Methylidyne-diyne coupling reactions onto a triruthenium cluster core

Article abstract of DOI:10.1016/S0020-1693(02)01444-5

Treatment of the methoxymethylidyne-bridged triruthenium cluster [Ru₃(μ-H)(μ-COMe)(CO)₁₀] (1) with the symmetric diynes RC≡CC≡CR (R=Me, Ph, CH₂OPh) led to separable mixtures of two regioisomers, [Ru₃(μ-H)(μ₃-η³-MeOCCR= CC≡CR)(CO)₉] and [Ru₃(μ-H)(μ₃-η³-MeOCC(C ≡CR)=CR)(CO)₉]. These products arise from the insertion of one of the alkyne moieties of the corresponding diyne into a Ru-C bond of the methylidyne ligand. In all cases, the second alkyne functionality remains uncoordinated. In contrast, the reactions of the trihydride cluster [Ru₃(μ-H)₃(μ₃-COMe)(CO)₉] (2) with diphenylbutadiyne led to a mixture of regioisomers in which one alkyne group of the original diyne has inserted into a Ru-C bond of the methylidyne ligand while the remaining triple bond has been hydrogenated to a double bond. The X-ray structures of the two regioisomers formed in the reaction of 1 with 2,4-hexadiyne are reported.

Full text of DOI:10.1016/S0020-1693(02)01444-5

Inorganica Chimica Acta 347 (2003) 107Á113
/
www.elsevier.com/locate/ica
MethylidyneÁ
/
diyne coupling reactions onto a triruthenium cluster
core
Javier A. Cabeza a,*, Iva´n da Silva a, Ignacio del R´ıo a, Santiago Garc´ıa-Granda b,
V´ıctor Riera a
a Departamento de Qu´ımica Orga´nica e Inorga´nica, Instituto de Qu´ımica Organometa´lica ‘Enrique Moles’, Facultad de Quimica, Universidad de Oviedo-
CSIC, E-33071 Oviedo, Spain
b Departamento de Qu´ımica-F´ısica y Anal´ıtica, Universidad de Oviedo, E-33071 Oviedo, Spain
Received 24 April 2002; accepted 18 July 2002
Dedicated to Professor Rafael Uso´n, an outstanding pioneer of Spanish organometallic chemistry
Abstract
Treatment of the methoxymethylidyne-bridged triruthenium cluster [Ru3(m-H)(m-COMe)(CO)10] (1) with the symmetric diynes
RCÅ
and [Ru3(m-H)(m3-h3-MeOCC(CÅ
corresponding diyne into a RuÃ
uncoordinated. In contrast, the reactions of the trihydride cluster [Ru3(m-H)3(m3-COMe)(CO)9] (2) with diphenylbutadiyne led to a
mixture of regioisomers in which one alkyne group of the original diyne has inserted into a RuÃC bond of the methylidyne ligand
/
CCÅ
/
CR (Rꢀ
/
Me, Ph, CH2OPh) led to separable mixtures of two regioisomers, [Ru3(m-H)(m3-h3-MeOCCRÄ
/
CCÅ
CR)(CO)9]. These products arise from the insertion of one of the alkyne moieties of the
C bond of the methylidyne ligand. In all cases, the second alkyne functionality remains
/
CR)(CO)9]
/
CR)Ä
/
/
/
while the remaining triple bond has been hydrogenated to a double bond. The X-ray structures of the two regioisomers formed in
the reaction of 1 with 2,4-hexadiyne are reported.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Ruthenium; Clusters; Methylidyne ligands; Diynes; Insertion reactions
1. Introduction
In this context, the reactions of the methylidyne-
bridged triruthenium clusters [Ru3(m-H)(m-COMe)-
(CO)10] (1) and [Ru3(m-H)3(m3-COMe)(CO)9] (2) toward
alkynes have been studied [2]. The interesting reactivity
Since the early 1980s, a rapid development of the
synthetic chemistry of the methylidyne cluster com-
plexes [M3(m-H)(m-CX)(CO)10] and [M3(m-H)3(m-
patterns observed, which involve CÃ/C bond forming
reactions along with hydrogenation processes made
these complexes to be regarded as potential models for
CX)(CO)9] (Mꢀ
/
Ru or Os; Xꢀa monovalent group)
/
has provided a large number of clusters of these types
[1]. Their reactivity, which has also been extensively
studied, generally involves: (a) modification of the
alkylidyne substituent; (b) ligand substitution or addi-
tion at the metal; (c) protonation and deprotonation
reactions; (d) reductive elimination of CX groups; and
FischerÁTropsch chain growth [2].
