Chemistry of ruthenium(II) alkyl binap complexes: Novel bonding, cyclometalation, and P-C bond splitting

Article abstract of DOI:10.1021/om0209778

Reactions of the bis-isopropyl and bis-cyclohexyl alkyl Binap ligands, 8 and 9, respectively, with [RuCl₂(η⁶-p-cymene)]₂ afford new dinuclear chloro-bridged Ru compounds which contain the Binap ligands as six- rather than four-electron donors. A backbone double bond proximate to one of the P-donors complexes the metal atom. NMR details of the olefin bonding plus isomerization reactions involving loss of the olefin complexation are reported. Reactions of 8 or 9 with [Ru(OAc)₂(η⁶-p-cymene)] result in slow P - C bond cleavage and cyclometalation, instead of affording the anticipated [Ru(OAc)₂(Binap)] complex. The new cyclometalated complexes, 15 and 16, contain the complexed R₂P - O(C=O)CH₃ ligand and arise (presumably) via acetate attack at phosphorus with the electrons in the P - C bond moving to the ruthenium atom. The solid-state structure of one of these, the cyclohexyl analogue, 16, is reported and represents a rare structural example of a molecule with three different chelate ligands. The complexed R₂P - O(C=O)CH₃ ligand is readily hydrolyzed in wet triflic acid to afford the R₂P(OH) donor and an η⁶-arene ligand (via Ru - C protonation).

Full text of DOI:10.1021/om0209778

Organometallics 2003, 22, 1443-1451
1443
Ch em istr y of Ru th en iu m (II) Alk yl Bin a p Com p lexes:
Novel Bon d in g, Cyclom eta la tion , a n d P -C Bon d
Sp littin g
Tilmann J . Geldbach and Paul S. Pregosin*
Laboratory of Inorganic Chemistry, ETHZ, Ho¨nggerberg, 8093 Zu¨rich, Switzerland
Alberto Albinati
Department of Structural Chemistry (DCSSI), University of Milan, 20133 Milan, Italy
Received December 2, 2002
Reactions of the bis-isopropyl and bis-cyclohexyl alkyl Binap ligands, 8 and 9, respectively,
with [RuCl2(η6-p-cymene)]2 afford new dinuclear chloro-bridged Ru compounds which contain
the Binap ligands as six- rather than four-electron donors. A backbone double bond proximate
to one of the P-donors complexes the metal atom. NMR details of the olefin bonding plus
isomerization reactions involving loss of the olefin complexation are reported. Reactions of
8 or 9 with [Ru(OAc)2(η6-p-cymene)] result in slow P-C bond cleavage and cyclometalation,
instead of affording the anticipated [Ru(OAc)2(Binap)] complex. The new cyclometalated
complexes, 15 and 16, contain the complexed R2P-O(CdO)CH3 ligand and arise (presumably)
via acetate attack at phosphorus with the electrons in the P-C bond moving to the ruthenium
atom. The solid-state structure of one of these, the cyclohexyl analogue, 16, is reported and
represents a rare structural example of a molecule with three different chelate ligands. The
complexed R2P-O(CdO)CH3 ligand is readily hydrolyzed in wet triflic acid to afford the
R2P(OH) donor and an η6-arene ligand (via Ru-C protonation).
In tr od u ction
details on the organometallic chemistry of Ru-Binap
compounds are still scarce.
Interest in homogeneous catalysis using Binap, 1, and
related auxiliaries continues unabated.1-8 Specifically,
chiral Binap complexes of Ru(II) are now accepted as
excellent hydrogenation catalysts.9-12 Interestingly,
(1) Oestreich, M.; Dennison, P. R.; Kodanko, J . J .; Overman, L. E.
Angew. Chem., Int. Ed. 2001, 40, 1439.
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1998; p 239. Overman, L. E.; Rosen, M. D. Angew. Chem., Int. Ed.
2000, 39, 4596.
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Chem. Soc. 2001, 123, 7473.
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2002, 21, 1662. Faller, J . W.; Parr, J . Organometallics 2000, 19, 1829.
Faller, J . W.; Parr, J . Organometallics 2000, 19, 3556.
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Albinati, A. Organometallics 2000, 19, 3591. Drago, D.; Pregosin, P.
S.; Tschoerner, M.; Albinati, A. J . Chem. Soc., Dalton Trans. 1999,
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F. Organometallics 1997, 16, 4268.
We have begun to follow the reactions of Ru-Binap
(and the related MeO-Biphep, 2) complexes when (a)
weakly bound ligands (such as acetate) are removed
from the coordination sphere and (b) at the same time
no suitable strong donors are available. Interestingly,
both the complexed Binap and MeO-Biphep find a way
to donate additional electrons in that a double bond
proximate to one of the P-donors complexes the metal,
e.g., 3;13 see Scheme 1. Recently, more than a dozen
complexes of type 414 have been reported. As indicated
in the scheme, there are additional examples of this
bonding mode.15-17 The last examples in the scheme are
illustrative in that they involve the ubiquitous triphen-
(8) Brown, J . M.; Torrente, J . J . P. Organometallics 1995, 14, 1195.
(9) Kumobayashi, H. Rec. Trav. Chim. Pays-Bas 1996, 115, 201.
(10) Zhang, X.; Mashima, K.; Koyano, K.; Sayo, N.; Kumobayashi,
H.; Akutagawa, S.; Takaya, H. J . Chem. Soc., Perkin Trans. 1994, 2309.
(11) Mashima, K.; Kusano, K.; Ohta, T.; Noyori, R.; Takaya, H. J .
Chem. Soc., Chem. Commun. 1989, 1208. Ohta, Takaya, H.; Noyori,
R. Inorg. Chem. 1988, 27, 566. Noyori, R.; Takaya, H. Acc. Chem. Res.
1990, 23, 345. Noyori, R. Asymmetric Catalysis in Organic Synthesis;
J ohn Wiley and Sons: London, 1994.
(13) den Reijer, C. J .; Wo¨rle, M.; Pregosin, P. S. Organometallics
2000, 19, 309.
(14) den Reijer, C. J .; Dotta, P.; Pregosin, P. S.; Albinati, A. Can. J .
Chem. 2001, 79, 693.
(15) Pathak, D. D.; Adams, H.; Bailey, N. A.; King, P. J .; White, C.
J . Organomet. Chem. 1994, 479, 237.
(16) Cyr, P. W.; Rettig, S. J .; Patrick, B. O.; J ames, B. R. Organo-
metallics 2002, 21, 4672.
(17) Feiken, N.; Pregosin, P. S.; Trabesinger, G.; Scalone, M.
Organometallics 1997, 16, 537. Feiken, N.; Pregosin, P. S.; Trabesinger,
G.; Albinati, A.; Evoli, G. L. Organometallics 1997, 16, 5756.
(12) Miyake, T.; Seido, N.; Kumobayashi, H.; Takaya, H. J . Org.
Chem. 1995, 60, 357.
10.1021/om0209778 CCC: $25.00 © 2003 American Chemical Society
Publication on Web 02/27/2003

1444 Organometallics, Vol. 22, No. 7, 2003
Geldbach et al.
Sch em e 1
ylphosphine,18,19 thereby indicating that this type of
bonding is not limited to biaryl bis-phosphines such as
Binap.
