Remote chirality transfer within a coordination sphere by the use of a ligand possessing a concave cavity

Article abstract of DOI:10.1021/om060234c

The possibility to enhance the effect of a modest chiral element in a metal ligand by the use of a second ligand possessing a concave cavity has been examined for the examples of 1,3- and 1,4-chirality transfer within the metal coordination sphere. Complexation of Ru(C₆₀Me₅)Cl(CO) ₂ with (R)-prophos [(R)-1,2-bis(diphenylphosphino)propane] took place with excellent diastereoselectivity to give a configurationally stable chiral-at-metal complex, Ru(C₆₀Me₅)Cl((R)-prophos). This complex was converted, with good to perfect diastereoselectivity, into a variety of cationic complexes, [Ru(C₆₀Me₅)((R)-prophos)L]- [SbF₆] (L = MeCN, ^tBuCN, methacrolein, acetone, CO, BnNC, 2,6-Me₂C₆H₃NC), and a vinylidene complex, [Ru(C₆₀Me₅)(=C=CPhH)((R)-prophos)][SbF₆]. The chirality transfer to the reactants reacting in the outer sphere of the coordination resulted in an asymmetric Diels-Alder reaction, albeit with modest selectivity.

Full text of DOI:10.1021/om060234c

2826
Organometallics 2006, 25, 2826-2832
Remote Chirality Transfer within a Coordination Sphere by the Use
of a Ligand Possessing a Concave Cavity
Yutaka Matsuo,† Yuichi Mitani,‡ Yu-Wu Zhong,† and Eiichi Nakamura*,†,‡
Nakamura Functional Carbon Cluster Project, ERATO, Japan Science and Technology Agency, and
Department of Chemistry, The UniVersity of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan
ReceiVed March 14, 2006
The possibility to enhance the effect of a modest chiral element in a metal ligand by the use of a
second ligand possessing a concave cavity has been examined for the examples of 1,3- and 1,4-chirality
transfer within the metal coordination sphere. Complexation of Ru(C60Me5)Cl(CO)2 with (R)-prophos
[(R)-1,2-bis(diphenylphosphino)propane] took place with excellent diastereoselectivity to give a
configurationally stable chiral-at-metal complex, Ru(C60Me5)Cl((R)-prophos). This complex was converted,
with good to perfect diastereoselectivity, into a variety of cationic complexes, [Ru(C60Me5)((R)-prophos)L]-
t
[SbF6] (L ) MeCN, BuCN, methacrolein, acetone, CO, BnNC, 2,6-Me2C6H3NC), and a vinylidene
complex, [Ru(C60Me5)(dCdCPhH)((R)-prophos)][SbF6]. The chirality transfer to the reactants reacting
in the outer sphere of the coordination resulted in an asymmetric Diels-Alder reaction, albeit with modest
selectivity.
Scheme 1. 1,n-Chirality Transfer in Organic and
Introduction
Organometallic Chemistry
Diastereoselective creation of a new stereogenic center under
the influence of an existing stereogenic center in some remote
location of the same molecule (chirality transfer) is a rather
difficult task, and its feasibility was studied extensively by
organic chemists in the 1980s and 1990s in the context of
synthesis of complex organic molecules. For instance, nucleo-
philic addition to a ketone shown in Scheme 1a (top) may take
place diastereoselectively under the influence of the stereogenic
center at the 3-position.1 Chirality transfer to a more remote
position such as 1,4-transfer is less straightforward, but can also
be achieved in some cases (Scheme 1a, bottom).1,2
Similar chirality transfer can be envisaged in inorganic
chemistry; for instance, addition of a ligand L to a coordinatively
unsaturated metal may induce metal-centered chirality in a 1,3-
manner under the influence of a stereogenic center in the
phosphine ligand attached to the metal (Scheme 1b, top). The
reaction of L with a second reactant R1 may create a new
molecule L*R1, which may be optically active if the chiral
phosphine ligand is nonracemic. Such chirality transfer to
external reactants constitutes the basic principle of metal-assisted
asymmetric synthesis.3 Chirality transfer may occur during
formation of an organometallic compound as in Scheme 1b,
bottom, where the new stereogenic center on the added carbon
ligand may be controlled in a 1,4-manner.4,5
Achieving high diastereoselectivity in remote chirality transfer
within an organometallic complex however has not been an easy
issue6,7 because of the thermodynamic and kinetic instability
of the configuration of the metal-centered chirality.8 For
instance, the reaction of Ru(η5-Cp)Cl(PPh3)2 with a chiral
diphosphine ligand of modest steric demand, (R)-prophos [(R)-
1,2-bis(diphenylphosphino)propane], gives an essentially 1:1
(0-20% de) mixture of two diastereomers (eq 1).9 The
(2) Arai, M.; Nemoto, T.; Ohashi, Y.; Nakamura, E. Synlett 1992, 309.
(3) (a) ComprehensiVe Asymmetric Catalysis I-III; Jacobsen, E. N.,
Pfaltz, A., Yamamoto, H., Eds.; Springer: Berlin, 1999. (b) Ojima, I., Ed.
In Catalytic Asymmetric Synthesis, 2nd ed.; Wiley-VCH: New York, 2000.
(4) Consiglio, G.; Morandini, F. Chem. ReV. 1987, 87, 761.
(5) Brunner, H. Angew. Chem., Int. Ed. 1999, 38, 1194.
(6) (a) Attar, S.; Nelson, J. H.; Fischer, J.; de Cian, A.; Sutter, J.-P.;
Pfeffer, M. Organometallics 1995, 14, 4559. (b) Meneghetti, M. R.; Grellier,
M.; Pfeffer, M.; Dupont, J.; Fischer, J. Organometallics 1999, 18, 5560.
(c) Faller, J. W.; Lavoiw, A. R. Organometallics 2000, 19, 3957. (d)
Brunner, H.; Zwack, T.; Zabel, M.; Beck, W.; Bo¨hm, A. Organometallics
2003, 22, 1741.
* To whom correspondence should be addressed. E-mail: nakamura@
chem.s.u-tokyo.ac.jp.
† ERATO, Japan Science and Technology Agency.
‡ The University of Tokyo.
(1) Mengel, A.; Reiser, O. Chem. ReV. 1999, 99, 1191, and references
therein.
10.1021/om060234c CCC: $33.50 © 2006 American Chemical Society
Publication on Web 04/20/2006

Remote Chirality Transfer
Organometallics, Vol. 25, No. 11, 2006 2827
Scheme 2
Scheme 3
diastereoselectivity may be improved by the use of a sterically
more demanding pentamethylcyclopentadienide ligand (up to
95:5 for Ru(η5-C5Me5)Cl(PPh3)2).10
One can consider that installation of a ligand with a concave
structural motif on the metal center (Scheme 2) would limit
the conformational mobility of the other ligands (e.g., L1 and
L2) and hence would enhance the steric effect of one ligand to
the other. In other words, even a modest chirality element in
L1 would be reflected much more on the stereochemistry in L2
or that of the metal center. However, metal ligands possessing
a clearly defined concave cavity are rare (e.g., pyrazolylborate11).
We recently created a new class of cyclopentadienide ligands
where the cyclopentadienide (Cp) moiety is enclosed in a
concave cavity built on the skeleton of a fullerene molecule
(eq 2). Herein we report the first application of this concave
ligand for stereocontrol as illustrated for the coordination
behavior of ruthenium complexes (Scheme 3). The new ligand
much enhances the degree of the remote chirality transfer in
the case shown in eq 1.
