Syntheses of ketonated disulfide-bridged diruthenium complexes via C-H bond activation and C-S bond formation

Article abstract of DOI:10.1021/ic0000855

The α-C-H bonds of 3-methyl-2-butanone, 3-pentanone, and 2-methyl-3-pentanone were activated on the sulfur center of the disulfide-bridged ruthenium dinuclear complex [{RuCl(P(OCH₃)₃)₂}₂(μ-S₂)(μ-Cl)₂] (1) in the presence of AgX (X = PF₆, SbF₆) with concomitant formation of C-S bonds to give the corresponding ketonated complexes [{Ru(CH₃CN)₂(P(OCH₃)₃)₂}(μ-SSCHR¹COR²){Ru(CH₃CN)₃( P(OCH₃)₃)₂}]X₃ ([5](PF₆)₃, R¹ = H, R² = CH(CH₃)₂, X = PF₆; [6](PF₆)₃, R¹ = CH₃, R² = CH₂CH₃, X = PF₆; [7](SbF₆)₃, R¹ = CH₃, R² = CH(CH₃)₂, X = SbF₆). For unsymmetric ketones, the primary or the secondary carbon of the α-C-H bond, rather than the tertiary carbon, is preferentially bound to one of the two bridging sulfur atoms. The α-C-H bond of the cyclic ketone cyclohexanone was cleaved to give the complex [{Ru(CH₃CN)₂(P(OCH₃)₃)₂}(μ-SS-1-cyclohexanon-2-yl){Ru(CH₃CN)₃(P(OC H₃)₃)₂}](SbF₆)₃ ([8](SBF₆)₃). And the reactions of acetophenone and p-methoxyacetophenone, respectively, with the chloride-free complex [{Ru(CH₃CN)₃(P(OCH₃)₃)₂}₂(μ-S₂)]⁴⁺ (3) gave [{Ru(CH₃CN)₂(P(OCH₃)₃)₂}(μ-SSCH₂COAr){Ru(CH₃CN)₃(P(OCH₃)₃)₂}] (CF₃SO₃)₃ ([9](CF₃SO₃)₃, Ar = Ph; [10](CF₃SO₃)₃, Ar = p-CH₃OC₆H₄). The relative reactivities of a primary and a secondary C-H bond were clearly observed in the reaction of butanone with complex 3, which gave a mixture of two complexes, i.e., [{Ru(CH₃CN)₂(P(OCH₃)₃)₂}(μ-SSCH₂COCH₂-CH₃){Ru(CH₃CN)₃ (P(OCH₃)₃)₂}](CF₃SO₃)₃ ([11](CF₃SO₃)₃) and [{Ru(CH₃CN)₂(P(OCH₃)₃)₂} (μ-SSCHCH₃COCH₃){Ru(CH₃CN)₃(P(OCH₃)₃)₂}](CF₃SO₃)₃ ([12](CF₃SO₃)₃), in a molar ratio of 1:1.8. Complex 12 was converted to 11 at room temperature if the reaction time was prolonged. The relative reactivities of the α-C-H bonds of the ketones were deduced to be in the order 2°> 1°> 3°, on the basis of the consideration of contributions from both electronic and steric effects. Additionally, the C-S bonds in the ketonated complexes were found to be cleaved easily by protonation at room temperature. The mechanism for the formation of the ketonated disulfide-bridged ruthenium dinuclear complexes is as follows: Initial coordination of the oxygen atom of the carbonyl group to the ruthenium center, followed by addition of an α-C-H bond to the disulfide bridging ligand, having S=S double-bond character, to form a C-S-S-H moiety, and finally completion of the reaction by deprotonation of the S-H bond.

Full text of DOI:10.1021/ic0000855

3
948
Inorg. Chem. 2000, 39, 3948-3956
Ar ticles
Syntheses of Ketonated Disulfide-Bridged Diruthenium Complexes via C-H Bond
Activation and C-S Bond Formation
‡
‡
‡
,†
Hiroyasu Sugiyama, Md. Munkir Hossain, Yong-Shou Lin, and Kazuko Matsumoto*
Department of Chemistry, Advanced Research Center for Science and Engineering, Waseda University,
3
-4-1 Ohkubo, Shinjuku, Tokyo 169-8555, Japan, and Japan Science and Technology Corporation, 4-1-8
Honmachi, Kawaguchi, Saitama 332-0012, Japan
ReceiVed January 26, 2000
The R-C-H bonds of 3-methyl-2-butanone, 3-pentanone, and 2-methyl-3-pentanone were activated on the sulfur
center of the disulfide-bridged ruthenium dinuclear complex [{RuCl(P(OCH3)3)2}2(µ-S2)(µ-Cl)2] (1) in the presence
of AgX (X ) PF6, SbF6) with concomitant formation of C-S bonds to give the corresponding ketonated complexes
1
2
1
2
[
{Ru(CH3CN)2(P(OCH3)3)2}(µ-SSCHR COR ){Ru(CH3CN)3(P(OCH3)3)2}]X3 ([5](PF6)3, R ) H, R ) CH(CH3)2,
1
2
1
2
X ) PF6; [6](PF6)3, R ) CH3, R ) CH2CH3, X ) PF6; [7](SbF6)3, R ) CH3, R ) CH(CH3)2, X ) SbF6). For
unsymmetric ketones, the primary or the secondary carbon of the R-C-H bond, rather than the tertiary carbon,
is preferentially bound to one of the two bridging sulfur atoms. The R-C-H bond of the cyclic ketone cyclohexanone
was cleaved to give the complex [{Ru(CH3CN)2(P(OCH3)3)2}(µ-SS-1-cyclohexanon-2-yl){Ru(CH3CN)3(P-
(
OCH3)3)2}](SbF6)3 ([8](SbF6)3). And the reactions of acetophenone and p-methoxyacetophenone, respectively,
4
+
with the chloride-free complex [{Ru(CH3CN)3(P(OCH3)3)2}2(µ-S2)] (3) gave [{Ru(CH3CN)2(P(OCH3)3)2}(µ-
SSCH2COAr){Ru(CH3CN)3(P(OCH3)3)2}](CF3SO3)3 ([9](CF3SO3)3, Ar ) Ph; [10](CF3SO3)3, Ar ) p-CH3OC6H4).
The relative reactivities of a primary and a secondary C-H bond were clearly observed in the reaction of butanone
with complex 3, which gave a mixture of two complexes, i.e., [{Ru(CH3CN)2(P(OCH3)3)2}(µ-SSCH2COCH2-
CH3){Ru(CH3CN)3(P(OCH3)3)2}](CF3SO3)3 ([11](CF3SO3)3) and [{Ru(CH3CN)2(P(OCH3)3)2}(µ-SSCHCH3CO-
CH3){Ru(CH3CN)3(P(OCH3)3)2}](CF3SO3)3 ([12](CF3SO3)3), in a molar ratio of 1:1.8. Complex 12 was converted
to 11 at room temperature if the reaction time was prolonged. The relative reactivities of the R-C-H bonds of the
ketones were deduced to be in the order 2° > 1° > 3°, on the basis of the consideration of contributions from
both electronic and steric effects. Additionally, the C-S bonds in the ketonated complexes were found to be
cleaved easily by protonation at room temperature. The mechanism for the formation of the ketonated disulfide-
bridged ruthenium dinuclear complexes is as follows: initial coordination of the oxygen atom of the carbonyl
group to the ruthenium center, followed by addition of an R-C-H bond to the disulfide bridging ligand, having
SdS double-bond character, to form a C-S-S-H moiety, and finally completion of the reaction by deprotonation
of the S-H bond.