/
Recently, our group has been paying significant
attention to the reactivity of diynes toward ruthenium
carbonyl cluster complexes [3]. This research activity has
been motivated by the fact that, to date, only a few
reactions of ruthenium clusters with diynes have
(e) insertion of unsaturated molecules into the MÃ
bond [1].
/CX
appeared in the literature [3Á5], though these poly-
/
unsaturated molecules are expected to be more reactive
than monoalkynes and, therefore, lead to a richer
derivative chemistry. In the course of these studies,
* Corresponding author. Tel.: ꢁ
446.
E-mail address: jac@sauron.quimica.uniovi.es (J.A. Cabeza).
/
34-98-5103 501; fax: ꢁ
/
34-98-5103
results of special note were found, including CÃ
/
C [3]
and CÃN [3e] bond-forming reactions and unprece-
/
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 1 4 4 4 - 5

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J.A. Cabeza et al. / Inorganica Chimica Acta 347 (2003) 107Á113
/
dented cluster mediated [3ꢁ
/
2] cycloaddition processes
arrangements. Their 1H NMR spectra showed the
[3c].
incorporation of one molecule of diyne per cluster. In
all cases, the signal corresponding to the hydrogen
atoms of the original methylidyne ligand appeared as a
With these facts in mind, we embarked on the study of
the reactivity of 1 and 2 with conjugated diynes. In the
present work, we report on the synthesis of trinuclear
ruthenoallyl cluster complexes formed by insertion of
singlet at d :/4 ppm, while a singlet resonance at high
field (d : 19.5 ppm) indicated the presence of a
/
ꢂ
/
one of the alkyne moieties of diyne ligands into a RuÃ
/C
hydride ligand.
Although all these data are in accordance with the
bond of the methylidyne ligand. Hydrogenation of the
second alkyne group of the diyne ligands to the
corresponding alkene is observed when the trihydride
cluster 2 is used as starting material. The X-ray
structures of the two regioisomers formed in the reaction
of 1 with 2,4-hexadiyne are also described.
structures proposed for 3Á8 in Scheme 1, they were not
/
enough to unambiguously determine the ligand disposi-
tion within the cluster shell. Therefore, two regioi-
somers, the couple 3 and 4, were analyzed by X-ray
diffraction methods. Molecular plots for these com-
plexes are shown in Figs. 1 and 2, respectively. A
selection of bond distances is listed in Table 1. For
comparison purposes, a common labeling scheme has
been used in both structures where possible.
2. Results and discussion
The structure of 3 consists of a triruthenium core
triply bridged by an allyl ligand which arises from the
insertion of an alkyne group of the incoming diyne into
When complex 1 was treated with a stoichiometric
amount of diphenylbutadiyne, 2,4-hexadiyne or 1,6-
diphenoxy-2,4-hexadiyne, 1:1 mixtures of the two pos-
sible
insertion
regioisomers,
[Ru3(m-H)(m3-h3-
a RuÃ
/
C bond of the original methylidyne moiety. This
ligand binds Ru(2) through its three allylic carbon
atoms, C(1), C(15) and C(16) in a p-fashion, being
formally s-bonded to Ru(1) and Ru(3). The bond
MeOCCRÄ
/
CCÅCR)(CO)9] (Rꢀ
/
/
Me, 3; Ph, 5; CH2-
OPh, 7) and [Ru3(m-H)(m3-h3-MeOCC(CÅ
/
CR)Ä/CR)-
(CO)9] (Rꢀ
/
Me, 4; Ph, 6; CH2OPh, 8) were obtained
distances Ru(1)Ã
/
C(1), 2.074(4), and Ru(3)Ã
2.082(6) A, are shorter than those corresponding to
Ru(2)ÃC(1), Ru(2)ÃC(15) and Ru(2)ÃC(16), 2.403(6),
/
C(15),
(Scheme 1). In all cases, other products were also formed
in lower yields. The pure regioisomers were separated by
TLC.