Results and Discussion
Regioselective addition of an organocopper compound to [60]-
fullerene has made available a wide variety of pentaorgano
fullerene metal complexes that feature a cyclopentadiene or a
metal cyclopentadienide moiety embedded in the fullerene
framework (eq 2). When the added R groups are large enough
(e.g., biphenyl), the molecule resembles the shape of a bad-
minton shuttlecock and forms supramolecular one-dimensional
stacks in crystals or in liquid crystals.12
In addition to the supramolecular effect, the concave cavity
offers possibilities for organometallic chemistry; for instance,
the protruding R groups provide a new type of environment
for the metal group M. Unlike conventional cyclopentadienide
ligands that are flat and symmetric with regard to the plane
involving the 6π-aromatic five-membered ring, the fullerene
cyclopentadienide (FCp) is not. When the conical cavity around
the cyclopentadienide of 2 is deep enough (e.g., R ) phenyl),
the cavity provides steric protection of the center metal against
attachment of external reactants. For instance, a Ni(η3-C3H5)
complex of 2 (R ) Ph) is very stable to air (i.e., molecular
oxygen), whereas the corresponding ordinary Ni(η3-C3H5)(η5-
C5H5) complex is too unstable to be isolated (immediate
oxidative decomposition).13 We therefore conjectured that
modulation of the height of the wall (i.e., the size of the R group)
(7) (a) Kataoka, Y.; Shibahara, A.; Saito, Y.; Yamagata, T.; Tani, K.
Organometallics 1998, 17, 4338. (b) Kataoka, Y.; Iwato, Y.; Yamagata,
T.; Tani, K. Organometallics 1999, 18, 5423. (c) Matsushima, Y.; Onitsuka,
K.; Takahashi, S. Chem. Lett. 2000, 760. (d) Onitsuka, K.; Dodo, N.;
Matsushima, Y.; Takahashi, S. Chem. Commun. 2001, 521. (e) Onitsuka,
K.; Ajioka, Y.; Matsushima, Y.; Takahashi, S. Organometallics 2001, 20,
3274. (f) Kataoka, Y.; Nakagawa, Y.; Shibahara, A.; Yamagata, T.;
Mashima, K.; Tani, K. Organometallics 2004, 23, 2095. (g) Kataoka, Y.;
Shimada, K.; Goi, T.; Yamagata, T.; Mashima, K.; Tani, K. Inorg. Chim.
Acta 2004, 357, 2965. (h) Matsushima, Y.; Onitsuka, K.; Takahashi, S.
Organometallics 2004, 23, 2439. (i) Matsushima, Y.; Onitsuka, K.;
Takahashi, S. Organometallics 2004, 23, 3763. (j) Matsushima, Y.; Onitsuka,
K.; Takahashi, S. J. Chem. Soc., Dalton Trans. 2004, 547. (k) Pinto, P.;
Marconi, G.; Heinemann, F. W.; Zenneck, U. Organometallics 2004, 23,
374.
(8) (a) Brunner, H.; Zwack, T. Organometallics 2000, 19, 2423. (b)
Pfeffer, M. Organometallics 2000, 19, 2427.
(9) Morandini, F.; Consiglio, G.; Straub, B.; Ciani, G.; Sironi, A. J. Chem.
Soc., Dalton Trans. 1983, 2293.
(10) Morandini, F.; Dondana, A.; Munari, I.; Pilloni, G.; Consiglio, G.;
Sironi, A.; Moret, M. Inorg. Chim. Acta 1998, 282, 163.
(11) (a) Trofimenko, S. Acc. Chem. Res. 1971, 4, 17. (b) Trofimenko,
S. Chem. ReV. 1993, 93, 943. (c) Edelmann, T. F. Angew. Chem., Int. Ed.
2001, 40, 1656. (d) Carmona, E.; Paneque, M.; Santos, L. L.; Salazar, V.
Coord. Chem. ReV. 2005, 249, 1729.
(12) (a) Sawamura, M.; Kawai, K.; Matsuo, Y.; Kanie, K.; Kato, T.;
Nakamura, E. Nature 2002, 419, 702. (b) Matsuo, Y.; Muramatsu, A.;
Hamasaki, R.; Mizoshita, N.; Kato, T.; Nakamura, E. J. Am. Chem. Soc.
2004, 126, 432. (c) Okada, S.; Arita, R.; Matsuo, Y.; Nakamura, E.;
Oshiyama, A.; Aoki, H. Chem. Phys. Lett. 2004, 399, 157.
(13) Kuninobu, Y.; Matsuo, Y.; Toganoh, M.; Sawamura, M.; Nakamura,
E. Organometallics 2004, 23, 3259.

2828 Organometallics, Vol. 25, No. 11, 2006
Matsuo et al.
would control the coordination chemistry of the metal atom by
limiting the mobility of the ligand molecules (Scheme 2).
Diastereoselective Synthesis of Ru(η5-C60Me5)Cl((R)-pro-
phos). A previously described complex, Ru(η5-C60Me5)Cl(CO)2
(3),14 was synthesized, and the 1,3-chirality transfer during the
course of ligand exchange from CO to (R)-prophos was
examined. As a reference, the corresponding achiral diphos-
phine, 1,2-bis(diphenylphosphino)ethane (dppe), was also stud-
ied.
The reaction of 3 with dppe proceeds in 1,2-dichlorobenzene
at 150 °C to give the diphosphine complex Ru(η5-C60Me5)Cl-
(dppe) (4) as air-stable orange microcrystals in 47% yield
(Scheme 3). We examined the reaction with (R)-prophos under
the same conditions. To our pleasant surprise, the reaction even
at such a high temperature afforded Ru(η5-C60Me5)Cl((R)-
prophos) (5) as a single diastereomer in 51% yield. We carefully
determined the diastereomeric excess of 5 in the crude mixture
and found that the reaction is completely selective as determined
by 1H, 13C, and 31P NMR and HPLC analyses (Cosmosil
Buckyprep and Develosil RPFullerene). Thus, unlike the normal
Cp ligand, which gave a 60:40 diastereomeric mixture (eq 1),
the FCp ligand destabilizes one isomer more than the other.
The 1H NMR of 4 and 5 at room temperature displayed three
signals due to the methyl groups at δ 2.24, 2.25, and 2.36 and
five singlet signals at δ 1.44, 1.61, 2.06, 2.48, and 2.86,
respectively. Therefore, 4 and 5 are Cs and C1 symmetric,
respectively, indicating that the diphosphine ligands are fixed
in their location relative to the FCp methyl groups. The 13C
NMR spectra also supported this conclusion. The 31P{1H} NMR
spectrum of 4 exhibited a singlet signal due to the phosphine
ligand at δ 63.44, while 5 showed two doublet signals at 45.8
and 69.0 due to magnetically nonequivalent phosphine atoms.
The 31P signals of 4 and 5 appear at a lower field than that
of the free ligands (4, δ -12.70; 5, δ -20.98 and 1.35),
indicating that the diphosphine ligands are coordinated in a
bidentate fashion. Variable-temperature 1H and 31P NMR
measurements of 5 in a temperature range between 80 and -45
°C did not show any significant signal broadening, strongly
suggesting that the metal-centered chirality of 5 is very stable
both conformationally and configurationally.
Figure 1. Molecular structure of 4. Selected bond distances (Å)
and angles (deg): Ru-C(fullerene Cp, average) ) 2.27, Ru-
centroid(MeFCp) ) 1.92, Ru-Cl ) 2.44, Ru-P1 ) 2.37, Ru-P2
) 2.35, P1-Ru-P2 ) 82.3, Cl-Ru-P1 )84.3, Cl-Ru-P2 )
82.5.