Introduction
reactions are mostly additions of coordinated sulfides, disulfides,
7-14
12-18
and polysulfides either to CtC bonds
or to CdC bonds
Studies of transition metal sulfide and polysulfide complexes
have been recognized as an important field of basic and applied
inorganic chemistry. Although the reactivity of sulfide ligands
and there are few examples of C-H bond activations on sulfur
centers. Activation of the C-H bond of acetone on the disulfide
complex [{RuCl(P(OCH3)3)2}2(µ-S2)(µ-Cl)2] (1) in the presence
of 4 equiv of a silver salt has been reported to give [{Ru(CH3-
1-6
4
-6
in metal sulfides has been explored to some extent,
the
†
Waseda University.
Japan Science and Technology Corporation.
(7) Goodman, J. T.; Rauchfuss, T. B. Inorg. Chem. 1998, 37, 5040.
(8) Kuwata, S.; Andou, M.; Hashizume, K.; Mizobe, Y.; Hidai, M.
Organometallics 1998, 17, 3429.
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Soc. 1997, 119, 10346.
‡
(
(
(
1) M u¨ ller, A.; Diemann, E. In ComprehensiVe Coordination Chemistry;
Wilkinson, G., Gillard, R. D., McCleverty, J. A., Eds.; Pergamon
Press: Oxford, U.K., 1987; Vol. 2, p 515.
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Cofactors, and Model Systems; American Chemical Society: Wash-
ington, DC, 1993.
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Biological and Industrial Significance; ACS Symposium Series 653;
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1
0.1021/ic0000855 CCC: $19.00 © 2000 American Chemical Society
Published on Web 08/09/2000

Ketonated Disulfide-Bridged Diruthenium Complexes
Inorganic Chemistry, Vol. 39, No. 18, 2000 3949
Scheme 1
CN)2(P(OCH3)3)2}(µ-SSCH2COCH3){Ru(CH3CN)3(P(OCH3)3)2}]-
atoms.3
0-35
Previously, we reported that the reactions of the
(
CF3SO3)3 ([2](CF3SO3)3) through formation of the chloride-
disulfide-bridged diruthenium complex [{RuCl(P(OCH3)3)2}2(µ-
S2)(µ-Cl)2] (1) with 1, 2, and 4 equiv of a silver salt in
acetonitrile resulted in successive substitutions of the terminal
4+
free complex [{Ru(CH3CN)3(P(OCH3)3)2}(µ-S2)] (3) (Scheme
1
achieved on a monosulfide metal complex to produce (C5Me5)3-
RhRu2S3(SCH2COMe) . Very recently, activation of an allylic
C-H bond of an alkene on a disulfide bridging ligand in a
diruthenium complex accompanied by the formation of one or
two C-S bonds has been realized in our group.21 These C-H
bond activation reactions on sulfur centers contrast markedly
with the extensively studied organometallic chemistry on
transition metal centers.2
disulfide ligands in transition metal complexes have been little
studied and may open a new field not only of sulfur chemistry
but also of organometallic-like chemistry on sulfur centers.
1
9
). Activation of the C-H bond of acetone has also been
3
6,37
and bridge chloride ions with acetonitrile.
With 4 equiv of
III
III
+
20
the silver salt, 3, with an Ru SSRu core, was obtained as the
initial product, which was, however, easily reduced in CH3CN
to the more stable paramagnetic complex [{Ru(CH3CN)3(P-
3
+
II
III
(OCH3)3)2}(µ-S2)] (4), with an Ru SSRu core (Scheme
1
3
6,37
).
After a series of studies on the properties of S2-bridged
dinuclear ruthenium complexes with and without chloride
2-24
The chemical reactivities of
1
9,21,36-43
bridging ligands,
it has become clear that the sulfur
III
III
center in the Ru SSRu unit has, like many other transition
metal centers, a variety of reactivities toward many organic
substrates. In the present study, to explore the true mechanism
and the driving force operating in C-H bond activation on the
sulfur center of a disulfide-bridged complex, we have synthe-
sized various ketonated disulfide-bridged diruthenium complexes
via activation of the R-C-H bonds of the starting ketones. The
9,12,25-29
Disulfide diruthenium complexes such as 1 and others having
III
III
an Ru SSRu core have been reported to exhibit electron-
deficient, double-bond character on the two bridging sulfur
(
16) Koval, C. R.; Lopez, L. L.; Kaul, B. B.; Renshaw, S.; Green, K.;
Rakowski DuBois, M. Organometallics 1995, 14, 3440 and references
therein.
(30) Sellmann, D.; Lechner, P.; Knoch, F.; Moll, M. J. Am. Chem. Soc.
1992, 114, 922.
(
17) Birnbaum, J.; Haltiwanger, R. C.; Bernatis, P.; Teachout, C.; Parker,
T. K.; Rakowski DuBois, M. Organometallics 1991, 10, 1779.
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R. C.; Rakowski DuBois, M. J. Am. Chem. Soc. 1983, 105, 5329.
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Waszcyak, J. V. J. Am. Chem. Soc. 1983, 105, 336.
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1987, 26, 2017.
(
(
(
36, 1360.
(
(
21) Hossain, M. M.; Lin, Y.-S.; Sugiyama, H.; Matsumoto, K. J. Am.
Chem. Soc. 2000, 122, 172.
22) Murai, S. Topics in Organometallic Chemistry; Springer-Verlag:
Berlin, 1999; Vol. 3.
(35) Brulet, C. R.; Isied, S. S.; Taube, H. J. Am. Chem. Soc. 1973, 95,
4758.
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Nishide, T.; Sato, T. J. Am. Chem. Soc. 1996, 114, 3597.
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(38) Matsumoto, K.; Koyama, T.; Furuhashi, T. In Transition Metal Sulfur
Chemistry. Biological and Industrial Significance; Stiefel, E. I.,
Matsumoto, K., Eds.; ACS Symposium Series 653; American Chemi-
cal Society: Washington, DC, 1996; p 251 and references therein.
(39) Koyama, T.; Koide, Y.; Matsumoto, K. Inorg. Chem. 1999, 38, 3241.
(40) Matsumoto, K.; Sano, Y. Inorg. Chem. 1997, 36, 4405.
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(42) Kawano, M.; Uemura, H.; Watanabe, T.; Matsumoto, K. J. Am. Chem.
Soc. 1993, 115, 2068.
(
(
23) Shilov, A. E.; Shul’pin, G. B. Chem. ReV. 1997, 97, 2879.
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Metal Complexes; Reidel: Dordrecht, The Netherlands, 1984.
25) Weberg, R.; Haltiwanger, R. C.; Rakowski DuBois, M. Organome-
tallics 1985, 4, 1315.