7a and its Binap analogue, 7b.22 Aspects of this chem-
istry have been summarized.23
This six-electron bonding mode for Binap induces
considerable strain in the naphthyl backbone17 with the
result that P-C bond cleavage becomes facile.13 Reac-
tion of [Ru(OAc)2(Binap)] with slightly more than 2
equiv of wet triflic acid in 1,2-dichloroethane at 363 K
gave the product 5 in good yield.13
Formally, the H+ protonates the complexed acetate
ligands and the water adds across the P-C bond. The
metal, which is already complexed to the Binap π-sys-
tem via the proximate double bond, need only slide
across the face of the complexed olefin to reach a
distorted η6 mode. Attempts to generate an open coor-
dination position in 5 by solvolyzing the weakly bound
triflate ligand in simple alcohols resulted in the unusual
compounds 6 (see eq 1).20
While this represents interesting chemistry, it sty-
mies all attempts to generate potential solvent-stabi-
lized cationic catalysts. With a view to further under-
standing this P-C bond splitting chemistry and possibly
circumventing unwanted P-phenyl migration reactions,
we synthesized the alkyl Binap ligands 8 and 9 and
report on some of their Ru(II) complexes as well as one
or two unusual aspects of this new chemistry.
Resu lts a n d Discu ssion
6e Don or Com p lexes. The new alkyl-substituted
Binap ligands were prepared as shown in eq 2. The
ligand 9 has been prepared previously, though in a
different manner,24 whereas 8 represents a new deriva-
tive.
In contrast to the reaction with the classical phenyl-
substituted Binap, which affords [RuCl(Binap)(η6-p-
cymene)]Cl, reaction of 1 equiv of the cymene complex
The complexes 6 arise from migration of a P-phenyl
fragment21 and subsequent (or concomitant) attack of
the alcohol on the P-center. In protic solvents containing
water this type of reaction leads to complete stripping
of the P-phenyl groups, i.e., the MeO-Biphep complex
(18) Cheng, T.; Szalda, D. J .; Bullock, R. M. J . Chem. Soc., Chem.
Commun. 1999, 1629.
(19) Aneetha, H.; J emenez-Tenorio, M.; Carmen Puerta, M.; Valerga,
P.; Mereiter, K. Organometallics 2002, 21, 628.
(20) Geldbach, T. J .; Drago, D.; Pregosin, P. S. J . Chem. Soc., Chem.
Commun. 2000, 1629.
(21) Geldbach, T. J .; Pregosin, P. S.; Bassetti, M. Organometallics
2001, 20, 2990.
(22) Geldbach, T. J .; Pregosin, P. S.; Albinati, A.; Rominger, F.
Organometallics 2001, 20, 1932.
(23) Geldbach, T. J .; Pregosin, P. S. Eur. J . Inorg. Chem. 2002, 1907.
(24) Zhang, X.; Kazushi, M.; Koyano, K.; Sayo, N.; Kumobayashi,
H.; Akutagawa, S.; Takaya, H. Tetrahedron Lett. 1991, 32, 7283.

Ruthenium(II) Alkyl Binap Complexes
Organometallics, Vol. 22, No. 7, 2003 1445
F igu r e 1. 13C,1H long-range spectrum of 11, revealing the η2-coordination from the backbone (d4-methanol, 400 MHz).
Sch em e 2
1). These 13C chemical shifts are in good agreement with
previous examples from the literature.13-19
In contrast to previous reports,15 there are no ex-
change cross-peaks present in the phase-sensitive NOE-
SY spectrum of either 10 or 11. This indicates that these
complexes are configurationally stable.
It is interesting to note that the η2-olefin coordination
mode is not present when complex 10 is measured in
methylene chloride instead of methanol. In the former
solvent the chloride anion coordinates to ruthenium and,
accordingly, 31P resonances for both phosphorus atoms
are found in the same region, δ(31P) ≈ 73 ppm. This
chloride exchange reaction is reversible, as indicated
[RuCl2(η6-p-cymene)]2 with 1 equiv of either racemic 8
or 9 afforded the new dinuclear products, 10 and 11;
in eq 3.
see Scheme 2. Complexes 10 and 11 can be isolated in
good yield as red solids and were fully characterized via
NMR and microanalytical data.
The 31P NMR spectra in methanol show the antici-
pated AX spin systems; however, the chemical shifts, δ
86.3 and 25.0 for 10 and δ 83.5 and 15.8 for 11, were
somewhat unexpected. The low-frequency shift of one
of the two phosphorus nuclei provides an indication of
the presence of a metal-olefin bond. The 13C NMR data,
obtained from long-range 13C,1H 2D spectra, reveal
peaks at δ 87.4 and 62.3 for 10 and δ 87.4 and 61.7 for
11, which stem from the carbon atoms C1 and C6 of
the binaphthyl backbone, respectively, and thus strongly
On the basis of 13C and 31P NMR data, loss of olefin
coordination is also observed for solutions of 10 and 11
support the η2-bonding mode (see Figure 1 and Table

1446 Organometallics, Vol. 22, No. 7, 2003
Ta ble 1. Selected 13C NMR Da ta for Com p lexes 10-12
Geldbach et al.
C1
C2
C3
C4
C5
C6
P1
P2
10 (d4-MeOH)a
10 (CD2Cl2)b
87.4
87.9
139.3
139.0
87.4
145.0
145.1
133.6
133.3
144.7
144.8
130.9
130.8
133.6
134.0
130.9
131.0
134.9
134.0
126.8
128.6
134.3
133.6
124.9
128.0
130.7
128.5
128.3
125.2
62.3
63.1
144.5
132.4
61.7
86.3
86.7
73.8
67.3
83.5
86.1
25.0
24.8
72.5
63.5
15.8
19.1
10 (CD2Cl2)c
10 (CD3CN)c
11 (d4-MeOH)d
12 (d4-MeOH)d,e
87.0
65.9
Anion: Cl-, 500 MHz. Anion: PF6-, 500 MHz. c Anion: Cl-, 500 MHz. 400 MHz. e Two isomers; data given for main isomer (>60%).
a
b
d
Sch em e 3
in acetonitrile. If the chloride anion in these species is
alcohols.29 Further, formation of such face-bridged di-
nuclear compounds is facile; see eq 4.30
exchanged for a noncoordinating PF6 anion, the η2-
-
olefin coordination is maintained in methylene chloride.
To some degree, it is surprising that in methanol the
η2-olefin coordination is present, since related complexes
react quickly at ambient temperature with the alcohol
to afford the corresponding ruthenium hydride.14,25
However, even after 24 h in methanol at 80 °C, no
change in the 31P NMR spectrum for 10 or 11 was
observed. Further, the reactions with terminal alkynes
do not afford carbene complexes as expected from
comparable reactions reported in the literature.26-28
The dinuclear complex 12, formed when a second
equivalent of 8 complexes to ruthenium, has NMR
characteristics similar to those of 10; that is, the Binap
chelate functions as a six-electron donor. However, we
note that this reaction (see bottom of Scheme 2) leads
to two isomers, which reveal identical mass spectro-
scopic and similar NMR spectroscopic properties. Pos-
sibly, these isomers arise from pseudo-cis/trans configu-
rations with respect to the complexed olefin double bond,
and/or from the diastereomers (R,R/S,S and R,S/S,R)
which are most likely present.
Cyclom eta la tion a n d P -C Bon d Clea va ge Rea c-
tion s. The different steric and electronic properties of
the new aliphatic Binap ligands relative to their phenyl
analogues become obvious during the reactions of 8 and
9 with [Ru(OAc)2(η6-p-cymene)] (see Scheme 3). Instead
of affording the anticipated Binap bis-acetate complex,
e.g., 13, slow P-C bond cleavage and cyclometalation
occur after several days in toluene solution at 90 °C to
give complexes 15 and 16, respectively. Conceivably,
these products arise via the two complexes 13 and 14
as outlined in Scheme 3. The 31P NMR spectrum of the
reaction solution for the cyclohexyl compound revealed
resonances at δ 83.7 and 19.1, which are indicative of a
complexation mode similar to intermediate 14. Attempts
to synthesize the initially envisaged bis-acetate complex
13 were not successful with these new ligands.