Figure 2. Molecular structure of 5. Selected bond distances (Å)
and angles (deg): Ru-C(fullerene Cp, average) ) 2.28 Å, Ru-
centroid(fullerene Cp) ) 1.92 Å, Ru-Cl ) 2.437(3) Ru-P1 )
2.344(3), Ru-P2 ) 2.341(3), P1-Ru-P2 ) 80.5(1), Cl-Ru-P1
) 86.2(1), Cl-Ru-P2 ) 81.4(1). The phenyl group indicated by
an arrow is tilted due to the methyl group in the prophos ligand.
The structures of 4 and 5 were unambiguously determined
by X-ray crystallographic analysis. Slow diffusion of ethanol
to a toluene solution of 4 and 5 gave single crystals having
centrosymmetric (P21/c) and chiral (P21) space groups, respec-
tively (Figures 1 and 2). The two structures are very similar to
each other except the presence of an extra methyl group of the
(R)-prophos ligand in 5 and twisting of the phenyl group (shown
by an arrow) next to the methyl group. The absolute configu-
ration at the Ru center of 5 was determined to be SRu, and the
methyl substituent on the ligand backbone was found to point
away from the chlorine atom on the Ru atom. All Ru-P and
Ru-C(fullerene-Cp moieties) bond distances of 4 and 5 (shown
in the caption of Figure 1) are slightly longer than those of the
normal CpRu-prophos complex, (S)-Ru(η5-C5H5)Cl{(R)-pro-
phos} [Ru-P ) 2.276 and 2.278 Å, Ru-C(Cp, averaged) )
2.20 Å],9 while the Ru-Cl distances of 4 and 5 are not very
different from that of (S)-Ru(η5-C5H5)Cl{(R)-prophos} (Ru-
Cl ) 2.444 Å). The long bond distances of Ru-P and Ru-
C(fullerene-Cp) can be ascribed to the steric repulsion between
the methyl groups of the C60Me5 ligand and the phenyl groups
of the diphosphine ligands. Taking into account the NMR and
X-ray data, we conclude that the concave shape of the C60Me5
ligand is responsible for the perfect 1,3-chiral induction from
the chiral center of the carbon atom of (R)-prophos to the
ruthenium center.
Diastereoselective Conversion to Cationic Complexes.
Having found excellent diastereoselectivity of the (R)-prophos
complex formation, we examined the reaction of the corre-
sponding cationic complex 6 with a nucleophile to see whether
1,3-chirality transfer to the metal center also occurs here with
high selectivity. To this end, the chlorine atom in 5 was removed
by AgSbF6 in CH2Cl2 to generate in situ a cationic complex 6,
which was allowed to react with neutral molecules, CO,
methacrolein, acetone, nitriles, and isonitriles to form complexes
7-13 in essentially quantitative yields. All reactions produced
one diastereomer in excess of another, and the diastereomeric
selectivity ranged from 84% to 100%.
The sense of the diastereoselectivity of the complex formation
t
was assigned for the BuCN complex 8. The 2D NOESY
spectrum of 8 exhibited a strong NOE effect between the tert-
butyl nitrile and the proton bound to the chiral center of (R)-
prophos. As can be seen in Figure 2, such proximity indicates
that the stereochemistry of 8 is the same as that of 5, that is,
SRu. The major diastereomers of other complexes showed NMR
spectra, 31P NMR, in particular,15 essentially the same as those
of 8, suggesting that all are in the same configuration. In
(14) Matsuo, Y.; Nakamura, E. Organometallics 2003, 22, 2554.

Remote Chirality Transfer
Organometallics, Vol. 25, No. 11, 2006 2829
Scheme 4
addition, when the acetonitrile complex 7 was treated with
MgBr2 in a mixture of THF and CH2Cl2, the neutral complex
14 was obtained in 100% ds (Scheme 3), and the absolute
configuration of the ruthenium center was the same as that in
5 as determined by the X-ray analysis. The ligand exchange
thus took place with overall retention of the stereochemistry at
the metal center. Only when the ligands were strong coordinating
isonitriles (12 and 13) did the selectivity erode to about 80%.
The similarity in the steric bulk of nitriles and isonitriles suggests
that the observed diastereoselectivity is related to both the
thermodynamics and kinetics of the complexation reaction.
We also found that 1,4-chirality transfer takes place with
excellent selectivity. Treatment of 7 with phenylacetylene in
CHCl3 at 60 °C afforded 15 as a single diastereomer.16 Its 13
C
NMR spectrum showed a characteristic low-field phosphorus-
coupled triplet at δ 343.92, which attests to the presence of the
1
vinylidene motif. The H NMR exhibited a singlet at δ 5.19
accelerated by BF3 etherate, but exo/endo selectivity was modest
in both cases. The CH3CN complex 7 accelerated the reaction
to a small degree, but diastereo- and enantioselectivities were
poor. We suspected that it is due to the sluggishness of CH3-
CN/methacrolein exchange and instead used the methacrolein
complex 9. The reaction took place faster indeed and with much
enhanced exo:endo ratio (23:1) and enantioselectivity (20% ee;
absolute stereochemistry of major isomer as indicated). The high
exo/endo selectivity suggests that the FCp complex is acting as
a bulky ligand, but the low enantioselectivity indicates that the
design of the chiral environment is yet to be improved.
The basic principle of the enhancement of the effect of the
modest chiral element in the prophos ligand by the use of the
concave FCp ligand has been proved. The availability of
numerous chiral ligands and η5-FCp complexes22 combined with
the preliminary data on asymmetric catalysis suggests that
suitable modification of the substituents in the ligand chirality
as well as that of the R groups on the fullerene would provide
us with new opportunities in asymmetric synthesis of organic
and inorganic compounds.
for the â-H of vinylidene. 2D NOESY measurement showed a
strong NOE effect between the proton bound to the chiral center
of (R)-prophos (Ha) and the aryl proton Hb. In addition, a weak
NOE was observed between Hb and the methyl groups of the
fullerene core, which in turn showed a weak NOE with Hc (â-H
of vinylidene). All these pieces of information indicated the
major conformation of 15 in solution as that illustrated in
Scheme 3, in which the plane containing the vinylidene ligand
is orthogonal to the plane containing the centroid of the fullerene
Cp ligand/the ruthenium atom/the R-carbon of the vinylidene
ligand, with the phenyl group of vinylidene directed toward the
chiral center of (R)-prophos. The spatial orientation of the phenyl
group is consistent with the steric environment found in the
X-ray structure of 5 (Figure 2), where the tilted phenyl group
(indicated by an arrow) provides a chiral space to accommodate
the vinylidene group above it. Overall, the suggested conforma-
tion corroborates with previous theoretical analyses17 and X-ray
analyses of similar structures bearing a cyclopentadienyl,16b,18
pentamethyl cyclopentadienyl,19 or indenyl ligand.20
The chiral space in which the chlorine atom of 5 or the
vinylidene group of 15 is located is not particularly conspicuous
because of the lack of any intentional design at this stage.
Nonetheless, we examined if this modest steric effect can induce
any chirality in the reaction in the outer sphere of coordination.
Following the lead by Ku¨ndig, we examined the asymmetric
Diels-Alder reaction between cyclopentadiene and methacrolein
(Scheme 4).21 The reaction was very slow by itself and was
Experimental Section
General Procedures. All experiments were carried out under
argon using standard Schlenk techniques. THF and toluene were
distilled from Na/K alloy, and 1,2-dichlorobenzene was distilled
A. E.; Saudan, C. M.; Viton, F.; Weber, J. J. Am. Chem. Soc. 2004, 126,
4843. (d) Davenport, A. J.; Davis, D. L.; Fawcett, F.; Russell, D. R. J.