(
(
(
26) Kubas, G. J.; Vergamini, P. J. Inorg. Chem. 1981, 20, 2667.
27) Halbert, T. R.; Pan, W.-H.; Stiefel, E. I. J. Am. Chem. Soc. 1983,
105, 5476.
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5158.

3950 Inorganic Chemistry, Vol. 39, No. 18, 2000
Sugiyama et al.
Scheme 2
mechanism is considered on the basis of these reactions carried
out under different conditions.
quantitative recovery of the ketone along with generation of
the chloride-free complex 3. The reaction was confirmed by
1
31
H and P NMR analysis. When HCl is used, the ruthenium
Results and Discussion
complexes [{RuCl(P(OCH3)3)2}(µ-S2)(µ-Cl)2{Ru(CH3CN)(P-
+
(
OCH3)3)2}] and 1 are formed by the replacement of the
Syntheses of the Ketonated Complexes. In contrast to the
3
6
coordinated CH3CN with chloride ions. The former complex
is further totally converted to the 1 if the reaction time is
extended to several days in the presence of excess HCl.
The easy protonation of the ketonated complexes accompa-
nied by the scission of the C-S bond can be regarded as the
reverse of the C-H bond activation of ketones by ruthenium
complex 3. Similar reversible formation of covalent C-S bonds
on a high-valent molybdenum monosulfide complex was
previous synthesis of the ketonated disufide-bridged diruthenium
1
9
complex 2, a more simplified method has been developed for
the syntheses of ketonated complexes from various symmetric
and unsymmetric ketones via activation of the R-C-H bonds
on the sulfur center of a disulfide-bridged diruthenium complex.
This is a modification of the previous method used for the
preparation of complex 2.19 Treatment of 1 with 4 equiv of a
silver salt and large excesses of the linear ketones 3-methyl-2-
butanone, 3-pentanone, and 2-methyl-3-pentanone, respectively,
in CH3CN at room temperature resulted in the formation of the
pale green ketonated complexes [{Ru(CH3CN)2(P(OCH3)3)2}(µ-
16,18,44,45
previously reported.
It is well-known that desulfurization
of organic sulfides, especially thiophene and its derivatives, is
a very important process in the petroleum industry.46 The fact
that the C-S bonds in ketonated disulfide complexes can be
readily cleaved by simple protonation at room temperature
provides useful information for studies of desulfurization
reactions in which dinuclear transition metals that sandwich
sulfide ligands may play a key role in the C-S bond cleavage
process.
A Modified Method for the Preparation of Complex 3 and
Formation of Ketonated Complexes Directly from 3. (a)
Preparation of Complex 3. Complex 3 is considered to be a
reactive intermediate in the C-H bond activation reactions for
the ketonated complexes. Formerly, 3 was prepared by adding
1
2
1
SSCHR COR ){Ru(CH3CN)3(P(OCH3)3)2}]X3 ([5](PF6)3, R )
2
1
2
H, R ) CH(CH3)2, X ) PF6; [6](PF6)3, R ) CH3, R ) CH2-
1
2
CH3, X ) PF6; [7](SbF6)3, R ) CH3, R ) CH(CH3)2, X )
SbF6) in 61-66% yields (Scheme 2). Analogously, the cyclic
ketone cyclohexanone with AgSbF6 as the silver salt gave the
corresponding complex [{Ru(CH3CN)2(P(OCH3)3)2}(µ-SS-1-
cyclohexanon-2-yl){Ru(CH3CN)3(P(OCH3)3)2}](SbF6)3 ([8](Sb-
F6)3) in a 69% yield (Scheme 2).
1
All complexes obtained were identified by H NMR spec-
troscopy and elemental analyses (see Experimental Section). The
structures of 7 and 8 were confirmed by X-ray analyses (vide
infra).
4
equiv of a silver salt to 1, but this procedure often gives a
mixture of 3 and 4. As a more convenient synthesis of 3, the
acetonated complex 2 was treated with CF3SO3H to give 3 in
high yield. Complex 3 can be isolated and stored as the staring
material for further reactions (Scheme 3).
In contrast to the preceding ketones, (CH3)3CCOC(CH3)3 (no
R-hydrogen) failed to react under conditions similar to those
described above. Furthermore, we carried out the reactions with
CH3COOCH3 and acetylacetone, which have higher contribu-
tions of their enol forms, but no product with a C-S bond was
obtained. Only the Ru /Ru complex 4 was recovered after
workup, indicating failure of the C-S bond to form.
Protonation of the Ketonated Complexes. The newly
formed C-S bonds in the ketonated disulfide complexes are
relatively susceptible to protonation. Addition of an excess
amount of acid, for example, HClO4 or CF3SO3H, to a CD3CN
solution of a ketonated complex at room temperature im-
mediately leads to the cleavage of the C-S bond with
(b) Reactions of 3 with Ketones. The aromatic ketonated
II
III
complexes [{Ru(CH CN) (P(OCH ) ) }(µ-SSCH COAr){Ru-
3
2
3 3 2
2
(
[
CH3CN)3(P(OCH3)3)2}](CF3SO3)3 ([9](CF3SO3)3, Ar ) Ph;
10](CF3SO3)3, Ar ) p-CH3OC6H4) can be prepared from the
reactions of complex 3 with acetophenone and p-methoxy-
(
(
44) Birnbaum, J.; Rakowski DuBois, M. Organometallics 1994, 13, 1014.
45) Birnbaum, J.; Laurie, J. C. V.; Rakowski DuBois, M. Organometallics
1990, 9, 156.
(46) Bianchini, C.; Meli, A. Acc. Chem. Res. 1998, 31, 109.

Ketonated Disulfide-Bridged Diruthenium Complexes
Inorganic Chemistry, Vol. 39, No. 18, 2000 3951
Scheme 3
1
acetophenone, respectively (Scheme 3). [9](CF3SO3)3 can also
be obtained from the reaction of 1 with acetophenone in the
presence of 4 equiv of AgCF3SO3. However, preparations of
the ketonated complexes from complex 3 provide cleaner results
with higher yields. Derivatives bearing electron-withdrawing
groups such as NO2 or CH3C(O) in the para positions did not
react, nor did the C-H bonds in the aromatic rings of the
substrates.
complexes 11 and 12 were clearly observed in the H NMR
spectrum of the reaction mixture. A doublet at δ 1.62 is assigned
to the methyl protons in the â-position with respect to the
carbonyl group in 12. A multiplet around δ 4.2 is due to the
overlapping resonances of the methylene and the methine
protons bound to one of the two sulfur atoms in 11 and 12,
respectively (see Experimental Section). The relative molar ratio
of 11 to 12 and the total yield of the mixture of 11 and 12 were
NMR Spectroscopy. The 31P{ H} NMR spectra of the
1
1
determined from an integration of the H NMR signals using
ketonated complexes consist of two well-separated doublets
benzene as an internal reference. The molar ratio of 11 to 12
was 1:1.8 with a total yield of 74% when the reaction was
carried out for 60 min at 5 °C, whereas the ratio increased to
(∆δ ) 3.7-5.3 ppm) and two less separated doublets or a broad
singlet corresponding to an AB pattern. The former can be
assigned to the two phosphorus nuclei on the carbonyl-
coordinated ruthenium center, and the latter can be assigned to
the two phosphorus nuclei on the other ruthenium center,
surrounded by two P donors, three N donors, and one S donor.
