-CH3); 119Sn NMR
(111.8 MHz, C6D6, 258C): d = À133.0 ppm; GPC (THF, versus
polystyrene): Mn = 2.7 ” 105, Mw/Mn = 2.28; elemental analysis: calcd
for C28H30RuSn (%): C 57.36, H 5.16; found: C 57.67, H 5.38.
Received: February 13, 2004 [Z54022]
Keywords: cyclopentadienyl ligands · ring-opening
.
polymerization · ruthenium · stannanes · strained molecules
Experimental Section
4: TMEDA (4.12 mL, 27.3 mmol) and nBuLi (1.6m solution in
hexanes, 21.2 mL, 33.9 mmol) were added to a suspension/solution of
ruthenocene (3.11 g, 13.5 mmol) in hexanes (100 mL), and the
mixture was stirred at room temperature for 60 h. The resulting
light yellow precipitate was collected by filtration, washed with
hexanes until the washings were colorless, and dried in vacuo (4.05 g,
84%). The solid should be stored at À308C.
[1] a) M. Herberhold, Angew. Chem. 1995, 107, 1985; Angew. Chem.
Int. Ed. Engl. 1995, 34, 1837; b) H. Braunschweig, F. M.
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[2] D. A. Foucher, B. Z. Tang, I. Manners, J. Am. Chem. Soc. 1992,
114, 6246.
[3] a) I. Manners, Chem. Commun. 1999, 857; b) I. Manners, Science
2001, 294, 1664.
5: Solid [Cl2ZrCp02][22] (1.32 g, 3.26 mmol) was added to
a
suspension of 4 (1.17 g, 3.26 mmol) in Et2O (50 mL) at À708C. The
solution was allowed to warm to room temperature overnight and the
solvent was then removed in vacuo. Extraction with hot hexanes,
filtration, and concentration of the resulting solution yielded 5 as a
[4] a) J. C. Green, Chem. Soc. Rev. 1998, 27, 263; b) A. Berenbaum,
F. Jäkle, A. J. Lough, I. Manners, Organometallics 2002, 21, 2359;
c) A. Berenbaum, H. Braunschweig, R. Dirk, U. Englert, J. C.
Green, F. Jäkle, A. J. Lough, I. Manners, J. Am. Chem. Soc. 2000,
122, 5765; d) T. Mizuta, Y. Imamura, K. Miyoshi, J. Am. Chem.
Soc. 2003, 125, 2068.
1
pale yellow powder (650 mg, 35%) on storage at À558C. H NMR
3
(300 MHz, C6D6, 258C): d = 5.92 (t, J(H, H) = 5.1 Hz, 4H; CptBu),
5.33 (t, 3J(H, H) = 5.1 Hz, 4H; CptBu), 4.86 (t, 3J(H, H) = 3 Hz, 4H;
Cp), 4.52 (t, 3J(H, H) = 3 Hz, 4H; Cp), 1.31 ppm (s, 18H; tBu);
13C NMR (75 MHz, C6D6, 258C): d = 162.5 (s; ipso CpRu), 138.3 (s;
ipso-CpZr), 104.8 (s; CpZr), 104.6 (s; CpZr), 87.1 (s; CpRu), 74.4 (s;
CpRu), 33.3 (s; C(CH3)3), 33.2 ppm (s; C(CH3)3); MS: m/z (%): 562
(100) [M+], 547 (15) [M+ÀCH3], 506 (25) [M+ÀC4H8], 232 (56)
[RuCp2+]; UV/Vis (CH2Cl2): lmax (e) = 310 nm (shoulder); elemental
analysis: calcd for C28H34RuZr (%): C 59.75, H 6.09; found: C 59.58,
H 6.32.
[5] a) A. G. Osborne, R. H. Whiteley, J. Organomet. Chem. 1980,
193, 345; b) F. Jäkle, R. Rulkens, G. Zech, D. A. Foucher, A. J.
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F. Cervantes-Lee, J. S. Mahmoud, K. H. Pannell, Organometal-
lics 1999, 18, 399; d) T. Baumgartner, F. Jäkle, R. Rulkens, G.