˚
/
/
/
˚
The elemental analyses and mass spectra of com-
2.278(9) and 2.309(10) A, respectively, accordingly with
a stronger s-interaction in the first two cases. These
bond distances are comparable to those reported pre-
viously for analogous triruthenium allylic systems [6].
pounds 3Á8 clearly indicated their trinuclear nature,
/
while their IR spectra displayed similar patterns in the
carbonyl stretching region, suggesting analogous ligand
The bond distances within the allyl fragment, C(1)Ã
/
˚
˚
C(15), 1.427(6) A, are
C(16), 1.443(7) A and C(16)Ã
/
similar, accounting for its electronic delocalization. The
central atom of the allylic moiety, C(16), bears a
terminal methyl group of the original 2,4-hexadiyne
ligand, while C(15) supports the uncoordinated alkyne
fragment. A hydride ligand symmetrically spans the
Ru(1)Ã
/
Ru(3) edge, positioned trans to two terminal
Ru(3) distance, 2.934(13)
A, is some 0.15 A longer than those corresponding to
Ru(1)ÃRu(2) and Ru(2)ÃRu(3), respectively, as ob-
carbonyl ligands. The Ru(1)Ã
/
˚
˚
/
/
served previously for related systems [6]. The cluster
shell is completed with nine terminal CO ligands.
As outlined in Section 4, the structure of 4 suffered
from some crystallographic unpleasantness of uncertain
nature, giving two possible independent positions for the
molecule in the crystal. The major position was treated
giving a 90% occupancy to their metal atoms and a
100% occupancy to the remaining atoms, whereas the
minor position was treated giving a 10% occupancy to
the metal atoms, maintaining unlocated its non-metallic
atoms. An entirely analogous problem, the nature of
which remains unknown, was found by Keister et al. in
the crystals of the related compound [Ru3(m-H)(m3-h3-
Scheme 1.

J.A. Cabeza et al. / Inorganica Chimica Acta 347 (2003) 107Á
/
113
109
Fig. 1. Molecular structure of compound 3. Ellipsoids are drawn at the 30% probability level.
Table 1
Selected interatomic distances (A) in compounds 3 and 4
˚
3
4
Ru(1)Ã
Ru(1)Ã
Ru(2)Ã
Ru(1)Ã
Ru(2)Ã
Ru(2)Ã
Ru(2)Ã
Ru(3)Ã
Ru(1)Ã
Ru(3)Ã
/
Ru(2)
Ru(3)
Ru(3)
C(1)
2.778(12)
2.934(13)
2.778(12)
2.074(7)
2.403(6)
2.082(6)
2.309(10)
2.278(9)
1.79(5)
2.784(4)
2.925(3)
2.760(3)
2.059(12)
2.423(13)
2.278(12)
2.279(12)
2.088(12)
1.85(2)
/
/
/
/C(1)
/
C(15)
C(16)
C(15)
H(1)
/
/
/
/H(1)
1.75(4)
1.85(2)
C(1)Ã
/
C(16)
1.443(7)
1.364(5)
1.415(6)
1.427(6)
1.428(18)
1.364(14)
1.378(16)
1.443(18)
C(1)Ã
/
O(1)
C(11)Ã
/O(1)
C(15)Ã
/C(16)
C(15) atom accounts for the difference of approximately
˚
0.2 A observed in the C(15)Ã
/
Ru(2) and C(15)Ã
/
Ru(3)
Fig. 2. Molecular structure of compound 4. Ellipsoids are drawn at
the 30% probability level.
distances when compared to those in 3. The remaining
structural features are entirely analogous to those
described above for 3.
In the case of complexes 5Á8, their IR and NMR data
/
MeCCMeCSEt)(CO)9] [6a], for which they performed
an analogous structure treatment.