1
:1.1 after the reaction mixture was warmed to 20 °C for 20
min (82%) and further changed to 1:0.5 with a yield of 95%
after the mixture was maintained for 2 h at the same temperature.
The amount of 12 dropped considerably, nearing zero after 20
1
In the H NMR spectra of 5-8, the sulfide-bound methylene
1
h, and that of 11 rose to 92% based on the analysis of the H
or methine proton signals lie in the range δ 4.22-3.98 as a
broad singlet (5), a quadruplet (6, 7), or a multiplet (8), which
is similar to that of complex 2, whereas the signals of the
diastereotopic methylene protons bound to the sulfur atoms in
complexes 9 and 10 appear as two doublets with AB patterns
at δ 4.95 and 4.53 (Jgem ) 19 Hz) for 9 and at δ 4.91 and 4.36
NMR spectrum. These results demonstrate that complex 12,
formed from the activation of the secondary C-H bond of
butanone, is the predominant product in the early stage and then
begins to decompose at ambient temperature in the presence of
III
III
protons released from butanone to regenerate the Ru SSRu
complex 3, which again activates the primary and secondary
C-H bonds of butanone to give complexes 11 and 12. Upon
repetition of this process, the relative ratio of the two products
inclines more toward 11. The fact that the isolated complex 12
is sufficiently stable in solution indicates that 12 is decomposed
by protonation to recover butanone and complex 3 under the
reaction conditions, where a small amount of acid is generated
from the reaction. A broad signal appearing around δ 10 in the
(
Jgem ) 18 Hz) for 10. The protons of the methyl groups attached
to the chelating rings in complexes 6 and 7 exhibit doublets
around δ 1.6-1.5 in the H NMR spectra.
1
Reaction with Butanone. The reactions of complex 1 with
3
-methyl-2-butanone and 2-methyl-3-pentanone, both having
asymmetric R-protons, exclusively afford complexes 5 and 7
in the presence of a silver salt by the activation of the R-C-H
bonds of the R-methyl and R-methylene groups, respectively,
indicating that the preferred orders for the R-C-H bonds are
respectively as follows: 1° > 3°; 2° > 3°. To compare the
relative reactivities of the R-C-H bonds of a primary versus a
secondary carbon atom, butanone was treated with 3 in CD3CN
1
H NMR spectrum of the reaction mixture confirms the release
of H ions. A representation of the conversion is shown in
+
Scheme 4. One can regard 12 as a kinetic product and 11 as a
thermodynamic one. Thus, the R-C-H bond on the secondary
carbon is more easily cleaved than that on the primary carbon.
In summary, the order of the relative reactivities of the C-H
bonds can be expressed as 2° > 1° > 3°. The lowest reactivity
of the tertiary C-H bond may reflect the greatest steric
hindrance of the branched groups. Reversible olefin binding to
the sulfur center of a sulfide-bridged dinulcear molybdenum
1
in an NMR tube and the reaction was monitored with H NMR
spectroscopy, which revealed a mixture of the following com-
plexes: [{Ru(CH3CN)2(P(OCH3)3)2}(µ-SSCH2COCH2CH3){Ru-
(CH3CN)3(P(OCH3)3)2}](CF3SO3)3 ([11](CF3SO3)3) and [{Ru-
(CH3CN)2(P(OCH3)3)2}(µ-SSCHCH3COCH3){Ru(CH3CN)3(P-
(OCH3)3)2}](CF3SO3)3 ([12](CF3SO3)3). The distinct signals of

3952 Inorganic Chemistry, Vol. 39, No. 18, 2000
Sugiyama et al.
Scheme 4
Figure 1. ORTEP drawing of cation 7. Thermal ellipsoids are drawn
at the 30% probability level.
Figure 2. ORTEP drawing of cation 8. Thermal ellipsoids are drawn
at the 30% probability level.
complex, another very rare reversible C-S bond reaction, was
observed previously.1
6,18,44,45
On the basis of the above experiment, one can expect to obtain
complex 11 as the main product by prolonging the reaction time
or raising the reaction temperature, whereas, for complex 12,
the reaction should be carried out at a lower temperature for a
short period. Indeed, complex 11 was obtained as the sole
product when the CH3CN solution of 1 containing 4 equiv of
the silver salt was stirred overnight at room temperature in the
presence of butanone. Unfortunately, the attempt to isolate pure
1
2 or to obtain single crystals suitable for X-ray analysis was
not successful. The fact that the secondary R-C-H bond is more
reactive than the primary one implies that a radical pathway
might be involved in the reaction. However, addition of a
t
radical-trapping agent, Bu3C6H2OH (10 equiv to Ru2S2 complex
1
or [3](CF3SO3)4), or irradiation of the reaction mixture by a
Figure 3. ORTEP drawing of cation 10. Thermal ellipsoids are drawn
at the 30% probability level.
mercury lamp did not significantly change the relative molar
ratio of 11 to 12 or the total yield, indicating that a radical
mechanism can be excluded for the present C-H bond
activation and C-S bond formation reaction.
Crystallographic Analyses of the Ketonated Complexes.
The structures of [7](PF6)3, [8](SbF6)3, [10](CF3SO3)3, and
is surrounded by two P atoms, three N atoms and one S atom.
One of the two bridging sulfur atoms is bonded to the R-C atom,
forming a five-membered chelate system. The S-S bond
distances of these complexes range from 2.040(7) to 2.069(4)
Å, which are comparable to that of 2 (2.067(6) Å)19 and are
similar to or slightly longer than those found in other nonalky-
[
11](PF6)3 were determined by X-ray crystallography, and the
ORTEP diagrams of their complex cations are shown in Figures
-4, respectively. These four structures possess the same
coordination mode as the acetonated complex reported previ-
3
6,39-43
1
lated disulfide complexes (2.01-2.05 Å).
The oxidation
states of the two ruthenium atoms in complexes 7, 8, 10, and
11 are considered to be 3+ on the basis of the Ru-P distances
1
9
ously, in which one ruthenium atom is coordinated by two P
atoms of P(OCH3)3, two N atoms of CH3CN, one S atom of
µ-S22 , and one O atom of the ketonated moiety and the other
19
(2.21-2.25 Å), as discussed previously. Selected bond lengths,
-
bond angles, and torsion angles for these complexes are

Ketonated Disulfide-Bridged Diruthenium Complexes
Inorganic Chemistry, Vol. 39, No. 18, 2000 3953
Figure 4. ORTEP drawing of cation 11. Thermal ellipsoids are drawn
at the 30% probability level.