Chem. Soc., Dalton Trans. 2004, 1481. (e) Hoshi, T.; Shionoiri, H.; Katano,
M.; Suzuki, T.; Hagiwara, H. Tetrahedron: Asymmetry 2002, 13, 2167. (f)
Ishihara, K.; Kurihara, H.; Matsumoto, M.; Yamamoto, H. J. Am. Chem.
Soc. 1998, 120, 6920. (g) Carmona, D.; Cativiela, C.; Gar´ıia-Correas, R.;
Lahoz, F. J.; Lamata, M. P.; Lo´pez, J. A.; Lo´pez-Ram de V´ıu, M. P.; Oro,
L. A.; San Jose´, E.; Viguri, F. Chem. Commun. 1996, 1247.
(22) (a) Sawamura, M.; Iikura, H.; Nakamura, E. J. Am. Chem. Soc. 1996,
118, 12850. (b) Sawamura, M.; Kuninobu Y.; Nakamura E. J. Am. Chem.
Soc. 2000, 122, 12407. (c) Sawamura, M.; Kuninobu, Y.; Toganoh, M.;
Matsuo, Y.; Yamanaka, M.; Nakamura, E. J. Am. Chem. Soc. 2002, 124,
9354. (d) Nakamura, E. Pure Appl. Chem. 2003, 75, 427. (e) Nakamura,
E.; Tahara, K.; Matsuo, Y.; Sawamura, M. J. Am. Chem. Soc. 2003, 125,
2834. (f) Toganoh, M.; Matsuo, Y.; Nakamura, E. Angew. Chem., Int. Ed.
2003, 42, 3530. (g) Toganoh, M.; Matsuo, Y.; Nakamura, E. J. Organomet.
Chem. 2003, 683, 295. (h) Toganoh, M.; Matsuo, Y.; Nakamura, E. J. Am.
Chem. Soc. 2003, 125, 13974. (i) Matsuo, Y.; Kuninobu, Y.; Ito, S.;
Nakamura, E. Chem. Lett. 2004, 33, 68. (j) Matsuo, Y.; Tahara, K.;
Sawamura, M.; Nakamura, E. J. Am. Chem. Soc. 2004, 126, 8725. (k)
Nakamura, E. J. Organomet. Chem. 2004, 689, 4630. (l) Matsuo, Y.;
Iwashita, A.; Nakamura, E. Organometallics 2005, 24, 89. (m) Matsuo,
Y.; Nakamura, E. J. Am. Chem. Soc. 2005, 127, 8457. (n) Herber, R. H.;
Nowik, I.; Matsuo, Y.; Toganoh, M.; Kuninobu, Y.; Nakamura, E. Inorg.
Chem. 2005, 44, 5629. (o) Matsuo, Y.; Isobe, H.; Tanaka, T.; Murata, Y.;
Murata, M.; Komatsu, K.; Nakamura, E. J. Am. Chem. Soc. 2005, 127,
17148.
(15) 31P NMR signals of major diastereomers (5, 7-15) appear around
δ 45 and 70. See Exparimental Section.
(16) (a) Bruce, M. I.; Wallis, R. C. Aust. J. Chem. 1979, 32, 1471. (b)
Consiglio, G.; Morandini, F.; Ciani, G. F.; Sironi, A. Organometallics 1986,
5, 1976. (c) Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res. 1999, 32, 311.
(d) Bruce, M. I. Chem. ReV. 1991, 91, 197. (e) Katayama, H.; Ozawa, F.
Coord. Chem. ReV. 2004, 248, 1703. (f) Puerta, M. C.; Valerga, P. Coord.
Chem. ReV. 1999, 193-195, 977.
(17) (a) Schilling, B. E. R.; Hoffman, R.; Lichtenberger, D. L. J. Am.
Chem. Soc. 1979, 105, 585. (b) Cadierno, V.; Gamasa, M. P.; Gimeno, J.;
Perez-Carreno, E.; Garcia-Granda, S. Organometallics 1999, 18, 2821.
(18) Bruce, M. I.; Wong, F. J.; Skeleton, B. W.; White, A. H. J. Chem.
Soc., Dalton Trans. 1982, 2203.
(19) (a) Aneetha, H.; Jimenez-Tenorio, M.; Puerta, M. C.; Valerga, P.;
Mereiter, K. Organometallics 2003, 22, 2001. (b) Bustelo, E.; Carbo, J. J.;
Liedos, A.; Mereiter, K.; Puerta, M. C.; Valerga, P. J. Am. Chem. Soc.
2003, 125, 3311.
(20) (a) Gamasa, M. P.; Gimeno, J.; Martin-Vaca, B. M.; Borge, J.;
Garcia-Granda, S.; Perez-Carreno, E. Organometallics 1994, 13, 4045. (b)
Cadierno, V.; Gamasa, M. P.; Gimeno, J.; Borge, J.; Garcia-Granda, S.
Organometallics 1997, 16, 3178.
(21) (a) Ku¨ndig, E. P.; Saudan, C. M.; Bernardinelli, G. Angew. Chem.,
Int. Ed. 1999, 38, 1220. (b) Ku¨ndig, E. P.; Saudan, C. M.; Alezra, V.; Viton,
F.; Bernardinelli, G. Angew. Chem., Int. Ed. 2001, 40, 4481. (c) Alezra,
V.; Bernardinelli, G.; Corminboeuf, C.; Frey, U.; Ku¨ndig, E. P.; Merbach,

2830 Organometallics, Vol. 25, No. 11, 2006
Matsuo et al.
3
3
from CaH2 before use. All solvents were thoroughly degassed by
trap-to-trap distillation and stored under argon. Ru(C60Me5)Cl(CO)2
(3) was prepared according to the previous report.14 A THF solution
of KOtBu and (R)-1,2-bis(diphenylphosphino)propane were pur-
chased from Sigma-Aldrich Co. and were used as received.
i-Ph), 134.12 (d, JP-C ) 8.6 Hz, 2C, m-Ph), 134.88 (d, JP-C
)
6.3 Hz, 2C, m-Ph), 137.58 (d, 3JP-C ) 10.9 Hz, 2C, m-Ph), 138.83
3
(d, JP-C ) 12.8 Hz, 2C, m-Ph), 143.06-143.89, 144.21, 147.20,
148.10-148.40, 151.44, 152.75, 152.91, 153.08, 153.46, 153.80,
154.03, 154.92 (50C, C60(sp2)); 31P NMR (200 MHz, CDCl3) δ
2
2
45.8 (d, JP-P ) 32.3 Hz, 1P, RuPPh2), 69.0 (d, JP-P ) 32.3 Hz,
1P, RuPPh2); IR (powder, cm-1) 2923 (m), 2892 (m), 2865 (m)
(νC-H), 1459 (m), 1447 (m), 1432 (m), 1090 (m), 1067 (m), 1027
(m) (νP-C); UV-vis (4.46 × 10-6 M in CH2Cl2; λmax/nm (ꢀ)) 276
(1.22 × 105), 348 (3.13 × 104), 392 (1.82 × 104); APCI-HRMS
(-) calcd for C92H41ClP2Ru (M-) 1344.1416, found 1344.1457.