The structure of 4 is similar to that described above
for 3, although in this case the central atom of the allylic
fragment supports the uncoordinated alkyne group,
while the terminal methyl group is bonded to C(15).
strongly indicate that they are isostructural to 3 and 4,
although these data are not enough to unequivocally
establish the correct diyne position in each regioisomeric
couple. Therefore, the ligand arrangement was assigned
by comparison of their TLC elution order. However, a
different assignment cannot be completely ruled out.
The reactivity of the trihydride cluster [Ru3(m-H)3(m3-
COMe)(CO)9] (2) towards simple monoalkynes has been
reported previously [2]. In these reactions, the first
process observed is the hydrogenation of one molecule
The hydride-bridged edge, Ru(1)Ã
slightly longer than the other two unbridged edges. In
the allylic fragment, the C(1)ÃRu(1), C(1)ÃRu(2) and
C(16)ÃRu(2) distances are similar to those found in
complex 3. In contrast, the different substituent at the
/Ru(3), is again
/
/
/

110
J.A. Cabeza et al. / Inorganica Chimica Acta 347 (2003) 107Á113
/
of alkyne to afford an unsaturated monohydride inter-
mediate that undergoes further reaction with a second
molecule of alkyne to give an allylic derivative similar to
those obtained when 1 is used as starting material. In
our case, the use of diyne ligands instead of simple
monoalkynes made possible that these processes took
place at the same molecule, leading to novel organic
fragments.
cluster intermediate which reacts either with the enynes
to give 9Á12 or with the remaining diyne to give 5 and 6.
/
3. Conclusions
The results reported herein indicate that when 1 is
used as starting material, diynes behave as asymmetric
alkynes, since all the isolated products contain a
pendant (non-coordinated) alkyne fragment, affording
allylic compounds similar to those formed in the
reaction of 1 and 2 with mono-alkynes. In contrast,
when the trihydride derivative 2 is treated with sym-
metric diynes, hydrogenation and insertion processes
take place at the same diyne molecule, resulting in novel
organic fragments. Unfortunately, the isolation of the
pure products obtained in this latter reaction has not
been accomplished yet.
Thus, treatment of 2 with diphenylbutadiyne led to
derivatives 9Á12 (Scheme 2), in which the hydrogena-
/
tion of one of the two alkyne functionalities took place,
while the second alkyne group underwent insertion into
a RuÃ
/
C bond of the methylidyne fragment to afford an
allyl fragment similar to those described above. Hydro-
genation of the alkene functionality or insertion of the
alkene group into a RuÃ
/
C bond of the methylidyne were
not observed in any case.
The cis- and trans-alkene isomers of the two alkyne
insertion regioisomers were observed in the reaction
mixture by 1H NMR spectroscopy, along with small
amounts of complexes 5 and 6 and decomposition
products. TLC chromatography, using multiple elution
with hexanes, allowed the separation of all the insertion
regioisomers, but the cis and trans isomers of the alkene
4. Experimental
products 9Á12 were not separated. We managed to
/
1
4.1. General data
obtain most of their H NMR data from the spectra of
different chromatography fractions. Again, the TLC
elution order was used to distinguish between the two
couples of insertion regioisomers.
Thus, the reaction pathway seems to be as follows:
compound 2 reacts with the diyne to give a mixture of
cis and trans enynes and an unsaturated monohydride
Solvents were dried over sodium benzophenone ketyl
(THF, hydrocarbons) or CaH2 (CH2Cl2) and distilled
under nitrogen prior to use. The reactions were carried
out under nitrogen and were monitored by solution IR
and spot TLC. All reagents were obtained from
commercial sources. Compounds 1 and 2 were prepared
according to literature methods [7]. IR spectra were
recorded in solution on a PerkinÁElmer Paragon 1000
/
FT spectrophotometer. NMR spectra were run on AC-
200, AC-300 or DPX-300 instruments, using the residual
solvent peak as reference. Microanalyses were obtained
from the University of Oviedo Analytical Service. FAB-
MS were obtained from the University of Santiago de
Compostela Mass Spectrometric Service; data given
refer to the most abundant molecular ion isotopomer.