Complexes related to 12 were recently synthesized in
connection with the catalytic oxidation of secondary
The 31P NMR spectra of cyclometalated complexes 15
and 16 show AX spin systems, with the resonances for
the phosphorus-acetate chelate found at unexpectedly
high frequency, δ 240.0 and 237.7 for the isopropyl and
(25) Currao, A.; Feiken, N.; Macchioni, A.; Nesper, R.; Pregosin, P.
S.; Trabesinger, G. Helv. Chim. Acta 1996, 79, 1587. Trabesinger, G.;
Albinati, A.; Feiken, N.; Kunz, R. W.; Pregosin, P. S.; Tschoerner, M.
J . Am. Chem. Soc. 1997, 119, 6315.
(26) den Reijer, C. J .; Drago, D.; Pregosin, P. S. Organometallics
2001, 20, 2982.
(27) Touchard, D.; Dixneuf, P. H. Coord. Chem. Rev. 1998, 178-
180, 409, and references therein.
(28) Cadierno, V. M.; Gamasa, P.; Gimeno, J . Eur. J . Inorg. Chem.
2001, 571, and references therein.
(29) da Silva, A. C.; Piotrowski, H.; Mayer, P.; Polborn, K.; Severin,
K. Eur. J . Inorg. Chem. 2001, 685.
(30) Amoroso, D.; Yap, G. P. A.; Fogg, D. E. Organometallics 2002,
21, 3335. Amoroso, D.; Snelgrove, J . L.; Conrad, J .; Yap, G. P. A.; Fogg,
D. E. Adv. Synth. Catal. 2002, 344, 757.

Ruthenium(II) Alkyl Binap Complexes
Organometallics, Vol. 22, No. 7, 2003 1447
F igu r e 2. 13C,1H long-range correlation spectrum of 15, revealing the high-frequency resonance of the σ-bound carbon
atom, C6 (left), and aliphatic region of the 1H NMR spectrum, showing the well-dispersed diastereotopic CH3 groups (right);
CD2Cl2, 300 MHz.
Sch em e 4
cyclohexyl derivatives, respectively. It is known that P
atoms included in a five-membered chelate ring reveal
signals that are shifted to higher frequency.31 However,
the observed chemical shifts in 15 and 16 are certainly
unusually high and may also develop to some extent
from the better donor capabilities of the more electron-
rich alkyl groups on the phosphorus donors.
and 16 represent rare examples for a P-O-CdO
chelate. Further, as can be seen from the scheme, the
complexes presented were prepared by adding a pre-
formed P-O chelate to a suitable ruthenium or rhodium
precursor, whereas 15 and 16 arise (presumably) via
intramolecular acetate attack at phosphorus with the
electrons in the P-C bond moving to the ruthenium
atom.
2
The P-P coupling constant J PP ≈ 31 Hz is modest
and indicates a cis arrangement (of the two spins). The
σ-coordination of the naphthyl moiety is established
from the typical high-frequency 13C position32 of C6, δ
171.4 and 174.1 for 15 and 16, respectively (see Figure
2a). The proton NMR is straightforward, except for the
diastereotopic alkyl substituents, which display well-
separated resonances due to strong local anisotropic
effects (e.g., one methyl in 15 is observed at -0.30 ppm,
see Figure 2b).
Solid -Sta te Str u ctu r e of 16, a Molecu le w ith
Th r ee Differ en t Ch ela t e Liga n d s. Crystals of 16
suitable for X-ray diffraction studies were obtained upon
slow evaporation of a methylene chloride solution, and
a view of the molecule is shown in Figure 3. Selected
bond lengths and bond angles are given in Table 2. The
immediate coordination sphere around the ruthenium
is best described as distorted octahedral. The phospho-
rus atom P1 of the dicyclohexyl-binaphthyl phosphine
and the σ-bound arene, C6, make up one chelate ring.
The phosphorus atom P2 of the Cy2P-O-CdO(22)CH3
chelate and its oxygen atom, O22, make up a second
chelate, and the remaining two coordination positions
are filled by the two oxygen atoms of the acetate. The
Scheme 4 shows several structurally related com-
plexes from the literature;33-35 however, compounds 15
(31) Garrou, P. Inorg. Chem. 1975, 14, 1435.
(32) Mann, B. E.; Taylor, B. F. 13C NMR Data for Organometallic
Compounds; Academic Press: London, 1981; p 107
(33) Braunstein, P.; Matt, D.; Dusausoy, Y. Inorg. Chem. 1983, 22,
2043.
(34) Borowski, A. F.; Iraqi, A.; Cupertino, D. C.; Irvine, D. J .; Cole-
Hamilton, D. J .; Harmon, M. H.; Hursthouse, M. B. J . Chem. Soc.,
Dalton Trans. 1990, 29.
(35) Irvine, D. J .; Preston, S. A.; Cole-Hamilton, D. J .; Barnes, J . C.
J . Chem. Soc., Dalton Trans. 1991, 2413.

1448 Organometallics, Vol. 22, No. 7, 2003
Geldbach et al.
F igu r e 3. ORTEP view of 16, together with a ball-and-stick representation of the immediate coordination environment
around the metal center.
Ta ble 2. Selected Dista n ces (Å) a n d An gles (d eg)
for 16
Sch em e 5
Ru-P1
2.262 (1)
2.187 (1)
2.051 (4)
2.255 (3)
2.180 (2)
2.164 (3)
1.267 (4)
1.252 (4)
1.332 (4)
1.236 (4)
C6-Ru-O22
C6-Ru-O2
C6-Ru-P2
O22-Ru-P2
O22-Ru-O2
O1-Ru-O2
O1-Ru-O22
P1-Ru-P2
P1-Ru-O22
93.21 (13)
94.31 (12)
100.65 (10)
80.54 (8)
83.90 (10)
58.55 (9)
80.05 (10)
103.26 (4)
174.30 (8)
Ru-P2
Ru-C6
Ru-O1
Ru-O2
Ru-O22
C11-O1
C11-O2
C121-O21
C121-O22
three relatively strong donors, P1, P2, and C6, are all
trans to oxygen donors, with P1 trans to O22.
The µ2-acetate ligand is rotated with respect to the
coordination plane (defined by atoms Ru,C6,P2,O1,O2);
the O1 atom lies ca. -0.02 Å below this plane, while
O2 lies ca. 0.1 Å above it. The ruthenium atom is
situated ca. 0.2 Å below this plane. There is almost
perfect delocalization of the negative charge in the
acetate ligand, in that the C11-O1 and C11-O2 bond
lengths, 1.267(4) and 1.252(4) Å, respectively, are not
significantly different. Within the P,O chelate, the bond
from the carbonyl carbon C121 to the P-bound oxygen,
C121-O21 ) 1.332(4) Å, is relatively long, whereas the
C121-O22 bond is significantly shorter, 1.236(4) Å, and
better described as a double bond. The ruthenium-
carbon bond distance, Ru-C6, 2.051(4) Å, is in the
expected range,36 as is the Ru-P1 bond, 2.262(1) Å.
However, the Ru-P2 distance is rather short, 2.187(1)
Å. The Ru-P separation in the related structure from
Braunstein et al. (see Scheme 4) at 2.363(1) Å is
markedly longer.33 The coordination angles all vary
significantly from 90°, with P1-Ru1-P2, ca. 103°, the
largest, and the acetate O1-Ru1-O2, ca. 59°, the
smallest. Interestingly, the two rings of the cyclometa-
lated binaphthyl moiety are no longer coplanar: the
angle between the two fused rings is ca. 8°. Moreover,
while the C1′-C6′ ring is still approximately planar (the
only significant deviation is for C1′, ca. 0.02 Å), for the
C1-C6 ring the deviations are more pronounced with
atomsC1 and C6 at ca. 0.07 and -0.06 Å away, respec-
tively, from the best plane for these six atoms.