HPLC analyses were performed on Shimadzu LC-10A system
equipped with SPD-M10A diode array detector and a Cosmosil-
Buckyprep column (4.6 × 250 mm, Nacalai Tesque Co.). Prepara-
tive HPLC separations were performed by the use of a Buckyprep
column (20 mm × 250 mm) using toluene/2-propanol (7:3 or 1:1)
1
as eluent. All H (400 MHz, 500 MHz), 13C{1H} (100 MHz, 125
MHz), and 31P{1H} NMR (200 MHz) spectra were recorded on
JEOL ECX400 and ECA500 spectrometers. Spectra were reported
in parts per million from internal tetramethylsilane (δ 0.00 ppm)
Preparation of [Ru(η5-C60Me5)((R)-prophos)(CH3CN)]+-
[SbF6]- (7). In the presence of AgSbF6 (3.8 mg, 0.0111 mmol)
acetonitrile (7.8 µL, 0.1486 mmol) was added to a solution of 5
(10 mg, 0.00743 mmol) in dichloromethane (2 mL), and the mixture
was stirred at room temperature for 1 h. The mixture was diluted
with dichloromethane and poured onto a silica gel column eluted
with dichloromethane to obtain complex 7 (9.0 mg, 90% yield) as
a brown solid: 1H NMR (500 MHz, CDCl3) δ 1.11 (m, 3H,
CHCH3), 1.19 (s, 3H, C60Me5), 1.91 (s, 3H, C60Me5), 1.92 (m, 1H,
CH2PPh2), 2.08 (s, 3H, CH3CN), 2.12 (s, 3H, C60Me5), 2.23 (s,
3H, C60Me5), 2.40 (s, 3H, C60Me5), 2.70 (m, 1H, CH2PPh2), 2.75-
1
or residual protons of the deuterated solvent for H NMR, from
solvent carbon (e.g., δ 77.00 ppm for chloroform) for 13C{1H}
NMR, and from external H3PO4 (δ 0.00 ppm) for 31P{1H} NMR.
High-resolution mass spectra were measured on a JEOL JMS-
T100LC APCI/ESI-TOF mass spectrometer. IR and UV-vis spectra
were recorded on Applied Systems Inc. React-IR 1000 and JASCO
V-570.
Preparation of Ru(η5-C60Me5)Cl(dppe) (4). To a solution of
Ru(η5-C60Me5)Cl(CO)2 (3; 50 mg, 0.051 mmol) in 1,2-dichloroben-
zene (10.0 mL) was added 1,2-bis(diphenylphosphino)ethane (dppe)
(101 mg, 0.25 mmol). The mixture was stirred and heated at 150
°C for 4 days, and the progress of the reaction was monitored by
HPLC. After the solvent was evaporated under reduced pressure,
purification by preparative HPLC afforded orange crystals of 4 (31
mg, 47% yield): 1H NMR (500 MHz, CDCl3) δ 2.18 (m, 2H, Ph2-
PCH2CH2PPh2), 2.25 (s, 6H, C60Me5), 2.36 (s, 9H, C60Me5), 3.01-
3.05 (m, 2H, Ph2PCH2CH2PPh2), 7.40-7.53 (m, 12H, PPh2), 7.81
(t, 4H, PPh2), 8.30 (t, 4H, PPh2); 13C NMR (125 MHz, CS2/C6D6)
δ 30.92 (br, 2C, PCH2CH2P), 31.96 (s, C60Me5), 32.18 (s, C60Me5),
32.18 (s, C60Me5), 32.39 (s, C60Me5), 51.68 (br, C60Me5), 136.40
(s, PPh2), 137.65 (s, PPh2), 144.25 (br, C60), 147.79 (br, C60), 148.81
(br, C60); 31P NMR (200 MHz, CDCl3) δ 63.44 (s, 2P, Ph2PCH2-
CH2PPh2); IR (powder, cm-1) 2964 (m), 2923 (m), 2854 (m) (νC-H),
1459 (m), 1447 (m), 1434 (m), 1414 (m), 1090 (m), 1067 (m),
1027 (m) (νP-C); APCI-HRMS (-) calcd for C91H39ClP2Ru (M-)
1330.1259, found 1330.1307.
3
2.91 (m, 1H, CHCH3), 7.38-7.87 (m, 14H, PPh2), 7.86 (t, JH-H
3
) 8.30 Hz, 2H, PPh2), 8.14 (t, JH-H ) 8.87 Hz, 2H, PPh2), 8.36
(t, JH-H ) 9.18 Hz, 2H, PPh2); 13C NMR (125 MHz, CD2Cl2) δ
3
2
3
5.33 (s, 1C, CH3CN), 15.10 (dd, JP-C ) 16.69 Hz, JP-C ) 4.76
Hz, PPh2CHCH3), 25.97 (s, 1C, C60Me5), 27.24 (s, 1C, C60Me5),
28.73 (s, 1C, C60Me5), 31.74 (s, 2C, C60Me5), 32.10 (dd, JP-C
1
)
29.81, 2JP-C ) 10.74 Hz, 1C, CH2PPh2 or PPh2CHCH3), 35.40 (dd,
1JP-C ) 29.81, 2JP-C ) 15.50 Hz, CH2PPh2 or PPh2CHCH3), 50.61
(s, 1C, C60(sp3)), 51.89 (s, 4C, C60(sp3)), 92.78 (s, 1C, C60(CCp)),
95.63 (s, 1C, C60(CCp)), 108.27 (s, 1C, C60(CCp)), 114.50 (s, 1C,
C60(CCp)), 118.29 (s, 1C, C60(CCp)), 127.67-153.52 (C60 and Ph);
31P NMR (200 MHz, CDCl3) δ 44.16 (d, JP-P ) 32.28 Hz, 1P),
2
71.43 (d, JP-P ) 32.28 Hz, 1P); IR (powder, cm-1) 2973 (m)
2
(νC-H), 1958 (m) (νC-N), 1437 (m), 1096 (m) (νP-C); APCI-HRMS
(+) calcd for C94H44NP2Ru [M - SbF6
- +
]
1350.1975, found
1350.1926.
Preparation of [Ru(η5-C60Me5)((R)-prophos)(tBuCN)]+[SbF6]-
(8). This compound was prepared in a manner similar to that for 7.