4.2. General procedure for the reactions of 1 with diynes
In a typical reaction, a solution of 1 in THF (50 ml)
was stirred at reflux temperature with the appropriate
amount of diyne until complete consumption of the
starting material 1 (IR monitoring), whereupon the
color changed from pale orange to brown. The solvent
was concentrated under reduced pressure to approxi-
mately 2 ml and the residue was applied onto silica gel
preparative TLC plates. Repeated elution with hexanes
afforded the products.
Scheme 2.

J.A. Cabeza et al. / Inorganica Chimica Acta 347 (2003) 107Á
/
113
111
4.2.1. Synthesis of [Ru3(m-H)(m3-h3-MeOCC(Me)Ä
CCÅ
CMe)(CO)9] (3) and [Ru3(m-H)(m3-h3-
MeOCC(CÅCMe)ÄCMe)(CO)9] (4)
/
Calc. for C27H14O10Ru3 (801.6): C, 40.45; H, 1.76;
Found: C, 40.72; H, 1.90%.
/
/
/
Reactants: 1 (350 mg, 0.56 mmol); 2,4-hexadiyne (56.5
4.2.3. Synthesis of [Ru3(m-H)(m3-h3-
mg, 0.725 mmol). Reaction time: 2 h 30 min.
Data for 3: TLC second band (yellow). Yield: 45 mg
(12%). IR (CH2Cl2) nCO: 2093(m), 2066(s), 2041(s),
MeOCC(CH2OPh)Ä
[Ru3(m-H)(m3-h3-MeOCC(CÅ
CCH2OPh)(CO)9] (8)
/
CCÅ
/
CCH2OPh)(CO)9] (7) and
/
CCH2OPh)Ä
/
1
2019(m), 2005(m), 1991(w) cmꢂ1. H NMR (CD2Cl2):
Reactants: 1 (100 mg, 0.16 mmol); 1,6-diphenoxy-2,4-
hexadiyne (50 mg, 0.20 mmol). Reaction time: 60 min.
Data for 7: Yield: 28 mg (21%). TLC band: second,
yellow. IR (CH2Cl2) nCO: 2096(m), 2068(s), 2040(s),
dꢀ
Me), ꢂ
(CD2Cl2): dꢀ
/
3.92 (s, 3H, OMe), 2.19 (s, 3H, Me), 2.06 (s, 3H,
19.50 (s, 1H, m-H) ppm. 13C{1H) NMR
232.9 (COMe); 198.5, 197.5, 192.9,
/
/
191.6 (2 C), 189.5 (2C), 189.4 (2 C) (9 COs); 159.4
(C), 115.3 (C), 103.7 (C), 88.9 (C); 65.0 (COMe), 22.4
(Me), 5.5 (Me) ppm. FAB-MS: m/z: 679 [Mꢁ]. Anal.
Calc. for C17H10O10Ru3 (677.5): C, 30.13; H, 1.48;
Found: C, 30.55; H, 1.63%.
1
2020(m), 2007(m), 1988(w) cmꢂ1. H NMR (CD2Cl2):
dꢀ
(d, Jꢀ
(s, 3H, OMe), ꢂ
/
7.50Á
/
7.02 (m, 10H, Ph), 4.78 (s, 2H, CH2), 4.77
/
13.8, 1H, CH2), 4.69 (d, Jꢀ
/13.8, 1H, CH2), 3.97
/
19.43 (s, 1H, m-H) ppm. FAB-MS: m/z:
863 [Mꢁ]. Anal. Calc. for C29H18O12Ru3 (861.3): C,
40.42; H, 2.10; Found: C, 40.13; H, 2.02%.