Table 1. Selected Bond Distances (Å)
[8](SbF
6
)
3
[10](CF
3
SO )
3 3
[11](PF
6
)3
6
[7](PF )
3
Ru1-S1
Ru2-S2
Ru1-P1
Ru1-P2
Ru2-P3
Ru2-P4
Ru1-O1
S1-S2
2.348(2)
2.367(2)
2.243(3)
2.218(3)
2.231(3)
2.227(3)
2.157(5)
2.049(3)
1.853(9)
1.54(1)
2.342(3)
2.373(3)
2.241(3)
2.225(3)
2.225(4)
2.237(4)
2.179(7)
2.069(4)
1.86(1)
2.340(1)
2.373(2)
2.252(2)
2.231(2)
2.231(2)
2.231(2)
2.148(4)
2.060(2)
1.815(5)
1.512(8)
1.228(7)
2.320(6)
2.354(6)
2.234(7)
2.207(8)
2.217(6)
2.234(7)
2.14(2)
2.040(7)
1.86(3)
1.58(4)
S1-C1
C1-C2
C2-O1
1.50(2)
1.20(1)
1.21(1)
1.22(3)
Table 2. Selected Bond Angles and Torsion Angles (deg)
7]- [8]- [10]-
PF (SbF (CF SO
Bond Angles
[
[11]-
(PF )
6 3
(
6
)
3
)
6 3
3
3
)
3
Ru1-S1-S2
Ru2-S2-S1
Ru1-O1-C2
Ru1-S1-C1
S1-C1-C2
S2-S1-C1
106.6(1)
107.9(1)
121.8(6)
99.9(3)
110.7(6)
103.0(3)
109.2(1) 109.83(7)
109.2(1) 107.05(7)
120.1(7) 121.6(4)
97.8(4) 97.2(2)
114.5(8) 111.3(4)
103.4(4) 101.5(2)
108.5(3)
108.3(3)
124(2)
97.1(10)
115(2)
Figure 5. Newman-type projections of 7, 8, 10, and 11 (from top to
bottom).
of the aceotophenone derivative suppresses the reaction and is
apparently contradictory to a mechanism in which simple
deprotonation of the ketone initiates the nucleophilic attack on
the sulfur atom. In our recent studies, allylic C-H bonds were
101.7(9)
Torsion Angles
Ru1-S1-S2-Ru2 -167.91(9) -168.2(1) 170.55(6)
Ru1-S1-C1-C2 -15.5(8) -8.8(8) 31.9(4)
Ru1-O1-C2-C1 -14(1) -2(1) 8.5(7)
Ru2-S2-S1-C1 87.4(3)
172.9(3)
19(2)
0(4)
III
III
21
found to be cleaved in the Ru SSRu complexes 3 and 1.
III
III
88.5(4) 87.37(19) -85(1)
To explain the remarkable reactivity of the Ru SSRu core
toward various olefins, double-bond character for the disulfide
compared in Tables 1 and 2. The torsion angles Ru1-S1-C1-
C2 and Ru1-O1-C2-C1 in the ketonated complexes are
clearly different, as shown in Table 2. This may reflect the
difference in bulk for the ketonated moieties.
21
unit was suggested. The present reactions of various ketones
with the same ruthenium complex further support the SdS
double-bond character and the mechanism of C-H addition to
the SdS bond (Scheme 5). A ketone approaches the Ru center
with the carbonyl group to replace one of the three coordinated
CH3CN molecules that is trans to one of the two P(OCH3)3
ligands. When the R-C-H bond of a ketone is directed parallel
to the S2 moiety, addition of the C-H σ bond to the SdS π
bond occurs to form a C-S and an S-H bond (Scheme 5).
The nucleophilic addition is facilitated by the strong electron-
It is noteworthy that high diastereoselectivity is obtained in
the formation of the ketonated complexes, in which a larger
group on the carbon atom bonded to one of the two bridging
sulfide atoms always occupies a position farther away from the
sulfur atom that is not bound to the ketonate group to avoid the
steric congestion. This situation is seen clearly in the Newman-
type projections of 7, 8, 10, and 11 shown in Figure 5.
Proposed Mechanism for the Formation of Ketonated
Complexes. A plausible mechanism for the reaction of 3 with
ketones to give the corresponding ketonated complexes is shown
in Scheme 5. Although the relative reactivities of the C-H
bonds found in this study are in the order 2° > 1° > 3°, the
fact that a radical-trapping agent or irradiation does not affect
the reaction indicates that a radical process is not involved in
the formation of the ketonated complexes. An electron-
withdrawing substituent at the para position of acetophenone
retards the reaction, which implies that an increase in the acidity
III
withdrawing ability of the two Ru atoms. Complex 4, with
II
III
the same structure as 3 but with an Ru SSRu core, did not
react with either ketones or olefins, which supports the nucleo-
philic addition process. The reaction is completed by depro-
tonation of the S-H bond. The double-bond character of a
30-36
coordinated SdS unit has been reported previously.
Ad-
dition of a C-H bond to a double CdC bond promoted by
47,48
other ruthenium complexes was recently reported.
Although
(
47) Kakiuchi, F.; Sato, T.; Yamauchi, M.; Chatani, N.; Murai, S. Chem.
Lett. 1999, 19 and references therein.

3954 Inorganic Chemistry, Vol. 39, No. 18, 2000
Sugiyama et al.
Scheme 5
1
CN, δ, 270 MHz, 293 K): 3.86 (vt, 3JPH ) 6 Hz, 36H, 4P(OCH
) ),
3 3
we could not detect the S-H bond by H NMR spectroscopy,
(CD
3
2
1
2.71 (s, 6H, 2CH CN trans to S), 1.95 (s, 12H, 4CH CN, overlapped
with the signals of CD HCN).
2
the olefin reactions support the presence of such bonds.
3
3
Conclusions
Syntheses of [{Ru(CH CN) (P(OCH ) ) }(µ-SSCHR
1
COR
, R1 ) H, R2 ) CH(CH
CH , X ) PF ; [7](SbF
2
) {Ru-
3
2
3 3 2
(
CH
X ) PF
R ) CH
3
CN)
3
(P(OCH
3
)
3
)
2
1
}]X
3
([5](PF
6
)
3
3
)
)
2
,
,
The R-C-H bonds of various ketones have been activated
on the sulfur center of a disulfide ruthenium dinuclear complex
to form the corresponding ketonated complexes having C-S
bonds. Although the Ru atoms are not directly involved in the
C-H splitting process, they play an important role in modifying
the nature of the disulfide bridge. Nucleophilic addition of the
R-C-H bonds of ketones to SdS bonds is proposed as the key
step in the activation of the C-H bonds and formation of the
C-S bonds.