Complex 8 was isolated in 95% yield: 1H NMR (500 MHz, CDCl3)
δ 1.21 (s, 9H, t-BuCN), 1.30 (dd, 3JP-H ) 11.45 Hz, 3JH-H ) 6.85
Hz, 3H, CHCH3), 1.37 (s, 3H, C60Me5), 1.97 (m, 1H, PCH), 1.98
(s, 6H, C60Me5), 2.37 (s, 3H, C60Me5), 2.62 (m, 1H, PCH), 2.67 (s,
3H, C60Me5), 3.13 (m, 1H, PCH), 7.43 (m, 5H), 7.69 (m, 3H), 7.79-
7.94 (m, 8H), 8.36 (m, 4H); 13C NMR (125 MHz, CDCl3) δ 15.00
(dd, 2JP-C ) 16.27 Hz, 3JP-C ) 5.74 Hz, CH3(prophos)), 26.41 (s,
1C, C60Me5), 27.17 (s, 3C, NCCMe3), 27.60 (s, 1C, C60Me5), 27.98
Preparation of Ru(η5-C60Me5)Cl((R)-prophos) (5). To a solu-
tion of 3 (50 mg, 0.051 mmol) in 1,2-dichlorobenzene (10.0 mL)
was added [R-(+)-1,2-bis(diphenylphosphino)propane] ((R)-pro-
phos) (104 mg, 0.25 mmol). The mixture was stirred and heated at
150 °C for 16 h, and the progress of the reaction was monitored
by HPLC. After the solvent was evaporated under reduced pressure,
purification by preparative HPLC afforded orange crystals of 5 (28
mg, 41% yield): 1H NMR (500 MHz, CDCl3) δ 1.09 (dd, 3JH-H
)
1
6.9 Hz, 3JP-H ) 10.6 Hz, 3H, PCHMe), 1.44 (s, 3H, C60Me5), 1.61
(s, 3H, C60Me5), 1.87-1.95 (m, 1H, PCH2), 2.06 (s, 3H, C60Me5),
2.48 (s, 3H, C60Me5), 2.57-2.73 (m, 1H, PCHMe), 2.86 (s, 3H,
C60Me5), 3.54-3.57 (m, 1H, PCH2), 7.33-7.96 (m, 14H, PPh2),
(1C, C60Me5), 31.51 (2C, C60Me5), 32.70 (dd, JP-C ) 29.68 Hz,
2JP-C ) 10.54 Hz, CH(prophos)), 34.65 (dd, JP-C ) 28.73 Hz,
1
2JP-C ) 15.31 Hz, CH2(prophos)), 50.21 (s, 1C, C60(sp3)), 51.16
(s, 1C, C60(sp3)), 51.52 (s, 3C, C60(sp3)), 92.88 (s, 1C, C60(CCp)),
95.33 (s, 1C, C60(CCp)), 110.03 (s, 1C, C60(CCp)), 113.05 (s, 1C,
C60(CCp)), 116.99 (s, 1C, C60(CCp)), 127.29, 127.60, 128.01, 128.09,
128.66, 128.74, 129.53, 129.63, 129.70, 129.87, 130.19, 131.26,
131.91, 132.42, 132.61, 132.66, 133.25, 133.32, 133.53, 135.26,
135.35, 137.42, 137.52, 138.51, 138.84, 141.31, 142.50-143.90
(m), 147.15, 148.31, 151.12, 151.76, 153.13 (C60 and Ph); 31P NMR
3
3
8.24 (t, JH-H ) 8.0 Hz, 2H, PPh2), 8.39 (t, JH-H ) 8.0 Hz, 2H,
PPh2), 8.46 (t, JH-H ) 8.6 Hz, 2H, PPh2); 13C NMR (100 MHz,
CDCl3) δ 15.53 (dd, JP-C ) 15.9 Hz, JP-C ) 5.7 Hz, 1C, CH3),
23.62 (s, 1C, C60Me5), 24.59 (s, 1C, C60Me5), 27.37 (s, 1C, C60Me5),
3
2
3
1
31.77 (s, 1C, C60Me5), 32.06 (s, 1C, C60Me5), 32.67 (dd, JP-C
)
2
1
32.3 Hz, JP-C ) 11.7 Hz, 1C, Ph2PC), 37.92 (dd, JP-C ) 27.2
2
Hz JP-C ) 16 Hz 1C, Ph2PC), 51.05 (s, 1C, C60(sp3)), 51.29 (s,
2
(200 MHz, CDCl3) δ 44.90 (d, JP-P ) 38.30 Hz, 1P), 70.48 (d,
2JP-P ) 38.30 Hz, 1P); IR (powder cm-1) 2930 (m), 2868 (m)
1C, C60(sp3)), 51.36 (s, 1C, C60(sp3)), 51.54 (s, 1C, C60(sp3)), 53.62
(s, 1C, C60(sp3)), 87.62 (s, 1C, C60(Cp)), 92.51 (s, 1C, C60(Cp)),
108.37 (s, 1C, C60(Cp)), 110.02 (s, 1C, C60(Cp)), 110.43 (s, 1C,
(νC-H), 2210 (m) (νC-N), 1440 (m), 1090 (m) (νP-C); ESI-HRMS
(+) calcd for C97H50NP2Ru [M - SbF6
- +
]
1392.2462, found
2
2
1392.2472.
C60(Cp)), 126.82 (d, JP-C ) 9.3 Hz, 2C, o-Ph), 127.04 (d, JP-C
) 9.5 Hz, 2C, o-Ph), 127.73 (d, 2JP-C ) 8.2 Hz, 2C, o-Ph), 127.81
(d, 2JP-C ) 8.2 Hz, 2C, o-Ph), 129.62 (s, 1C, p-Ph), 129.91 (s, 1C,
p-Ph), 130.53 (s, 1C, p-Ph), 131.37 (s, 1C, i-Ph), 131.68 (s, 1C,
i-Ph), 131.75 (s, 1C, p-Ph), 133.45 (s, 1C, i-Ph), 133.82 (s, 1C,
Preparation of [Ru(η5-C60Me5)((R)-prophos)(methacrolein)]+-
[SbF6]- (9). This compound was prepared in a manner similar to
that for 7. Complex 9 was isolated in 80% yield: 1H NMR (500
3
3
MHz, CDCl3) δ 1.00 (m, 3H), 1.36 (dd, JP-H ) 13.75 Hz, JH-H

Remote Chirality Transfer
Organometallics, Vol. 25, No. 11, 2006 2831
Table 1. Crystal Data and Data Collection Parameters for 4,
5 and 14
) 6.3 Hz, 3H), 2.00 (m, 15H, C60Me5), 2.40 (m, 1H), 2.67 (m,
1H), 2.80 (m, 1H), 4.30-5.07 (m, 2H), 7.50-8.43 (m, 20H, HAr),
2
9.58 (br, 1H); 31P NMR (200 MHz, CDCl3) δ 38.71 (d, JP-P
48.46 Hz, 1P), 68.38 (d, JP-P ) 53.82 Hz, 1P).
)
4
5
14
2
formula
cryst syst
space group
C91H39ClP2Ru
monoclinic
P21/c (No. 14)
C92H41ClP2Ru
monoclinic
P21 (No. 4)
C92H41BrP2Ru
monoclinic
P21 (No. 4)
Preparation of [Ru(η5-C60Me5)((R)-prophos)(acetone)]+-
[SbF6]- (10). This compound was prepared in a manner similar to
that for 7. Complex 10 was isolated in 80% yield: 1H NMR (500
R, Rw (I > 2σ(I)) 0.0714, 0.1865 0.0774, 0.2104
R1, wR2 0.0808, 0.1979 0.0846, 0.2219
0.057, 0.1461
0.062, 0.1517
3
3
MHz, CDCl3) δ 1.31 (dd, JP-H ) 13.20 Hz, JH-H ) 6.30 Hz,
3H), 1.95 (m, 15H, C60Me5), 2.02 (s, 6H, CH3COCH3), 2.38 (m,
1H, CH2PPh2), 2.66 (m, 1H, CH2PPh2), 2.74-2.85 (m, 1H,
CHCH3), 7.48-7.86 (m, 16H, PPh2), 8.03 (m, 2H, PPh2), 8.38 (m,
2H, PPh2); 31P NMR (200 MHz, CDCl3) δ 45.90 (d, 2JP-P ) 48.44
(all data)
GOF on F2
a, Å
b, Å
1.061
1.049
1.039
12.919(9)
23.937(18)
17.951(9)
90
99.741(4)
90
10.615(5)
29.500(5)
19.502(5)
90
95.533(5)
90
10.5860(3)
26.7560(13)
21.8930(9)
90
94.366(3)
90
c, Å
2
R, deg
â, deg
γ, deg
V, Å3
Hz, 1P), 72.35 (d, JP-P ) 53.84 Hz, 1P).