Data for 4: Yield: 37 mg (10%). TLC band: fourth,
yellow. IR (CH2Cl2) nCO: 2092(m), 2065(s), 2040(s),
Data for 8: Yield: 20 mg (16%). TLC band: third,
yellow. IR (CH2Cl2) nCO: 2096(m), 2071(s), 2042(s),
1
2022(m), 2006(m), 1992(w) cmꢂ1. H NMR (CD2Cl2):
dꢀ
Me), ꢂ
(CD2Cl2): dꢀ
/
4.04 (s, 3H, OMe), 3.00 (s, 3H, Me), 2.04 (s, 3H,
19.55 (s, 1H, m-H) ppm. 13C{1H} NMR
232.3 (COMe); 205.6, 197.3, 196.2,
1
2027(m), 2013(m), 1990(w) cmꢂ1. H NMR (CD2Cl2):
/
dꢀ
/
7.50Á
/
7.00 (m, 10H, 2 Ph), 5.13 (d, Jꢀ
/
13.9, 1H,
13.9, 1H, CH2),
/
CH2), 4.92 (s, 2H, CH2), 4.84 (d, Jꢀ
/
192.5, 191.9, 191.5, 190.3, 190.0, 189.8 (9 COs); 187.6
(C), 102.4 (C), 90.2 (C), 76.6 (C); 64.6 (COMe), 39.6
(Me), 4.0 (Me) ppm. FAB-MS: m/z: 679 [Mꢁ]. Anal.
Calc. for C17H10O10Ru3 (677.5): C, 30.13; H, 1.48;
Found: C, 30.46; H, 1.59%.
4.02 (s, 3H, OMe), ꢂ19.70 (s, 1H, m-H) ppm. FAB-MS:
/
m/z: 861.9 [Mꢁ]. Anal. Calc. for C29H18O12Ru3 (861.3):
C, 40.42; H, 2.10; Found: C, 40.74; H, 2.21%.
4.3. Reaction of 2 with diphenylbutadiyne
4.2.2. Synthesis of [Ru3(m-H)(m3-h3-MeOCC(Ph)Ä
CCÅ
CPh)(CO)9] (5) and [Ru3(m-H)(m3-h3-
MeOCC(CÅCPh)ÄCPh)(CO)9] (6)
/
A solution of 2 (100 mg, 0.166 mmol) in THF (50 ml)
was stirred for 3 h at room temperature with 37 mg
(0.182 mmol) of diphenylbutadiyne. The color changed
/
/
/
Reactants: 1 (100 mg, 0.16 mmol); diphenylbutadiyne
to redÁbrown. The solvent was concentrated under
/
(38.7 mg, 0.20 mmol). Reaction time: 40 min.
Data for 5: Yield: 20 mg (16%). TLC band: first,
yellow. IR (CH2Cl2) nCO: 2096(m), 2071(s), 2042(s),
vacuum to approximately 2 ml and the residue was
applied onto silica gel preparative TLC plates. Repeated
elution with hexanes afforded three yellow bands. The
first band contained approximately 5 mg of complex 5.
The second band (12 mg) was a mixture of complexes 6,
9 and 10 in a 3:10:5 ratio, respectively (1H NMR
integration). The third band contained approximately
10 mg of complexes 11 and 12 in a 1:1 ratio.
1
2027(m), 2013(m), 1990(w) cmꢂ1. H NMR (CD2Cl2):
dꢀ
/
7.22Á
/
6.99 (m, 10 H, Ph), 4.12 (s, 3H, OMe), ꢂ
/
19.56
(s, 1H, m-H) ppm. 13C{1H} NMR (CD2Cl2): dꢀ
/
226.3
(COMe); 196.3, 196.0, 191.9, 191.5, 191.4, 190.3, 189.4,
188.6, 188.5 (9 COs); 152.1 (C), 105.1 (C), 92.5 (C), 88.0
(C); 130.6, 130.5, 128.7, 128.2, 127.7, 127.6, 127.5, 127.1,
126.0, 125.9, 121.5, 121.3 (2 Ph); 64.5 (COMe) ppm.
FAB-MS: m/z: 803 [Mꢁ]. Anal. Calc. for
C27H10O10Ru3 (801.6): C, 40.45; H, 1.76; Found: C,
40.63; H, 1.61%.
Selected 1H NMR data for cis-[Ru3(m-H)(m3-
h3MeOCC(Ph)Ä
/
CCHÄ
7.9, 1H, CH), 4.01 (d, Jꢀ
3.96 (s, 3H, OMe), ꢂ18.00 (s, 1H, m-H) ppm.