2
6
; [6](PF
)
6 3
, R ) CH
, R ) CH(CH
mixture of 1 (100.0 mg, 0.11 mmol) and AgPF
in CH CN (10 mL) was added an excess amount of 3-methyl-2-
3
, R ) CH
3
2
6
6
3
1
2
3
3
)
2
, X ) SbF
6
). General procedure: To a
(170.0 mg, 0.49 mmol)
6
3
butanone (3 mL). After being stirred for 7 h at room temperature, the
reaction mixture was filtered to remove AgCl. The pale green filtrate
was evaporated to dryness, and the residue was dissolved in a mixture
of CH
kept under ether diffusion to give the complex [{Ru(CH
}(µ-SSCH COCH(CH ){Ru(CH CN) (P(OCH
) as pale green crystals (61% yield). H NMR (CD
MHz, 293 K): 4.17 (br s, 2H, SCH ), 3.8-3.6 (m, 36H, 4P(OCH
), 2.46 (s, 3H, CH CN), 2.35 (s,
CN, overlapped with the signals of
HCN), 1.23 (d, J ) 7.0 Hz, 3H, CH(CH )CH ), 1.20 (d, J ) 7.0
CN, δ, 109.4 MHz, 293
3
CN and CH
2
Cl
2
. This solution was filtered, and the filtrate was
CN) (P(OC-
}](PF ([5]-
CN, δ, 270
),
3
2
H
(
3
)
PF
3
)
2
2
)
3 2
3
3
1
3 3
) )
2
6 3
)
6
)
3
3
Experimental Section
2
3 3
)
All experiments were carried out under nitrogen, by using standard
Schlenk tube techniques or a glovebox. The solvent CD
3
3
.12 (sept, J ) 7.0 Hz, 1H, CH(CH
H, CH CN), 1.97 (s, 9H, 3CH
3
)
2
3
3
CN was dried
3
3
over CaH and then purified by trap-to-trap distillation prior to use.
2
CD
Hz, 3H, CH(CH
2
3
3
Other solvents that were purchased dry were used without further
purification. Complex 1 was prepared as described in the literature.49
The NMR spectra were recorded on a JEOL Lambda 270 spectrometer,
operating at 270 MHz for H and 109 MHz for P, or on a JEOL
Lambda 500, spectrometer operating at 500 MHz for H. The chemical
shifts are reported in δ units (ppm) downfield from Me
3 4
H PO (85%, external reference) for P. Carbon, hydrogen, and nitrogen
analyses were carried out on a Perkin-Elmer PE 2400II elemental
analyzer.
31
1
3
)CH
3 3
). P{ H} NMR (CD
2
2
2
K): 135.3 (d, JPP ) 86 Hz), 133.8 (d, JPP ) 87 Hz), 133.4 (d, JPP
)
6
).
2
1
8
7 Hz), 130.0 (d, JPP ) 86 Hz), -145.6 (sept, JPF ) 106 Hz, PF
1
31
Anal. Calcd for C27 Ru : C, 21.80; H, 4.06; N, 4.71.
H
60
F N
18 5
O
13
P
7
S
2
2
1
Found: C, 21.62; H, 4.06; N, 4.44. The same procedure as described
above was used for the syntheses of complexes 6 and 7, but with
1
4
Si for H and
3
1
AgSbF
6
as the anion source in the preparation of 7.
1
[6](PF
)
6 3
: pale green crystals, 66% yield. H NMR (CD
3
CN, δ, 270
), 3.8-3.6 (m, 36H,
), 2.46 (s, 3H, CH CN),
CN, overlapped with the signals
HCN), 1.57 (d, J ) 8.1 Hz, 3H, SCHCH ), 1.14 (t, J ) 7.0 Hz,
CN, δ, 109.4 MHz, 293 K): 133.6
MHz, 293 K): 4.14 (q, J ) 8.1 Hz, 1H, SCHCH
3
A Modified Method for the Preparation of [{Ru(CH
OCH (µ-S )](CF SO ([3](CF SO ). The modified method
is based on the reported one for the preparation of [3](CF SO . A
mixture of 1 (90.4 mg, 0.10 mmol), AgCF SO (103.9 mg, 0.40 mmol),
CH CN (0.5 mL), and acetone (1.5 mL) was stirred for 2 h at room
3 3
CN) (P-
4
2
P(OCH
3
)
3
), 2.86 (q, J ) 7.0 Hz, 2H, CH
CN), 1.97 (s, 9H, 3CH
2
CH
3
3
(
3
3
) )
2
}
2
2
3
3
)
4
6
3
3 4
)
.34 (s, 3H, CH
3
3
3
3
3 4
)
of CD
H, CH
2
3
3
3
3
1
1
3
(
-
P
2
CH
3 3
). P{ H} NMR (CD
3
2
2
d, JPP ) 87 Hz), 132.7 (br s, 2P(OCH
3
)
3
), 129.3 (d, JPP ) 87 Hz),
). Anal. Calcd for C27
2
: C, 21.80; H, 4.06; N, 4.71. Found: C, 21.48; H, 3.99; N,
temperature. The resulting mixture was centrifuged to remove AgCl,
and the pale green supernate was evaporated to dryness in vacuo. The
1
144.8 (sept, JPF ) 106 Hz, PF
Ru
.47.
7](SbF
70 MHz, 293 K): 4.22 (q, 1H, J ) 7.9 Hz, SCHCH
6H, 4P(OCH ), 3.24 (sept, J ) 7.0 Hz, 1H, CH(CH
CN), 2.34 (s, 3H, CH CN), 1.97 (s, 9H, 3CH CN, overlapped with
the signals of CD HCN), 1.49 (d, J ) 7.9 Hz, 3H, SCHCH ), 1.21 (d,
J ) 6.6 Hz, 3H, CH(CH )CH ), 1.18 (d, J ) 6.9 Hz, 3H, CH(CH )CH ).
CN, δ, 109.4 MHz, 293 K): 133.2 (d, JPP ) 88
6
60 18 5 13
H F N O -
7
S
2
residue was washed with Et
complex 2. This crude product of 2 was dissolved in CH
the solution was treated with CF SO H (0.06 mL), and the mixture
was stirred for 30 min at room temperature. After removal of the
volatiles under reduced pressure, the residue was washed with Et
2
O (3 × 2 mL) to give the acetonated
4
3
CN (1.0 mL),
1
[
)
6 3
: pale green crystals, 62% yield. H NMR (CD
), 3.8-3.6 (m,
), 2.45 (s, 3H,
3
CN, δ,
3
3
2
3
3
3
)
3
3 2
)
2
O
CH
3
3
3
(
3 × 2 mL) to give [{Ru(CH
3
CN)
3
(P(OCH
3
) )
3 2
}
2
(µ-S
2 3 3 4
)](CF SO )
1
2
3
([3](CF SO ) as a dark blue powder (140.5 mg, 88%). H NMR
3
3 4
)
3
3
3
3
31
1
2
P{ H} NMR (CD
Hz), 132.7 (br s, 2P(OCH ), 129.5 (d, JPP ) 88 Hz). Anal. Calcd for
2
Sb Ru : C, 18.96; H, 3.52; N, 3.95. Found: C,
3
(48) Murai, S.; Kakiuchi, F.; Sekine, S.; Tanaka, Y.; Kamatani, A.; Sonoda,
M.; Chatani, N. Nature 1993, 366, 529.
2
)
3 3
(49) Matsumoto, T.; Matsumoto, K. Chem. Lett. 1992, 559.