Ru {P R2(OH)} Com p lexes. The complexes 15 and
16 react with 2 equiv of wet triflic acid to afford the
new hydroxydiphenylphosphino derivatives 17 and 18
(see Scheme 5). These are alkyl analogues of 3, and as
we have already reported13 the characterization of 3 and
related derivatives (including two solid-state structures),
there is no need for a lengthy description of their NMR
properties (see Experimental Part). We do note that
there is a marked high-frequency shift in the 31P
frequency of the PR2(OH) moiety (146.3 and 138.9 ppm
for 17 and 18, respectively) relative to the phenyl
derivative, 114.5 ppm. Obviously, after protonation of
the chelating acetate opens one or more coordination
positions, the complexed P-O(CdO)CH3 ligand is sus-
ceptible to acid-assisted hydrolysis to afford the PR2-
(OH) donor.
Primarily, compounds 17 and 18 were synthesized to
test whether the observed P-phenyl migration leading
to 6 and 7 could be suppressed. Consequently, complex
17 was dissolved in methanol, which presumably sol-
volyzes the triflate anion.21,37 Indeed, no P-alkyl migra-
tion takes place; however, the presumed 16e complex
formed slowly reacts with methanol at room tempera-
(36) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
D. G.; Taylor, R. J . Chem. Soc., Dalton 1989, S1.

Ruthenium(II) Alkyl Binap Complexes
Organometallics, Vol. 22, No. 7, 2003 1449
Ta ble 3. Cr ysta l a n d Str u ctu r e Refin em en t Da ta
for 16
ture to form the hydride complex 19. This was unam-
biguously identified via the typical low-frequency hy-
1
dride H NMR resonance at δ -13.45 as a doublet of
chemical formula
fw
C48H62O4P2Ru
865.99
doublets due to the two phosphorus nuclei. The 31P
spectrum reveals two resonances, δ 157.7 and 83.5 with
2J PP ) 30 Hz. The η6-arene is still present, as indicated
by its 13C NMR characteristics (see Experimental Part).
Clearly, although the tendency to split the remaining
P-C bonds of the PR2(OH) moiety has been reduced,
the distorted η6-arene bonding in this type of complex23
readily opens a coordination position thereby facilitating
â-H elimination.
data coll T, K
diffractometer
cryst syst
space group
a, Å
293(2)
Bruker SMART CCD
triclinic
P1h
11.7221(8)
13.1315(9)
15.3555(10)
89.318(2)
b, Å
c, Å
R, deg
â, deg
75.723(2)
66.728(2)
2.094(5)
γ, deg
V, Å3
Con clu sion s. Compared to their phenyl counter-
parts, the ruthenium isopropyl and cyclohexyl Binap
analogues show some similar bonding properties, e.g.,
the η2-olefin 6e coordination mode; however, these are
housed in rather different molecular structures. It is
tempting to believe that the observed slower reactions
with the alkyl compounds allow the isolation of inter-
mediates such as 10 and 11, or 15 and 16, which were
only fleeting for the phenyl-substituted complexes. The
Ru complexes of ligands 8 and 9 do not undergo multiple
P-C bond breaking; nevertheless, the strain introduced
as a consequence of the η2-olefin 6e coordination mode
still facilitates the first P-C bond scission. As might
be expected, the η2-olefin bond from the Binap is not
very strong and can be substituted by either a coordi-
nating anion, such as chloride, or acetonitrile. The
cyclometalated compounds 15 and 16 should be a
possible source of new “MOP” type ligands,38 and studies
in this direction are under consideration.
Z
2
F
calcd, g cm-3
1.373
4.95
µ, cm-1
radiation
Mo KR (graphite monochromated
λ ) 0.71079 Å)
(h, (k, (l
1.37 < θ < 28.08
1.0000-0.8754
21 971
measured reflns
θ range, deg
transmn coeff
no. of data coll
no. of ind data
9687
no. of obsd reflns (no)
no. of params refined (nv)
4573 [|Io| > 2.0σ(|I|)]
496
a
Rav
0.0392
R, Rw (obsd reflns)b
0.0466, 0.0796
0.1223, 0.0943
0.723
2
R, Rw (all data)b
2
GOF
a
2
2
2
Rav ) ∑|Fo - Fo ,av|/∑|Fo |; R ) ∑(|Fo - (1/k)Fc|)/∑|Fo|.
Rw2 ) [∑w(Fo2 - (1/k)Fc2)2/∑w|Fo | ]; GOF ) [∑w(Fo2 - (1/k)Fc2)2/
b
2 2
(no - nv)]1/2
.
anomalous dispersion, were taken from the literature.42 All
calculations were carried out by using the PC version of the
SHELX-97 programs.41
Exp er im en ta l P a r t
Syn th esis. All organometallic manipulations were carried
out under a nitrogen atmosphere using standard Schlenk
techniques. Pentane and diethyl ether were distilled from
sodium-potassium alloy, dichloromethane and 1,2-dichloro-
ethane from CaH2, methanol from magnesium, and toluene
from potassium. 2,2′-Dibromo-1,1′-binaphthyl43 and [Ru(OAc)2-
(η6-p-cymeme)]44 were prepared according to literature meth-
ods. All other chemicals were commercial products and were
used as received. Spectra were recorded with Bruker DPX-
300 and Avance 400 and 500 spectrometers. Chemical shifts
are given in ppm and coupling constants (J ) in Hz. Elemental
analyses and mass spectroscopic studies were performed at
the ETHZ.
Cr ysta llogr a p h y. Light yellow crystals of 16, suitable for
X-ray diffraction, were obtained by crystallization from CH2-
Cl2 and are air stable. A platelike single crystal was mounted
for the data collection on a glass fiber at a random orientation
on a Bruker SMART CCD diffractometer at room temperature.
The crystal symmetry was found to be triclinic, and the space
group, assumed to be P1h, was unambiguously confirmed by
the structure solution and refinement. Data were collected by
using ω scans, in steps of 0.3 deg, and counting time of 20 s
per frame. The collected intensities39 were corrected for
Lorentz and polarization factors and empirically for absorp-
tion.40
Syn th esis of 8. A solution of 2,2′-dibromo-1,1′-binaphthyl
(1.015 g, 2.46 mmol) in toluene (50 mL) was cooled to -75 °C
and tert-butyllithium (5.9 mL, 10.0 mmol) added dropwise from
a syringe. The resulting pale yellow solution was kept at -75
°C for 45 min. Slow warming to -30 °C was accompanied by
formation of a white precipitate. To this mixture was added a
solution of chlorodiisopropylphosphine (990 µL, 6.16 mmol) in
diethyl ether (5 mL) in a dropwise fashion. The clear solution
was stirred at -35 °C for 20 min and then allowed to warm to
RT, leading to precipitation of a white solid. After stirring at
RT for 1 h, the mixture was hydrolyzed and washed with brine,
and the organic phase was dried with sodium sulfate and then
evaporated to dryness. The remaining yellow crude product
was dissolved in 1:1 ethyl acetate/hexane and filtered through
Selected crystallographic and other relevant data are listed
in Table 3 and in Table S1. The standard deviations on
intensities were calculated in term of statistics alone, while
2
those on Fo were calculated as shown in Table S1. The
structure was solved by Patterson and Fourier methods and
refined by full matrix least squares,41 minimizing the function
[∑w(Fo - (1/k)Fc2)2]. Anisotropic displacement parameters
2
were used for all atoms. The contribution of the hydrogen
atoms, in their calculated position, was included in the
refinement using a riding model. No extinction correction was
found to be necessary. Upon convergence, the final Fourier
difference map showed no significant peaks. The scattering
factors used, corrected for the real and imaginary parts of the
(37) Geldbach, T. J .; den Reijer, C. J .; Wo¨rle, M.; Pregosin, P. S.
Inorg. Chim. Acta 2002, 330, 155.
(38) Hayashi, T.; Kawatsura, M.; Uozumi, Y. J . Am. Chem. Soc.