Selected 1H NMR data for trans-[Ru3(m-H)(m3-h3-
MeOCC(Ph)ÄCCHÄCHPh)(CO)9] (10): d (CD2Cl2):
6.65 (d, Jꢀ12.8, 1H, CH), 5.61 (d, Jꢀ12.8, 1H, CH),
3.84 (s, 3H, OMe), ꢂ19.02 (s, 1H, m-H) ppm.
Selected 1H NMR data for cis-[Ru3(m-H)(m3-
h3MeOCC(CHÄ
CHPh)ÄCPh)(CO)9] (11): d (CD2Cl2):
3.75 (s, 3H, OMe), ꢂ19.51 (s, 1H, m-H) ppm.
Selected 1H NMR data for trans-[Ru3(m-H)(m3-h3-
MeOCC(CHÄCHPh)ÄCPh)(CO)9] (12): d (CD2Cl2):
6.17 (d, Jꢀ11.8, 1H, CH), 6.05 (d, Jꢀ11.8, 1H, CH),
3.70 (s, 3H, OMe), ꢂ19.67 (s, 1H, m-H) ppm.
/
CHPh)(CO)9] (9): d (CD2Cl2):
6.35 (d, Jꢀ
/
/
7.9, 1H, CH),
/
Data for 6: Yield: 24 mg (18%). TLC band: second,
yellow. IR (CH2Cl2) nCO: 2095(m), 2070(s), 2044(s),
/
/
/
/
1
2024(m), 2009(m), 1990(w) cmꢂ1. H NMR (CD2Cl2):
/
dꢀ
19.30 (s, 1H, m-H) ppm. 13C{1H} NMR (CD2Cl2):
dꢀ231.8 (COMe); 205.2, 197.5, 196.2, 191.8, 191.5,
/
7.53Á/7.10 (m, 10 H, 2 Ph), 3.83 (s, 3H, OMe),
ꢂ
/
/
/
/
/
190.7, 190.4, 188.5, 188.3 (9 COs); 154.5 (C), 139.9 (C),
103.0 (C), 98.2 (C); 131.2, 130.4, 129.5, 128.0, 127.6,
127.3, 127.0, 126.8, 126.4, 124.0, 123.9, 122.0 (2 Ph);
64.7 (COMe) ppm. FAB-MS: m/z: 803 [Mꢁ]. Anal.
/
/
/
/
/

112
J.A. Cabeza et al. / Inorganica Chimica Acta 347 (2003) 107Á113
/
4.4. Crystallographic studies
the other hydrogen atom positions were geometrically
calculated and refined riding on their parent atoms.
Diffraction data were collected on a Nonius CAD-4
2u scan technique and a
diffractometer, with the v Á
/
4.4.2. X-ray structure of 4
variable scan rate, using graphite-monochromated Mo
Ka radiation. Lorentz and polarization corrections were
applied, and data were reduced to Fo2 values. Empirical
absorption corrections were applied using XABS2 [8]. The
structures were solved by Patterson interpretation using
the program DIRDIF-96 [9]. Isotropic and full-matrix
anisotropic least-squares refinements were carried out
using SHELXL-97 [10]. All non-H atoms were refined
anisotropically. The molecular plots were made with the
EUCLID program package [11]. The WINGX program
system [12] was used throughout the structure determi-
nations. Revelant crystal and refinement data are given
in Table 2.