Zech, A. J. Lough, I. Manners, J. Am. Chem. Soc. 2002, 124,
10062; e) M. Herberhold, F. Hertel, W. Milius, B. Wrackmeyer,
J. Organomet. Chem. 1999, 582, 352; f) R. Rulkens, D. P. Gates,
D. Balaishis, J. K. Pudelski, D. F. McIntosh, A. J. Lough, I.
Manners, J. Am. Chem. Soc. 1997, 119, 10976; g) H. Braunsch-
weig, R. Dirk, M. Müller, P. Nguyen, R. Resendes, D. P. Gates, I.
Manners, Angew. Chem. 1997, 109, 2433; Angew. Chem. Int. Ed.
Engl. 1997, 36, 2338; h) W. Uhl, I. Hahn, A. Jantschak, T. Spies, J.
Organomet. Chem. 2001, 637, 300.
6: Compound 4 (1.0 g, 2.78 mmol) in THF (6 mL) was added to a
[23]
suspension of finely ground Cl2SnMes2 (1.3 g, 3.04 mmol) in THF
(2 mL) at À708C. The mixture was stirred at low temperature for 4 h
and then allowed to slowly reach À308C. The solution was taken out
of the cold bath, and the solvent removed in vacuo. Extraction of the
residue with hexanes (50 mL) and removal of the solvent gave a crude
product, which was repeatedly recrystallized from Et2O to give 6 as a
pale yellow powder (210 mg, 13%). 1H NMR (300 MHz, C6D6, 258C):
d = 6.79 (s, 4J(117/119Sn,1H) = 22.0 Hz, 4H; m-H), 5.03 (t, 3J(H,H) =
[6] a) R. Broussier, A. Da Rold, B. Gautheron, Y. Dromzee, Y.
Jeannin, Inorg. Chem. 1990, 29, 1817; b) A. Bucaille, T.
Le Borgne, M. Ephritikhine, J. C. Daran, Organometallics
2000, 19, 4912.
3324
ꢀ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Angew. Chem. Int. Ed. 2004, 43, 3321 –3325

Angewandte
Chemie
[7] a) C. Elschenbroich, J. Hurley, B. Metz, W. Massa, G. Baum,
Organometallics 1990, 9, 889; b) K. C. Hultzsch, J. M. Nelson,
A. J. Lough, I. Manners, Organometallics 1995, 14, 5496.
[8] a) M. J. Drewitt, S. Barlow, D. OꢀHare, J. M. Nelson, P. Nguyen,
I. Manners, Chem. Commun. 1996, 2153; b) S. Fox, J. P. Dunne,
M. Tacke, D. Schmitz, R. Dronskowski, Eur. J. Inorg. Chem.
2002, 3039.
Solution and refinement as for 5, R1 = 0.0557, wR2 = 0.1296,
(R1 = ꢀ(FoÀFc)/ꢀFo observed data, wR2 = {ꢀ[w(F2oÀFc2)2]/
À3
ꢀ[w(F2o)2]}1/2 for all data), GOF = 1.015, D1max = 1.47 eŠ
.
CCDC-231377 (6) and -231378 (5) contain the supplementary
crystallographic data for this paper. These data can be obtained
free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or
from the Cambridge Crystallographic Data Centre, 12, Union
Road, Cambridge CB21EZ, UK; fax: (+ 44)1223-336-033; or
deposit@ccdc.cam.ac.uk).
[9] J. M. Nelson, A. J. Lough, I. Manners, Angew. Chem. 1994, 106,
1019; Angew. Chem. Int. Ed. Engl. 1994, 33, 989.
[10] For 3 the difference in the tilt angle a between the planes of the
Cp ligands for the Ru and Fe species is 88. (3 (M = Ru): a =
29.6(5)8, 3 (M = Fe): a = 21.6(5)8); see references [9] and [17].
[11] U. Vogel, J. M. Nelson, I. Manners, unpublished results.
[12] M. Herberhold, T. Bärtl, Z. Naturforsch. B 1995, 50, 1692.