1998, 120, 1681. Hayashi, T.; Hirate, S.; Kitayama, K.; Tsuji, H.; Torii,
A.; Uozumi, Y. J . Org. Chem. 2001, 66, 1441.
(39) SAINT: SAX Area Detector Integration; Siemens Analytical
Instrumentation, 1996.
(42) International Tables for X-ray Crystallography; Wilson, A. J .
C., Ed.; Kluwer Academic Publisher: Dordrecht, The Netherlands,
1992; Vol. C.
(43) Miyashita, A.; Takaya, H.; Souchi, T.; Noyori, R. Tetrahedron,
1984, 40, 1245. Takaya, H.; Akutagawa, S.; Noyori, R. Org. Synth.
1989, 67, 20.
(40) Sheldrick, G. M. SADABS, Universita¨t Go¨ttingen.
(41) Sheldrick, G. M. SHELX-97. Structure Solution and Refinement
Package; Universita¨t Go¨ttingen, 1997.
(44) Tocher, D. A.; Gould, R. O.; Stephenson, T. A.; Bennett, M. A.;
Ennett, J . P.; Matheson, T. W.; Sawyer, L.; Shah, V. K. J . Chem. Soc.,
Dalton Trans. 1983, 1571.

1450 Organometallics, Vol. 22, No. 7, 2003
Geldbach et al.
a layer of silica gel. The white residue was recrystallized from
Syn th esis of 11. A suspension of [RuCl2(η6-p-cymene)]2 (29
mg, 0.048 mmol) and ligand 9 (31 mg, 0.048 mmol) in methanol
(8 mL) was stirred for 3 days at room temperature, resulting
in a clear red solution. The solvent was evaporated and the
residue washed twice with a 1:1 mixture of diethyl ether and
pentane to afford 11 as a red solid. Yield: 50 mg (93%). 1H
NMR (d4-MeOH, 400 MHz): 7.99 (m, H,5 H5′), 7.87 (dd,
hot hexane to afford 8 as white microcrystals. Yield: 805 mg
3
(68%). 1H NMR (CDCl3, 400 MHz): 7.96 (d, J HH ) 8.5, 2H,
3
3
3
H4), 7.89 (d, J HH ) 8.3, 2H, H10), 7.77 (dd, J HH ) 8.4, J PH
)
)
1, 2H, H5), 7.41 (m, 2H, H9), 7.15 (m, 2H, H8), 6.97 (d, J HH
3
8.6, 2H, H7), 2.37 (m, 2H, CH), 1.70 (m, 2H, CH), 1.15 (m, 12H,
3
3
CH3), 0.82 (dd, J HH ) 7.1, J PH ) 11, 6H, CH3), 0.70 (dd,
3J HH ) 7.4, J PH ) 13, 6H, CH3). 13C NMR (CDCl3, 100 MHz):
3J PH ) 5.6, J HH ) 8.6, H4′), 7.83 (d, J HH ) 8.2, H10′), 7.74 (d,
3
3
3
145.4 (br, C1), 136.2 (br, C6), 134.2 (d, 3J CP ) 4, C2), 133.4 (C3),
3J HH ) 7.9, H10), 7.58 (dd, J PH ) 4.5, J HH ) 9.0, H5), 7.42-
3 3
3 3
129.1 (br, C5), 128.5 (C7), 128.2 (C10), 127.4 (C4), 126.4 (C9),
7.35 (m, H,9 H9′), 7.25 (dd, J HH ) 8.2, J HH ) 8.2, H8) 7.06
3 3 3
125.8 (C8), 25.9 (d, J CP ) 16), 23.2 (d, J CP ) 12), 22.6, 21.5
(d, 2J CP ) 16), 20.4 (d, 2J CP ) 18), 19.5 (d, 2J CP ) 10). 31P NMR
(CDCl3 162 MHz): -1.8 (s). MS (MALDI): 487.3 (M+, 100%),
444.2 (M+ - i-Pr). Anal. Calcd for C32H40P2: C, 78.98; H, 8.28.
Found: C, 79.05; H, 8.37.
(dd, J HH ) 7.0, J HH ) 7.1, H8′), 7.00 (d, J HH ) 8.1, H7), 5.87
3 3 3
1
1
(d, J HH ) 8.6, H7′), 5.64 (d, J HH ) 5.8, 1H), 5.56 (d, J HH
5.9, 1H), 5.47 (d, J HH ) 5.9, 1H), 5.31 (d, J HH ) 5.8, 1H),
3.81 (m, 1H), 3.40 (m, 1H), 2.82-1.06 (m, 46H), 0.88 (m, 1H),
0.47 (m, 2H), 0.05 (m, 1H), -0.66 (m, 1H), -0.92 (m, 1H). 13C
)
3
3
2
3
NMR (d4-MeOH, 100 MHz): 147.9 (dd, J PC ) 24, J PC ) 2,
Syn th esis of 9. A solution of 2,2′-dibromo-1,1′-binaphthyl
(1.00 g, 2.43 mmol) in toluene (50 mL) was cooled to -75 °C
and tert-butyllithium (5.9 mL, 10.0 mmol) added dropwise from
a syringe. The resulting pale orange solution was kept at -75
°C for 45 min. Slow warming to RT was accompanied by
formation of a white precipitate. To this mixture was added
dropwise chlorodicyclohexylphosphine (1.41 mL, 6.07 mmol).
The gray mixture was stirred at 60 °C overnight, hydrolyzed,
and washed with brine. The organic phase was dried with
sodium sulfate and then evaporated to dryness. The yellow
residue was washed with 10:1 hexane/ethyl acetate, the
residue was dissolved in toluene and filtered through a short
layer of silica, and the remaining colorless solution was
evaporated to dryness. Yield: 974 mg (62%). 1H NMR (CDCl3,
C1′), 144.7 (d, J PC ) 7, C2), 136.3 (d, J PC ) 42, C6′), 135.2 (d,
3
1
4J PC ) 2, C3′), 134.3 (d, J PC ) 6, C4), 133.3 (d, J PC ) 15, C2′),
3
3
130.9 (C3), 130.3 (d, 3J PC ) 6, C4′), 129.3 (C10), 128.4 (C10′), 128.3
(d, J PC ) 7, C5), 128.0 (C9′), 127.9 (C8), 127.7 (C7, C8′), 126.7
2
(C9), 125.7 (C7′), 125.6 (C5′), 101.5 (q-cym), 96.3 (q-cym), 87.4
(br, C1), 79.8 (cym), 78.9 (cym), 78.6 (cym), 61.7 (d, J PC ) 28,
1
C6), 43.6 (d, J PC ) 24, CH), 40.1 (d, J PC ) 21, CH), 39.0 (d,
1J PC ) 25, CH), 35.4 (d, J PC ) 13, CH2), 34.8 (d, J PC ) 10, CH2),
32.7 (d, J PC ) 5, CH2), 31.8 (s, CH2), 31.6 (d, J PC ) 8, CH2),
31.4 (s, CH2), 31.0 (d, J PC ) 6, CH2), 29.2 (d, J PC ) 6, CH2),
29.0 (s, CH2), 28.2-27.6 (m), 27.5 (d, J PC ) 6, CH2), 27.4 (s,
CH2), 27.2 (d, J PC ) 9, CH2), 26.9 (d, J PC )12, CH2), 26.3 (s,
CH2), 26.0 (s, CH2), 25.1 (s, CH2), 23.5 (s, CH2), 21.9 (s, CH2),
20.8 (s, CH2), 17.8 (s, CH2). 31P NMR (d4-MeOH, 162 MHz):
1
1
3
400 MHz): 7.94 (d, J HH ) 8.5, H4), 7.89 (d,3J HH ) 8.1, H10),
83.5 (d, J PP ) 34), 15.8 (d, J PP ) 34). MS (ESI): 1089.1 (M+,
100%), 783.1 (Ru-Binap). Anal. Calcd for C54H70Cl4P2Ru2: C,
57.65; H, 6.27. Found: C, 57.08; H, 6.48.