Suitable crystals were obtained by slow diffusion of
pentane into a benzene solution of complex 4. Max-
imum and minimum transmission factors 0.694 and
0.485, respectively. The position of the hydride atom
H(1) was calculated using the program XHYDEX [13], its
coordinates were fixed and its thermal parameters were
refined. All the remaining hydrogen atom positions were
geometrically calculated and refined riding on their
parent atoms. Refinement of this model converged
with a high discrepancy index (R1ꢀ12.6%). A differ-
/
ence-Fourier synthesis showed three prominent peaks
superimposed to the triangle of Ru atoms. Six different
data sets, using different crystals, were collected either in
this diffractometer or in a Kappa-CCD, but they all
gave analogous results. We included these three peaks in
the model, as atoms Ru(1b), Ru(2b) and Ru(3b), with
their site occupancy factors coupled to those of Ru(1),
Ru(2) and Ru(3), respectively. This gave occupancy
factors of approximately 0.10 for these new atoms and
0.90 for Ru(1), Ru(2) and Ru(3). Full-matrix least-
squares refinement of this model led to a significant
4.4.1. X-ray structure of 3
Suitable crystals were obtained by slow diffusion of
pentane into an acetone solution of complex 3. Max-
imum and minimum transmission factors 0.807 and
0.645, respectively. The position of the hydride atom
H(1) was located by Fourier difference maps and its
coordinates and thermal parameters were refined. All
reduction in the discrepancy index (R1ꢀ6.67%), with a
/
Goodness-of-fitꢀ
showed density in the range 1.047 to ꢂ
/
1.103. A final difference-Fourier map
ꢂ3
Table 2
Relevant crystal and refinement data for compounds 3 and 4
˚
1.131 e A
/
.
Compound
3
4
5. Supplementary material
Formula
M
C
17H10O10Ru3
C17H10O10Ru3
677.46
293(2)
0.71073
monoclinic
P21/c
677.46
293(2)
0.71073
orthorhombic
Pbca
Temperature (K)
˚
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC Nos. 184062Á184063 for com-
pounds 3 and 4, respectively. Copies of this information
may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
l(Mo Ka) (A)
Crystal system
/
Space group
˚
a (A)
˚
13.839(10)
12.5811(16)
24.59(11)
90
18.422(15)
7.033(3)
18.44(3)
90
b (A)
˚
c (A)
a (8)
b (8)
g (8)
(fax:
ac.uk or www: http://www.ccdc.cam.ac.uk).
ꢁ44-1223-336-033; e-mail: deposit@ccdc.cam.
/
90
90
116.68(7)
90
3
˚
V (A )
Z
4281(19)
8
2.102
2135(4)
4
2.108
Dcalc (g cmꢂ3
)
Acknowledgements
m (mmꢂ1
F(000)
)
2.138
2592
2.145
1296
Financial support form the Spanish DGESIC (grants
PB95-1042 and PB98-1555 to J.A.C., and BQU2000-
0219 to S.G.-G.) is gratefully acknowledged.
Crystyal size (mm)
u max (8)
h, k, l ranges
0.27ꢃ
25.97
175
155
305
/
0.20ꢃ
/
0.10 0.33ꢃ
25.99
225
05k 5
205l 5
/
0.23ꢃ0.17
/
ꢂ
/
/
h 5
k 5
l 5
/0,
ꢂ
/
/h 5/0,
ꢂ
/
/
/
0,
/
/8,
ꢂ/
/
/0
ꢂ/
/
/22
Measured reflections
Unique reflections
4166
4166
4338
4204
3065
299
References
Reflections with [I ꢀ
/
2s(I)] 2950
[1] A.K. Smith, in: E.W. Abel, F.G.A. Stone, G. Wilkinson, D.F.
Shriver, M.I. Bruce (Eds.), Comprehensive Organometallic Chem-
istry II, vol. 7, Pergamon, Oxford, 1995, p. 747.
Parameters
R1 (on F2, I ꢀ
275
0.0281
/
2s(I))
wR2 (on F2, all data)
0.0667
0.2004
1.103
0.0709
1.030
Goodness-of-fit on F2
[2] (a) L.R. Beanan, Z.A. Rahman, J.B. Keister, Organometallics 2
(1983) 1062;
(b) L.R. Beanan, J.B. Keister, Organometallics 4 (1985) 1713.
ꢂ3
˚
Min, max Dr (e A
)
ꢂ
/
0.463, 0.455
ꢂ/1.131, 1.047

J.A. Cabeza et al. / Inorganica Chimica Acta 347 (2003) 107Á
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/
(f) S.P. Tunik, E.V. Grachova, V.R. Denisov, G.L. Starova, A.B.
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¨
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/
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¨
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¨
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