C
28
H
62
F
18
N
5
O
13
P
4
S
2
3

Ketonated Disulfide-Bridged Diruthenium Complexes
Inorganic Chemistry, Vol. 39, No. 18, 2000 3955
Table 3. Summary of Crystallographic Data
[
7](PF
6
)
3
[8](SbF
6
)
3
[10](CF
3
SO
3
)
3
[11](PF
6
)
3
empirical formula
fw
a (Å)
b (Å)
c (Å)
C
28
H
63
O
N
13 5
F
18
7 2
P S Ru
2
C
28
H
61
O
13
N
5
18 4 2
F P S Ru
2
Sb
3
C
34
H
60
O
23
N
5 9 4 5
F P S Ru
2
C
26
H
59
O
13
N
5
F P S
18 7 2
Ru
2
1502.88
1773.19
1564.19
15.7178(7)
24.4198(11)
16.8492(8)
1474.83
25.000(5)
12.535(4)
12.341(3)
119.15(2)
92.61(1)
88.54(2)
3103(1)
2
20.993(3)
13.919(4)
21.258(3)
12.471(3)
21.72(1)
12.206(3)
101.96(3)
110.46(2)
84.28(3)
3029(1)
2
R (deg)
â (deg)
γ (deg)
94.95(1)
90.8310(10)
3
V (Å )
6188(1)
4
6466.5(5)
4
Z
space group (No.)
P 1h (2)
P2
1.903
20.44
AFC-7R
1
/n (14)
P2
1.557
8.24
1
/c (14)
P 1h (2)
-
3
d
calcd (g cm
)
1.608
1.617
-
1
µ (cm
)
8.39
AFC-7R
8.58
AFC-7R
diffractometer
SMART 1000
radiation, λ (Å)
Mo KR, 0.710 69
Mo KR, 0.710 69
Mo KR, 0.710 69
Mo KR, 0.710 69
2θmax (deg)
55
55
55
50
abs cor
ψ scan
11 630
6042 (I > 3σ(I))
745
0.058
0.072
+0.75, -0.34
ψ scan
10 971
5261 (I > 2σ(I))
708
0.062
0.201
+0.77, -0.63
SADABS
12 765
8450 (I > 2σ(I))
763
0.066
0.195
+1.01, -0.93
ψ scan
8143
4021 (I > 2σ(I))
568
0.098
0.108
+1.40, -0.95
no. of reflns measd
no of reflns obsd
no. of params
a
R1
b
wR2
3
residuals (e/Å )
a
| for observed data. wR2 ) [∑[w(F 2
b
- F 2
)2/∑w(F 2)2]1/2.
o
R1 ) ∑||F
o
| - |F
c
||/∑|F
o
o
c
1
8.37; H, 3.44; N, 3.73. The pale green crystals of [7](PF
6
)
3
suitable
[10](CF
as described for 9 by using p-CH
none (yield: 94%). The single crystals of [10](CF
X-ray analysis were obtained by recrystallization from CH
3
SO
3
)
3
was synthesized and purified in the same procedure
OC C(O)CH instead of acetophe-
SO suitable for
for the X-ray analysis were obtained by using AgPF
source.
6
as the anion
3
H
6 4
3
3
3 3
)
Synthesis of [{Ru(CH
-yl){Ru(CH CN) (P(OCH
cedure as described above for the synthesis of 5 was used in the
preparation of [8](SbF , but with AgSbF as the anion source. Pale
green crystals were obtained in a yield of 69%. H NMR (CD
3
CN)
2
(P(OCH
3
)
3
)
2
}(µ-SS-1-cyclohexanon-
3
CN and THF
1
2
3
3
) ) }](SbF )
3 3 2 6 3
([8](SbF ). The same pro-
6
)
3
at room temperature. H NMR (CD
(d, Jom ) 9 Hz, 2H, o-C OCH
(d, JHH′ ) 18 Hz, 1H, SCHH′), 4.36 (d, JHH′ ) 18 Hz, 1H, SCHH′),
3
CN, δ, 270 MHz, 293 K): 8.16
6
H
4
3 6 4 3
), 7.17 (d, 2H, m-C H OCH ), 4.91
2
2
6
)
3
6
1
3
3
CN, δ,
70 MHz, 293 K): 3.98 (m, 1H, SCH), 3.8-3.6 (m, 36H, 4P(OCH ),
.88 (m, 1H, COCHH′), 2.66 (m, 2H, COCHH′ and SCHCHH′), 2.12
CHH′), 1.98 (m, 1H, SCHCH CHH′), 1.73 (m, 2H,
SCHCHH′CHH′), 1.54 (m, 1H, COCH CHH′), 2.45 (s, 3H, CH CN),
CN, overlapped with the signals
CN, δ, 109.4 MHz, 293 K): 132.8
3.95 (s, 3H, C
3.7 (m, 27H, 3P(OCH
1.95 (s, 9H, 3CH CN, overlapped with the signals of CD
6 4
H
OCH
3
), 3.81 (d, JPH ) 11 Hz, 9H, P(OCH
), 2.52 (s, 3H, CH CN), 2.39 (s, 3H, CH
HCN).
3
P{ H} NMR (CD CN, δ, 109.4 MHz, 293 K): 137.9 (d, JPP ) 84
3
)
3
), 3.6-
3
2
2
)
3 3
3
)
3
3
CN),
3
2
3
1
1
2
(m, 1H, COCH
2
2
2
2
2
3
Hz), 135.9 (d, JPP ) 87 Hz), 135.5 (d, JPP ) 87 Hz), 132.3 (d,
2
2.34 (s, 3H, CH
3
1
CN), 1.97 (s, 9H, 3CH
3
J
PP ) 84 Hz). Anal. Calcd for C34
3.87; N, 4.48. Found: C, 25.73; H, 3.68; N, 4.20.
Reaction of [{Ru(CH CN) (P(OCH (µ-S
CF SO ) with Butanone. To a solution of 3 (32 mg, 0.02 mmol) in
CD CN (0.54 mL) were added butanone (0.089 mL, 1 mmol) and
60 9 5 23 4 5 2
H F N O P S Ru : C, 26.10; H,
3
1
of CD
2
HCN). P{ H} NMR (CD
3
2
2
(
d, JPP ) 87 Hz), 131.7 (br s, 2P(OCH
Anal. Calcd for C28 Sb Ru
Found: C, 19.02; H, 3.51; N, 4.01.
Protonation of the Ketonated Complexes 2 and 5-7. General
procedure: To a CD CN (0.6 mL) solution of acetonated complex 2
0.100 g, 0.068 mmol) was added HCl (37 wt % in water, 0.113 mL,
3
)
2
3
), 127.4 (d, JPP ) 87 Hz).
3
3
3
)
3
)
2
}
2
2 3 3 4
)](CF SO ) ([3]-
H F N O P S
60 18 5 13 4 2
3
: C, 18.98; H, 3.41; N, 3.95.