Preparation of [Ru(η5-C60Me5)((R)-prophos)(CO)]+[SbF6]-
(11). This compound was prepared in a manner similar to that for
7 under 1 atm of CO. Complex 11 was isolated in 81% yield: 1H
NMR (500 MHz, CDCl3, -40 °C) δ 1.13 (s, 3H, C60Me5), 1.22
5471.2(6)
4
6078(3)
2
6183.0(4)
2
Z
T, K
153(2)
153(2)
153(2)
3
3
cryst size, mm
D
0.85, 0.42, 0.2
1.615
0.80, 0.30, 0.20 0.45, 0.40, 0.20
(dd, JP-H ) 12.80 Hz, JH-H ) 6.00 Hz, 3H, CHCH3), 1.86(s,
6H, C60Me5), 2.06 (m, 1H, CH2PPh2), 2.16 (s, 3H, C60Me5), 2.81
(s, 3H, C60Me5), 2.81 (m, 1H, CH2PPh2), 2.96-3.07 (m, 1H,
CHCH3), 4.76-8.30 (20H, Ph); 13C NMR (125 MHz, CDCl3, 20
calcd, g/cm-3
1.469
1.591
2θmin, 2θmax
,
2.29, 25.56
2.05, 25.62
2.21, 25.72
deg
no. reflns (total)
no. reflns
42 910
10 127
39 175
9781
44 838
11 858
°C) δ 14.90 (dd, 2JP-C ) 17.88 Hz, 3JP-C ) 4.76 Hz, PPh2CHCH3),
1
(unique)
28.48 (s, 2C, C60Me5), 30.94 (s, 3C, C60Me5), 35.70 (dd, JP-C
)
no. reflns
8575
8719
10 890
32.80 Hz, 2JP-C ) 12.52 Hz, CH2PPh2 or PPh2CHCH3), 37.15 (dd,
(I > 2σ(I))
no. params
∆, e Å-3
1JP-C ) 34.50 Hz, JP-C ) 8.35 Hz, CH2PPh2 or PPh2CHCH3),
2
857
1.01, -0.941
1705
1.377, -0.84
1856
1.133, -1.015
51.58 (s, 5C, C60(sp3)), 123.78-150.62 (C60 and Ph), 203.74 (dd,
2JP-C ) 20.2 Hz, JP-C ) 17.9 Hz, CO); 31P NMR (200 MHz,
2
CDCl3) δ 44.26 (d, 2JP-P ) 26.92 Hz, 1P), 72.35 (d, 2JP-P ) 21.54
Hz, 1P); IR (powder, cm-1) 2930 (νC-H), 2864 (m), 2162 (m), 1972
C60Me5), 1.64 (s, 3H, C60Me5), 1.87 (m, 1H, CH2PPh2), 2.07 (s,
3H, C60Me5), 2.50 (s, 3H, C60Me5), 2.60-2.80 (m, 1H, CH2PPh2),
2.97 (s, 3H, C60Me5), 3.83 (m, 1H, CHCH3), 7.17-7.73 (14H, Ph),
(s) (νC-O), 1440 (m), 1090 (m) (νP-C); APCI-HRMS (+) calcd for
- +
C93H41OP2Ru [M - SbF6
] 1337.1676, found 1337.1689.
3
3
8.28 (t, JH-H ) 7.70 Hz, 2H, Ph), 8.39 (t, JH-H ) 8.50 Hz, 2H,
Preparation of [Ru(η5-C60Me5)((R)-prophos)(2,6-Me2C6H3-
NC)]+[SbF6]- (12). This compound was prepared in a manner
similar to that for 7. Complex 12 was isolated in 91% yield as a
mixture of two diastereomers: 1H NMR (500 MHz, CDCl3, major
isomer) δ 1.24 (dd, 3JP-H ) 12.9 Hz, 3JH-H ) 6.3 Hz, 3H, CHCH3),
1.45 (s, 3H, C60Me5), 1.58 (s, 3H, C60Me5), 1.96 (s, 3H, C60Me5),
2.22 (m, 1H, CH2PPh2), 2.45 (s, 3H, C60Me5), 2.49 (s, 6H, Ph-
(Me)2NC), 2.86 (s, 3H, C60Me5), 3.08 (m, 1H, CH2PPh2), 3.19 (m,
1H, CHCH3), 7.15-7.96 (23H, Ph); 31P NMR (200 MHz, CDCl3)
δ 53.12 (d, 2JP-P ) 21.54 Hz, 1P, major), 56.53 (d, 2JP-P ) 26.92
Hz, 1P, minor), 64.80 (d, 2JP-P ) 21.54 Hz, 1P, minor), 74.30 (d,
2JP-P ) 26.92 Hz, 1P, major); IR (powder, cm-1) 3290 (m), 3250
(m), 2972 (m) (νC-H), 2362 (m), 2061 (s) (νN-C), 1741 (s), 1430
Ph), 8.43 (t, JH-H ) 8.50 Hz, 2H, Ph); 13C NMR (CDCl3, 125
MHz) δ 16.00 (dd, JP-C ) 15.50 Hz, JP-C ) 5.95 Hz,
CH3(prophos)), 24.75 (s, 1C, C60Me5), 27.31 (s, 1C, C60Me5), 27.41
(s, 1C, C60Me5), 31.80 (s, 1C, C60Me5), 32.28 (s, 1C, C60Me5), 34.40
3
2
3
1
2
(dd, JP-C ) 33.38 Hz, JP-C ) 11.92 Hz, CH(prophos)), 37.48
1
2
(dd, JP-C ) 26.23 Hz, JP-C ) 16.70 Hz, CH2(prophos)), 50.87
(s, 1C, C60(sp3)), 51.29 (s, 1C, C60(sp3)), 51.34 (s, 1C, C60(sp3)),
51.71 (s, 1C, C60(sp3)), 53.90 (s, 1C, C60(sp3)), 88.58 (s, 1C, C60-
(CCp)), 92.62 (s, 1C, C60(CCp)), 107.83 (s, 1C, C60(CCp)), 109.79
(s, 1C, C60(CCp)), 110.52 (s, 1C, C60(CCp)), 126.77 (d, 2JP-C ) 9.53
2
Hz, 2C, o-Ph), 126.91 (d, JP-C ) 9.53 Hz, 2C, o-Ph), 127.50 (d,
2JP-C ) 8.34 Hz, 2C, o-Ph), 127.69 (d, 2JP-C ) 8.35 Hz, 2C, o-Ph),
129.56 (s, 1C, p-Ph), 129.92 (s, 1C, p-Ph), 130.44 (s, 1C, p-Ph),
131.64 (s, 1C, p-Ph), 133.68 (d, 3JP-C ) 5.96 Hz, 1C, i-Ph), 134.00
(s), 1370 (m), 1204 (s), 745 (s); APCI-HRMS (+) calcd for C101H50-
- +
3
3
NP2Ru [M - SbF6
] 1440.2445, found 1440.2426.
(d, JP-C ) 4.76 Hz, 1C, i-Ph), 134.13 (d, JP-C ) 8.35 Hz, 2C,
Preparation of [Ru(η5-C60Me5)((R)-prophos)(PhCH2NC)]+-
[SbF6]- (13). This compound was prepared in a manner similar to
that for 7. Complex 13 was isolated in 68% yield as a mixture of
m-Ph), 134.68 (d, JP-C ) 2.39 Hz, 1C, i-Ph), 135.00 (d, JP-C
)
1
1
2.38 Hz, 1C, i-Ph), 135.10 (d, 2JP-C ) 5.96 Hz, 2C, m-Ph), 137.76
3
3
(d, JP-C ) 10.76 Hz, 2C, m-Ph), 138.65 (d, JP-C ) 11.92 Hz,
2C, m-Ph), 142.87-144.24, 147.13-147.33, 148.03-148.40 (C60),
151.37, 152.54, 152.67, 152.79, 152.89, 153.40, 153.55, 153.79,
154.83 (s, C60(Câ)); 31P NMR (200 MHz, CDCl3) δ 45.99 (d, 2JP-P
1
two diastereomers. H NMR (500 MHz, CDCl3, major isomer) δ
3
3
0.93 (dd, JP-H ) 12.3 Hz, JH-H ) 6.9 Hz, 3H, CHCH3), 1.93-
2.34 (m, 15H, C60Me5), 2.78-2.93 (m, 3H, CH2CH), 4.74 (AB,
δA ) 4.70, δB ) 4.78, JAB ) 14.85 Hz, PhCH2NC), 6.82 (d, 3JH-H
) 6.85 Hz, 2H), 7.20-8.37 (m, 23H); 31P NMR (200 MHz, CDCl3)
2
) 30.64 Hz, 1P), 67.89 (d, JP-P ) 27.58 Hz, 1P); IR (powder,
cm-1) 2923 (m, νC-H), 1432 (m), 1260 (s), 1054 (m) (νP-C); APCI-
HRMS (-) calcd for C92H41BrP2Ru [M]- 1390.0921, found
1390.0962.