2
2
3
7.75 (d, J HH ) 8.5, H5), 7.41 (m, H9), 7.17 (m, H8), 7.01 (d,
2
3J HH ) 8.7, H7), 2.19 (br, 2H), 1.89 (br, d, J PH ) 12.0, 2H),
1.77 (m, 8H), 1.55-1.18 (m, 22H), 1.02-0.73 (m, 10H). 13C
3
NMR (CDCl3, 100 MHz): 145.6 (m, C1, C6), 134.5 (dd, J CP
)
Syn th esis of 12. A mixture of [RuCl2(η6-p-cymene)]2 (25 mg,
0.041 mmol) and ligand 8 (40 mg, 0.082 mmol) in methanol (5
mL) was stirred overnight at room temperature, resulting in
a clear red solution. The solvent was removed in vacuo and
the residue washed with pentane to afford 12 as a red-brown
solid. Yield: 51 mg (95%). 1H NMR (d4-MeOH, 400 MHz): 8.02
(m, H4), 7.87 (m, H4′), 7.76 (m, H,10 H10′), 7.67 (m, H,5 H5′), 7.36
(m, H9), 7.31 (m, H9), 7.11 (m, H8), 6.99 (m, H8′), 6.92 (d,
5, J CP ) 5, C2), 133.4 (C3), 129.5 (C5), 128.7 (C7), 128.1 (C10),
127.0 (C4), 126.2 (C9), 125.6 (C8), 36.7 (m), 33.6 (m), 32.1 (m),
31.8 (m), 31.0 (m), 29.8 (m), 28.1 (m), 27.7 (m), 27.2 (m), 26.7.
31P NMR (CDCl3 162 MHz): -8.4 (s). MS (EI): 647.4 (M+,
100%), 563.5 (M+ - Cy). Anal. Calcd for C44H56P2: C, 81.70;
H, 8.73. Found: C, 81.67; H, 8.51.
4
Syn th esis of 10. A suspension of [RuCl2(η6-p-cymene)]2 (25
mg, 0.041 mmol) and ligand 8 (20 mg, 0.041 mmol) in methanol
(8 mL) was stirred overnight at room temperature, resulting
in a clear red solution. The solvent was evaporated and the
residue washed twice with diethyl ether to afford 10 as a red
solid. Yield: 37 mg (94%). 1H NMR (d4-MeOH, 400 MHz): 8.04
3
3J HH ) 8.0, H7), 5.80 (d, J HH ) 8.6, H7′), 4.26 (m, CH), 2.98
(m, CH), 2.70 (m, CH), 1.90 (dd, 3J PH ) 19.0, 3J HH ) 7.6, CH3),
1.75 (m, 6H), 1.46 (dd, 3J PH ) 15.3, 3J HH ) 7.3, CH3), 1.16 (dd,
3
3
3
3J PH ) 14.6, J HH ) 7.4, CH3), 1.00 (dd, J PH ) 18.3, J HH
)
3
3
7.4, CH3), 0.87 (dd, J PH ) 15.6, J HH ) 7.0, CH3), 0.02 (dd,
3
3J PH ) 13.7, J HH ) 7.3, CH3), -0.52 (m, CH). 13C NMR (d4-
4
3
3
4
(dd, J PH ) 1.9, J HH ) 8.9, H4), 7.98 (dd, J PH ) 1.9, J HH
)
MeOH, 100 MHz): 148.1 (dd, J PC ) 22, C1′), 144.8 (d, J PC
)
2
3
8.6, H4′), 7.82 (m, H5′, H10′), 7.74 (dd, J HH ) 1.0, J HH ) 8.0,
4
3
7, C2), 136.9 (d, J PC ) 41, C6′), 134.9 (d, J PC ) 2, C3′), 134.0
1
4
H10), 7.65 (dd, J PH ) 4.7, J HH ) 9.0, H5), 7.38 (m, H,9 H9′),
3
3
(d, J PC ) 6, C2′), 133.6 (d, J PC ) 15, C4), 131.0 (C3), 129.9 (d,
3J PC ) 6, C4′), 129.8 (C10′), 128.5 (C7), 128.4 (C5), 128.2 (C10′),
127.9 (C8), 127.6 (C9′), 127.3 (C8′), 126.4 (C9), 125.8 (C7′), 125.2
3
3
7.24 (m, H8), 7.07 (m, H,7 H8′), 5.92 (d, J HH ) 8.6, H7′), 5.63
3
(d, J HH ) 5.9, H12), 5.56 (d, J HH ) 5.9, H16), 5.45 (d, J HH
)
3
3
3
5.9, H13), 5.37 (d, J HH ) 5.9, H15), 4.05 (m, 1H, CH), 3.58 (m,
3
2
1
(C5), 87.0 (d, J PC ) 7, C1), 65.9 (C6), 31.3 (d, J PH ) 26, CH),
3
1H, CH), 2.69 (septet, J HH ) 6.8, 1H, CH), 2.49 (m, 1H, CH),
1
1
29.7 (d, J PH ) 21, CH), 27.9 (d, J PH ) 27, CH), 23.5 (d,
2.10 (s, 3H, CH3), 1.86-1.72 (m, 9H), 1.68-1.58 (m, 9H), 1.24
1J PH ) 13, CH), 23.2 (d, 2J PH ) 9, CH3), 21.3 (d, 2J PH ) 3, CH3),
3
3
(d, J HH ) 6.9, 3H, CH3), 1.22 (d, J HH ) 6.9, 3H, CH3), 1.04
2
2
3
3
3
21.0 (CH3), 20.3 (CH3), 20.2 (d, J PH ) 5, CH3), 19.8 (d, J PH
)
(dd, J PH ) 18.7, J HH ) 7.5, 3H, CH3), 0.15 (dd, J PH ) 23.0,
3J HH ) 7.4, 3H, CH3), -0.33 (m, 1H, CH). 13C NMR (d4-MeOH,
100 MHz): 147.9 (C1′), 145.0 (d, 3J PC ) 7, C2), 137.1 (C6′), 135.1
6, CH3), 19.0 (CH3), 18.2 (d, J PH ) 3, CH3). 31P NMR
2
2
2
(d4-MeOH, 202 MHz): 86.1 (d, J PP ) 35), 19.1 (d, J PP ) 35).
MS (ESI): 1282.0 (M+), 623.1 (RuCl-Binap). Anal. Calcd for
(C3′), 134.9 (C4), 133.4 (C2′), 130.9 (C3), 130.5 (d, J PC ) 6, C4′),
3
129.2 (C10), 128.3 (C10′), 127.9 (C,7 C8′), 127.8 (C8), 127.7 (C5′,
C9′), 126.9 (C9), 125.7 (C7′), 124.9 (C5), 101.2 (C11), 96.4 (C14),
87.4 (br, C1), 79.7 (C16), 79.3 (C12), 78.7 (C13), 62.3 (C6), 32.4
C
64H80Cl4P4Ru2: C, 58.36; H, 6.12. Found: C, 58.51; H, 6.12.