(
3
3 4
)
3
benzene (0.009 mL, 0.1 mmol, as an internal reference) at 5 °C, and
1
3
the reaction was monitored by H NMR spectroscopy. A mixture of
(
[
{Ru(CH
CH }](CF
µ-SSCHCH COCH
) in a molar ratio of 1:1.8 was detected after 60 min at 5 °C in a
3
CN)
2
(P(OCH
SO ([11](CF
){Ru(CH
3
)
3
)
2
}(µ-SSCH
SO ) and [{Ru(CH
CN) (P(OCH }](CF
2
COCH
2
CH
3
){Ru(CH
CN) (P(OCH
3
SO ([12](CF -
3 3
CN) (P(O-
1
.36 mmol) at room temperature. The reaction mixture was analyzed
3
)
)
3 2
3
)
3 3
3
3
)
3
3
2
) ) }-
3 3 2
1
31
after 10 min by H and P NMR spectroscopy, which revealed the
formation of 1 and [RuCl{P(OCH
(
3
3
3
3
3
)
)
3 2
3
)
3 3
3
)
3
}
2
](µ-S
2
2 3
)(µ-Cl) [Ru(CH CN){P-
3 3
SO )
+
(OCH
3
3
) }
2
]
in a molar ratio of 1:2, along with the released acetone.
total yield of 78%. The reaction mixture was then warmed to 20 °C,
and the relative molar ratio of 11 to 12 and the total yield of 11 and 12
The same procedure as described for the protonation of 2 was used in
the reactions of complexes 5-7 with various acids.
1
were determined by the analysis of H NMR spectrum as described
Syntheses of [{Ru(CH
CH CN) (P(OCH }](CF
SO , Ar ) p-CH OC ). To a CH
3
CN)
2
(P(OCH
([9](CF
CN (1 mL) solution of 3 (80.7
3
)
3
3
)
2
}(µ-SSCH
2
COAr){Ru-
under Results and Discussion.
(
3
3
) )
3 3 2
3
SO
3
)
3
SO , Ar ) Ph; [10](CF
)
3 3
3
-
1H NMR for [11](CF
3
3 3 3
SO ) (CD CN, δ, 500 MHz, 293 K): 4.23
3
)
3
3
6
H
4
3
(
d, J ) 19.0 Hz, 1H, SCHH′), 4.18 (d, J ) 19.0 Hz, 1H, SCHH′),
.8-3.6 (m, 36H, 4P(OCH ), 3.00 (dq, J ) 18.9, 7.2 Hz, 1H,
CHH′CH ), 2.83 (dq, J ) 18.9, 7.2 Hz, 1H, CHH′CH ), 2.49 (s, 3H,
CH CN), 2.38 (s, 3H, CH CN), 1.97 (s, 9H, 3CH CN, overlapped with
the signals of CD HCN), 1.19 (t, J ) 7.2 Hz, 3H, CHH′CH ).
1NMR for [12](CF
SO (CD CN, δ, 500 MHz, 293 K): 4.17 (q,
), 3.8-3.6 (m, 36H, 4P(OCH ), 2.56 (s,
CO), 2.49 (s, 3H, CH CN), 2.38 (s, 3H, CH CN), 1.97 (s, 9H,
CN, overlapped with the signals of CD HCN), 1.62 (d, J ) 8.2
).
Isolation and Crystallization of [11](SbF
mg, 0.050 mmol) was added acetophenone, and the mixture was stirred
for 1 h at room temperature. The reaction solution became pale green,
3
3 3
)
3
3
whereupon Et
was removed via a syringe, and the residue was washed with THF (6
mL) and dried under reduced pressure to give [{Ru(CH CN) (P(OC-
}(µ-SSCH COPh){Ru(CH CN) (P(OCH }](CF SO ([9](CF
) as a pale green powder (64.4 mg, 81%). H NMR (CD CN, δ,
70 MHz, 293 K): 8.18 (d, Jom ) 8 Hz, 2H, o-C ), 7.88 (t, Jmp
), 4.95 (d, JHH′ ) 19 Hz, 1H,
2
O (6 mL) was added to give a precipitate. The supernate
3
3
3
2
3
3
2
3
)
3 3
3
H
SO
2
8
3
)
3
3
)
2
2
3
3
3
)
3
)
2
1
3
3
)
3
3
-
J ) 8.2 Hz, 1H, SCHCH
3
3 3
)
)
3
3
3
H, CH
3
3
3
6
2
H
5
)
3CH
3
2
6 5 6 5
Hz, 1H, p-C H ), 7.69 (t, 2H, m-C H
2
3
Hz, 3H, SCHCH
3
SCHH′), 4.53 (d, JHH′ ) 19 Hz, 1H, SCHH′), 3.82 (d, JPH ) 11 Hz,
6 3
) . This complex could
9
2
H, P(OCH
3
)
3
), 3.6-3.7 (m, 27H, 3P(OCH
3
)
3
), 2.54 (s, 3H, CH
CN, overlapped with the signals
CN, δ, 109.4 MHz, 293 K): 135.9
3
CN),
be isolated as a pure solid from the 1-butanone reaction solution after
standing at room temperature overnight in the presence of AgSbF6.
.39 (s, 3H, CH
3
1
CN), 1.95 (s, 9H, 3CH
3
3
1
of CD
2
HCN). P{ H} NMR (CD
3
2
2
2
Yield: 63%. Anal. Calcd for C H F N O P S Sb Ru : C, 17.88;
(d, JPP ) 84 Hz), 134.3 (d, JPP ) 88 Hz), 133.9 (d, JPP ) 88 Hz),
26 58 18
5
13
4
2
3
2
30.1 (d, 2JPP ) 84 Hz). Anal. Calcd for C33
H, 3.35; N, 4.01. Found: C, 17.78; H, 3.44; N, 3.95.
1
2
H
58
F
9
N
5
O
22
P
4
S
5
Ru
2
: C,
5.84; H, 3.81; N, 4.56. Found: C, 25.29; H, 3.64; N, 4.26.
The pale green crystals of [11](PF suitable for the X-ray analysis
6 3
)

3956 Inorganic Chemistry, Vol. 39, No. 18, 2000
Sugiyama et al.
were obtained by using AgPF
Et O diffusion.
X-ray Crystallographic Studies. Diffraction data for [7](PF
8](SbF , and [11](PF were collected on a Rigaku AFC 7R four-
circle diffractometer using graphite-monochromated Mo KR radiation
λ ) 0.710 69 Å). The unit cell parameters of 7, 8, and 11 were obtained
6
as the anion source in CH
3
CN with
data for [10](CF
3
SO
3
)
3
were collected on a Bruker SMART 1000 CCD
2
diffractometer using Mo KR radiation. All intensity data were processed
by the SAINT-Plus program package, and the structure solution was
performed with the SHELXTL software package. Details of all four
crystallographic analyses are summarized in Table 3.
6 3
) ,
[
6
)
3
6 3
)
(
by least-squares refinements of 25 reflections (25° < 2θ < 30°). Three
standard reflections were recorded every 150 reflections and used for
the decay corrections. The diffraction data were corrected for Lorentz
and polarization effects, and absorption corrections based on ψ scans
were applied. Structure solutions were performed with the TEXSAN
program package. Some atoms were treated isotropically to maintain
reasonable reflection:parameter ratios, and some rigid-group constraints
Supporting Information Available: X-ray crystallographic files,
6 3 6 3
in CIF format, for the structure determinations of [7](PF ) , [8](SbF ) ,
[10](CF SO , and [11](PF . This material is available free of charge
3
)
3 3
6 3
)
via the Internet at http://pubs.acs.org.
6
were applied for the highly disordered PF counteranions. Diffraction
IC0000855