[13] Crystallographic data for C28H34RuZr (5): monoclinic C2/c, a =
19.0368(4), b = 9.5493(4), c = 15.1497(4) Š, b = 124.306(2)8, V=
[14] C. P. Casey, R. F. Jordan, A. L. Rheingold, Organometallics
1984, 3, 504.
[15] C. P. Casey, R. F. Jordan, A. L. Rheingold, J. Am. Chem. Soc.
1983, 105, 665.
1
[16] Although the H NMR spectrum of the crude reaction mixture
showed the formation of 6 in approximately 40% yield, the
purification of the compound was difficult owing to the similar
solubilities of 6 and the by-products.
2274.9(1) Š3, Z = 4, m = 1.135 mmÀ1
,
1calcd = 1.643 MgmÀ3
,
150(1) K, Nonius Kappa-CCD diffractometer using graphite-
monochromated MoKa radiation (l = 0.71073 Š), pale yellow
crystal (0.30 ” 0.22 ” 0.16 mm3). Of 9615 reflections collected
(5.1 ꢀ 2q ꢀ 55.08), 2617 were independent (Rint = 0.0296), and
2279 were observed with Fo ꢁ 4s(Fo). Solution and refinement
with SHELXTL-PC v6.12, non-hydrogen atoms were refined
with anisotropic parameters, hydrogen atoms were refined on
calculated positions using a riding model, R1 = 0.0256, wR2 =
[17] a) J. M. Nelson, H. Rengel, I. Manners, J. Am. Chem. Soc. 1993,
115, 7035; b) J. M. Nelson, P. Nguyen, R. Peterson, H. Rengel,
P. M. Macdonald, A. J. Lough, I. Manners, N. P. Raju, J. E.
Greedon, S. Barlow, D. OꢀHare, Chem. Eur. J. 1997, 3, 573.
[18] Y. S. Sohn, D. N. Hendrickson, H. B. Gray, J. Am. Chem. Soc.
1971, 93, 3603.
[19] a) J. K. Pudelski, D. A. Foucher, C. H. Honeyman, A. J. Lough,
I. Manners, S. Barlow, D. OꢀHare, Organometallics 1995, 14,
2470; b) S. Barlow, M. J. Drewitt, T. Dijkstra, J. C. Green, D.
OꢀHare, C. Whittingham, H. H. Wynn, D. P. Gates, I. Manners,
J. M. Nelson, J. K. Pudelski, Organometallics 1998, 17, 2113.
0.0628,
(R1 = ꢀ(FoÀFc)/ꢀFo
observed
data,
wR2 =
{ꢀ[w(Fo2ÀF2c)2]/ꢀ[w(Fo2)2]}1/2 for all data), GOF = 1.102, D1max
=
0.896 eŠÀ3. Crystallographic data for C28H30RuSn (6): mono-
clinic P21/c, a = 17.8377(4), b = 12.4501(3), c = 31.9136(7) Š, b =
93.826(1)8, V= 7071.6(3) Š3, Z = 12, m = 1.712 mmÀ1, 1calcd
=
À
[20] The average bond length of 119 Ru Sn bonds found in a CSD
1.652 MgmÀ3
using graphite-monochromated
, 150(1) K, Nonius Kappa-CCD diffractometer
database search was 266(6) pm.
[21] S. Hermans, B. F. G. Johnson, Chem. Commun. 2000, 1955.
[22] R. A. Howie, G. P. McQuillan, D. W. Thompson, G. A. Lock, J.
Organomet. Chem. 1986, 303, 213.
MoKa
radiation
(l =
0.71073 Š), pale yellow crystal (0.26 ” 0.26 ” 0.03 mm3). Of
36931 reflections collected (5.1 ꢀ 2q ꢀ 55.08) 16057 were inde-
pendent Rint = 0.0657, and 10129 were observed with Fo ꢁ 4s(Fo).
[23] F. Jäkle, I. Manners, Organometallics 1999, 18, 2628.
Angew. Chem. Int. Ed. 2004, 43, 3321 –3325
www.angewandte.org
ꢀ 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3325