Syn th esis of 15. A solution of [Ru(OAc)2(η6-p-cymene)] (110
mg, 0.31 mmol) and ligand 8 (150 mg, 0.31 mmol) in toluene
(20 mL) was stirred in an ampule at 100 °C for 5 days. The
solvent was evaporated and the residue washed twice with
pentane (3 mL). 15 was obtained as a yellow solid. Yield: 156
1
1
(d, J PC ) 25, CH), 31.4 (CH cymene), 30.1 (d, J PC ) 22, CH),
1
1
29.9 (d, J PC ) 30, CH), 24.3 (d, J PC ) 15, CH), 23.1 (d,
2J PC ) 9, CH3), 21.4 (CH3 cymene), 21.2 (CH3 cymene), 20.7
2
2
3
(CH3), 20.0 (d, J PC ) 8, CH3), 19.7 (d, J PC ) 4, CH3), 19.0 (d,
mg (71%). 1H NMR (CD2Cl2, 300 MHz): 8.02 (d, J HH ) 8.8,
2J PC ) 6, CH3), 18.5 (CH3), 17.6 (CH3 cymene), 17.6 (d, J PC
)
H5), 7.84 (d, 3J HH ) 8.8, H10′), 7.80 (d, 3J HH ) 8.2, H4′), 7.70 (d,
3J HH ) 8.2, H10), 7.63 (dd, 3J HH ) 8.5, 2J PH ) 5.8, H5′), 7.41 (m,
2
2, CH3). 31P NMR (d4-MeOH, 162 MHz): 86.3 (d, J PP ) 36),
25.0 (d, 2J PP ) 36). MS (ESI): 928.9 (M+), 622.8 (RuCl-Binap).
Anal. Calcd for C42H54Cl4P2Ru2: C, 52.29; H, 5.64. Found: C,
52.47; H, 5.87.
2
3
2H, H9′, H4), 7.20 (d, J HH ) 8.8, H7′), 7.10 (m, 2H, H8′, H9),
3
6.87 (m, H8), 6.69 (d, J HH ) 8.8, H7), 2.97 (m, 1H), 2.47 (s,
3H, OAc), 2.22 (m, 1H), 1.98 (m, 1H), 1.89 (s, 3H, OAc), 1.52

Ruthenium(II) Alkyl Binap Complexes
Organometallics, Vol. 22, No. 7, 2003 1451
(dd, 2J PH ) 12.1, 3J HH ) 7.1, 3H), 1.39 (dd, 2J PH ) 16.2, 3J HH
)
)
0.046 mmol) and heated to 80 °C for 5 min. The orange solution
was pumped to dryness and washed with pentane to afford
18 as an orange solid. Yield: 11 mg (59%). H NMR (CD2Cl2,
400 MHz): 8.56 (br, OH), 8.29 (dd, 3J HH ) 8.6, 4J PH ) 2.0, H4′),
2
7.1, 3H), 1.19-1.02 (m, 9H), 0.72 (m, 1H), 0.34 (dd, J PH
3
2
3
1
13.5, J HH ) 7.1, 3H), 0.25 (dd, J PH ) 13.5, J HH ) 7.1, 3H),
-0.30 (dd, J PH ) 14.6, J HH ) 7.1, 3H). 13C NMR (CD2Cl2, 75
2
3
MHz): 184.7 (d, J PC ) 2, CO, C11), 179.5 (d, J PC ) 2, CO,
2
2
3
3
8.15 (d, J HH ) 8.1, H10′), 8.06 (m, H9), 7.88 (dd, J HH ) 8.6,
C12), 171.4 (m, C6), 149.8 (d, J PC ) 12, C1′), 140.0 (d, J PC
)
2
3
3J PH ) 5.8, H5′), 7.83 (d, J HH ) 8.4, H10), 7.76 (m, H9′), 7.59
3
11, C1), 136.5 (C5), 134.1 (d, J PC ) 2, C3′), 133.9 (d, J PC ) 9,
C2′), 132.7 (C2), 131.1 (C3), 128.8 (C7′), 128.0 (C10′), 127.9 (C10),
126.5 (C9′), 125.9 (d, 3J PC ) 7, C4′), 125.4 (C7), 125.2 (C8′), 124.9
4
3
(m, H7′, H8′), 7.40 (m, H5, H8), 7.00 (d, J HH ) 6.6, H4), 6.64 (d,
3
3J HH ) 8.9, H7), 5.09 (dd, J HH ) 5.3, J PH ) 2.0, H6), 2.98 (br,
3
2H), 2.60-1.00 (m, xH), 0.18 (br, 1H). 13C NMR (CD2Cl2, 100
MHz): 139.6 (C1′), 139.2 (C6′), 138.7 (C9), 134.8 (C3′), 134.0 (C2′),
132.2 (C7), 132.0 (C,7 C4′), 129.5 (C8′), 129.3 (C9′), 128.8 (C10′),
128.7 (C10), 125.7 (C5′), 124.8 (C7′), 119.4 (C3), 113.4 (C1), 106.3
(d, J PC ) 4, C5′), 123.9 (C8), 122.8 (C4), 122.2 (C9), 33.5 (d,
2
1J PC ) 19, CH), 29.7 (d, J PC ) 16, CH), 27.6 (d, J PC ) 23,
1
1
1
3
CH), 27.3 (d, J PC ) 24, CH), 24.2 (d, J PC ) 2, OAc), 20.6 (d,
2J PC ) 6, CH3), 20.4 (d, 3J PC ) 2, OAc), 19.9 (d, 2J PC ) 2, CH3),
(C2), 98.3 (C5), 89.3 (C4), 68.2 (C6), 49.9 (d, J PC ) 25, CH),
1
2
2
1
18.9 (s, CH3), 18.7 (d, J PC ) 3, CH3), 18.2 (d, J PC ) 3, CH3),
38.3 (d, J PC ) 21, CH), 30.9 (s, CH2), 30.2-26.5 (m), 26.1 (s,
2
2
CH2), 24.7 (s, CH2). 19F NMR (CD2Cl2, 282 MHz): -77.20 (s),
-79.23 (s). 31P NMR (CD2Cl2, 162 MHz): 138.9 (br), 58.7 (d,
2J PP ) 42).
17.9 (d, J PC ) 3, CH3), 17.7 (d, J PC ) 6, CH3), 14.4 (s, CH3).
31P NMR (CD2Cl2, 121 MHz): 240.0 (d, J PP )32), 74.6
2
(d, J PP ) 32). MS (ESI): 706.1 (M+, 100%), 530.0 (M+
-
2
P-iPr2, - OAc). Anal. Calcd for C36H46O4P2Ru: C, 61.27; H,
6.57. Found: C, 61.40; H, 6.78.
Syn th esis of 19. A solution of 17 (15 mg, 0.017 mmol) in
methanol (5 mL) was stirred at RT overnight, resulting in a
pale yellow solution. The solvent was removed in vacuo and
the yellow residue washed with pentane. Yield: 10 mg (81%).
Syn th esis of 16. A solution of [Ru(OAc)2(η6-p-cymene)] (33
mg, 0.093 mmol) and ligand 9 (60 mg, 0.093 mmol) in toluene
(8 mL) was stirred in an ampule at 110 °C for 5 days. The
solvent was evaporated and the residue washed twice with
pentane (3 mL). 16 was obtained as a yellow solid. Yield: 54
3
1H NMR (d8-thf, 500 MHz): 8.19 (d, J HH ) 8.6, H4′), 8.15 (d,
3
3
3J HH ) 8.3, H10′), 7.98 (d, J HH ) 8.6, H10), 7.86 (d, J HH ) 8.6,
H7), 7.82 (m, H5′, H9), 7.72 (dd, J HH ) 7.0, J HH ) 7.0, H9),
3
3
3
mg (67%). 1H NMR (CD2Cl2, 500 MHz): 8.11 (d, J HH ) 8.6,
7.59 (m, H8′), 7.48 (m, H8), 7.09 (d, J HH ) 8.6, H7), 6.63 (d,
3
3
4
H5), 7.88 (m, H10′), 7.82 (dd, J HH ) 8.3, J PH ) 1.5, H4′), 7.75
3J HH ) 6.2, H4), 6.55 (m, H5), 5.76 (d, J HH ) 4.9, H6), 2.79 (m,
3
(dd, J HH ) 8.3, J HH ) 1, H10), 7.56 (dd, J HH ) 8.6, J PH
)
)
3
4
3
3
3
CH, 2H), 2.41 (m, CH), 1.75 (m, CH), 1.46 (dd, J HH ) 6.8,
5.3, H5′) 7.45 (d, J HH ) 8.3, H4), 7.42 (m, H9′), 7.38 (d, J HH
3
3
3J PH ) 12.1, CH3), 1.29 (dd, 3J HH ) 6.6, 3J PH ) 15.6, CH3), 1.21
8.6, H7′), 7.16 (m, H8′), 7.14 (m, H9), 6.91 (m, H8), 6.79 (m, H7).