2
2
δ 47.50 (d, JP-P ) 21.52 Hz, 1P, major), 56.81 (d, JP-P ) 1.52
Hz, 1P, minor), 65.26 (d, 2JP-P ) 21.52 Hz, 1P, minor), 73.78 (d,
2JP-P ) 26.92 Hz, 1P, major); IR (powder, cm-1) 3255 (br), 2126
Preparation of [Ru(η5-C60Me5)((R)-prophos)(â-Ph-vinylidene]+-
[SbF6]- (15). A solution of ruthenium cation complex 7 (20 mg)
and phenylacetylene (0.5 mL) in chloroform (4 mL) was heated at
60 °C for 24 h. The solvent was then removed under vacuum. The
residue was dissolved in 2 mL of dichloromethane, and 20 mL of
n-hexane was added to precipitate the product 15 (19 mg, 90%):
1H NMR (500 MHz, CDCl3) δ 1.38 (m, 3H, CHCH3), 1.39 (s, 3H,
C60Me5), 1.71 (s, 3H, C60Me5), 1.93 (s, 3H, C60Me5), 2.33 (s, 3H,
C60Me5), 2.43 (m, 1H, CH2PPh2), 2.91(s, 3H, C60Me5), 3.36-3.46
(m, 1H, CH2PPh2), 3.64 (m, 1H, CHCH3), 5.19 (s, 1H, PhCH),
6.50 (d, JH-H ) 6.90 Hz, Ph), 7.13 (m, 3H, Ph), 7.42-7.99 (m,
(s) (νN-C), 1437 (s), 1096 (s) (νP-C); APCI-HRMS (+) calcd for
- +
C
100H48NP2Ru [M - SbF6 ] 1426.2306, found 1426.2264.
Preparation of Ru(η5-C60Me5)Br((R)-prophos) (14). To a
solution of 1 mL of CH2Cl2 containing compound 7 (2.3 mg,
0.00170 mmol) was added 36 mg of magnesium bromide diethyl
etherate complex in 1 mL of THF. After stirring for 5 h at 40 °C,
the mixture was concentrated and subjected to flash column
chromatography to afford 2.0 mg of the desired product as a yellow
solid, 14 (85% yield): 1H NMR (CDCl3, 500 MHz) δ 1.09 (dd,
3
3JH-H ) 6.9 Hz, JP-H ) 10.3 Hz, 3H, CHCH3), 1.58 (s, 3H,

2832 Organometallics, Vol. 25, No. 11, 2006
Matsuo et al.
16H), 8.15 (t, JH-H ) 8.00 Hz, 2H), 8.27 (t, JH-H ) 8.00 Hz, 2H);
X-ray Crystallographic Analysis. Single crystals of 4, 5, and
14 suitable for X-ray diffraction studies were grown and subjected
to data collection. The data sets were collected on a MacScience
DIP2030 imaging plate diffractometer using Mo KR (graphite
monochromated, λ ) 0.71069 Å) radiation. Crystal data and data
statistics are summarized in Table 1. The structures of 4, 5, and 14
were solved by the direct method (SIR97).23 The positional and
thermal parameters of non-hydrogen atoms were refined anisotro-
pically on F2 by the full-matrix least-squares method, using
SHELXL-97.24 Hydrogen atoms were placed at calculated positions
and refined with the riding mode on their corresponding carbon
2
13C NMR (125 MHz, CDCl3) δ 14.87 (d, JP-C ) 16.78 Hz,
prophos), 27.15 (s, 1C, C60Me5), 28.20 (s, 1C, C60Me5), 29.00 (1C,
C60Me5), 31.55 (s, 2C, C60Me5), 31.63 (s, 1C, C60Me5), 35.40 (d,
1JP-C ) 30.20 Hz, prophos), 36.20 (d, 1JP-C ) 33.55 Hz, prophos),
51.04 (s, 1C, C60(sp3)), 51.36 (s, 1C, C60(sp3)), 51.77 (s, 2C, C60-
(sp3)), 51.95 (s, 1C, C60(sp3)), 108.38 (s, 1C, C60(CCp)), 116.48 (s,
2C, C60(CCp)), 119.73 (s, 1C, C60(CCp)), 120.99 (s, 1C, CHPh),
126.23 (s, 1C, C60(CCp)), 124.88-151.73 (C60, Ph), 343.92 (dd,
2JP-C ) 23.48, 2JP-C ) 13.42 Hz, 1C, RuC); 31P NMR (200 MHz,
CDCl3) δ 49.57 (d, 2JP-P ) 24.52 Hz, 1P), 72.78 (d, 2JP-P ) 24.52
Hz, 1P); IR (powder, cm-1) 3256 (br), 2929 (m) (νC-H), 1652 (m)
atoms. In the subsequent refinement, the function ∑w(Fo - Fc2)2
2
(νCdC), 1436 (s), 1094 (m) (νP-C); ESI-HRMS (+) calcd for
was minimized, where |Fo| and |Fc| are the observed and calculated
- +
C
101H48P2Ru [M + H - SbF6
]
1412.2275, found 1412.2269.
structure factor amplitudes, respectively. The agreement indices are
Catalytic Diels-Alder Reaction of Methacrolein and Cyclo-
defined as R1 ) ∑(||Fo| - |Fc||)/∑|Fo| and wR2 ) [∑w(Fo2 - Fc2)2/
4
pentadiene.20 To a solution of 0.01 mmol of 9 and 2,6-di-tert-
butylpyridine in 1 mL of dichloromethane were added 0.02 mL
(0.2 mmol) of methacrolein and 0.033 mL (0.4 mmol) of cyclo-
pentadiene. After stirring at room temperature for 48 h, the reaction
was quenched by addition of 10 mL of n-hexane. The resulting
precipitate was removed by filtrating through a pad of silica gel.
1H NMR analysis of the concentrated residue showed an exo/endo
ratio of the adduct of 23:1 (δ 9.69 for CHO of the exo isomer, δ
9.40 for that of the endo isomer). Flash column chromatography
afforded 30 mg of the adduct in 80% yield. The ee value was
∑(wFo )]1/2
.
Supporting Information Available: Crystallographic data of
4, 5, and 14 (CIF files). This material is available free of charge
via the Internet at http://pubs.acs.org.
OM060234C
(23) Altomare, A.; Burla, M. C.; Camalli, M.; Cascarano, G. L.;
Giacovazzo, C.; Guagliardi, A.; Moliterni, A. G. G.; Polidori, G.; Spagna,
R. J. Appl. Crystallogr. 1999, 32, 115-119.
(24) Sheldrick, G. M. SHELXL-97, Programs for Crystal Structure
Analysis (Release 97-2); Institut fu¨r Anorganische Chemie der Universita¨t:
Tammanstrasse 4, D-3400 Go¨tingen, Germany, 1998.
1
determined by H NMR analysis after conversion to the acetal of
(2R,4R)-2,4-pentanediol (δ 4.70 for CHO2 of the major exo isomer,
δ 4.68 for that of the minor exo isomer).