(dd, 3J HH ) 6.8, 3J PH ) 16.7, CH3), 1.13 (dd, 3J HH ) 6.8, 3J PH
)
13C NMR (CD2Cl2, 125 MHz): 184.4 (d, J PC ) 2, CO), 179.2
2
3
3
12.0, CH3), 1.07 (dd, J HH ) 7.0, J PH ) 18.4, CH3), 0.85 (dd,
(d, 2J PC ) 2, CO), 174.1 (m, C6), 148.9 (d, 2J PC ) 12, C1′), 140.7
3J HH ) 6.4, J PH ) 17.1, CH3), 0.57 (dd, J HH ) 6.8, J PH
)
3
3
3
(d, J PC ) 11, C1), 136.5 (C5), 134.0 (C6′), 133.9 (C3′), 133.1 (d,
3
3
3
17.5, CH3), 0.19 (dd, J HH ) 7.3, J PH ) 16.8, CH3), -13.45
3J PC ) 8, C2′), 132.2 (C2), 131.1 (C3), 129.7 (C7′), 128.2 (C10′),
(dd, J PH ) 34.5, J PH ) 36.5). 13C NMR (d8-thf, 125 MHz):
2
2
127.9 (C10), 126.4 (C9′), 125.8 (d, J PC ) 7, C4′), 125.6 (C,7 C8′),
3
143.9 (d, J PC ) 36, C6′), 142.5 (d, J PC ) 18, C1′), 134.7 (d,
1
2
124.3 (d, J PC ) 4, C5′), 123.7 (C8), 122.6 (C4), 122.0 (C9), 43.2
2
4J PC ) 2, C3′), 132.3 (C5′), 132.1 (d, J PC ) 13, C2′), 130.5 (d,
3
1
1
1
(d, J PC ) 20, CH), 40.0 (d, J PC ) 15, CH), 39.0 (d, J PC ) 22,
CH), 34.5 (s, CH2), 30.4-25.7 (m), 24.1 (s, CH2), 22.7 (s, CH2),
20.4 (s, CH2), 14. (s, CH2). 31P NMR (CD2Cl2, 202 MHz): 237.7
(d, 2J PP ) 31), 65.8 (d, 2J PP ) 31). MS (ESI): 866.2 (M+, 100%),
807.3 (M+ - OAc). Anal. Calcd for C48H62O4P2Ru: C, 66.57;
H, 7.22. Found: C, 66.59; H, 7.32.
3J PC ) 6, C4′), 129.2 (C8), 128.5 (C10′), 128.4 (C9′), 128.2 (C7),
126.8 (C9), 126.4 (C10), 125.9 (C7′), 113.7 (C3), 112.7 (C2), 110.2
(dd, J PC ) 9, J PC ) 3, C1), 89.1 (d, J PC ) 4, C5), 85.2 (dd,
2
2
2
2J PC ) 9, J PH ) 1, C6), 82.6 (d, J PC ) 8, C4), 35.6 (d, J PC
)
4
2
1
1
1
21, CH), 31.2 (d, J PC ) 32, CH), 29.5 (d, J PC ) 19, CH), 26.0
(d, J PC ) 321, CH), 19.8 (d, J PC ) 3, CH3), 19.2 (d, J PC ) 1,
1
2
2
Syn th esis of 17. A solution of 15 (15 mg, 0.021 mmol) in
1,2-dichloroethane (2 mL) was treated with triflic acid (5 µL,
0.057 mmol) and heated to 80 °C for 5 min. The orange solution
was pumped to dryness and washed with pentane to afford
2
2
CH3), 19.1 (d, J PC ) 3, CH3), 18.0 (d, J PC ) 4, CH3), 17.9 (d,
2J PC ) 3, CH3), 17.7 (d, 2J PC ) 8, CH3), 17.0 (d, 2J PC ) 7, CH3),
15.7 (d, J PC ) 6, CH3). 19F NMR (d8-thf, 282 MHz): -79.45
2
(s). 31P NMR (d8-thf, 162 MHz): 157.7 (d, J PP ) 30), 83.5 (d,
2
1
17 as an orange solid. Yield: 12 mg (62%). H NMR (CD2Cl2,
2J PP ) 30). MS (ESI): 607.0 (M+, 100%). Anal. Calcd for
500 MHz): 8.59 (br, OH), 8.30 (dd, 3J HH ) 8.7, 4J PH ) 1.8, H4′),
C
33H43F3O4P2RuS‚1/2HOTf: C, 48.46; H, 5.22. Found: C, 48.64;
3
8.17 (d, J HH ) 8.4, H10′), 8.07 (m, H9), 7.86 (m, H5′, H10), 7.78
(m, H9′), 7.61 (m, H7′, H8′), 7.46 (m, H5), 7.41 (m, H8), 7.12 (d,
H, 5.87.
3
3J HH ) 6.7, H4), 6.65 (d, J HH ) 8.5, H7), 5.16 (m, H6), 3.35 (m,
3
CH), 3.15 (m, CH), 2.67 (m, CH, 2H), 1.72 (dd, J HH ) 7.3,
Ack n ow led gm en t. We thank R. Hartmann for
3J PH ) 18.3, CH3), 1.64 (dd, 3J HH ) 7.3, 3J PH ) 14.2, CH3), 1.59
carrying out detailed ESI mass spectroscopic measure-
ments. P.S.P. thanks the Swiss National Science Foun-
dation, the BBW, and the ETH Zu¨rich for financial
support. A.A. thanks MURST for support. We also
thank J ohnson Matthey for the loan of precious metal
salts.
(dd, 3J HH ) 7.0, 3J PH ) 13.3, CH3), 1.44 (dd, 3J HH ) 7.3, 3J PH
)
3
3
13.6, CH3), 1.39 (dd, J HH ) 7.3, J PH ) 18.0, CH3), 1.23 (dd,
3J HH ) 7.3, J PH ) 16.8, CH3), 0.94 (dd, J HH ) 7.2, J PH
)
3
3
3
3
3
18.2, CH3), 0.57 (dd, J HH ) 6.9, J PH ) 16.5, CH3). 13C NMR
(CD2Cl2, 125 MHz): 140.5 (C1′), 139.2 (C6′), 138.8 (C9), 134.9
(C3′), 132.1 (C8 C7), 132.0 (C4′), 131.9 (C2′), 129.6 (C9′), 129.3
,
(C8′), 128.9 (C,10 C9′), 128.8 (C10′), 125.4 (C5′), 124.4 (C7′), 119.3
(C3), 113.7 (C1), 106.9 (C2), 98.2 (C5), 89.4 (C4), 68.7 (C6), 41.9
(CH), 38.6 (CH), 29.3 (CH), 28.0 (CH), 20.3 (CH3), 20.2 (CH3),
19.2 (CH3), 18.6 (CH3), 18.4 (CH3), 18.0 (CH3), 17.4 (CH3), 16.7
(CH3). 19F NMR (CD2Cl2, 282 MHz): -77.23 (s), -79.45 (s).
Su p p or tin g In for m a tion Ava ila ble: Text giving experi-
mental details and a full listing of crystallographic data for
compound 16 including tables of positional and isotropic
equivalent displacement parameters, calculated positions of
the hydrogen atoms, anisotropic displacement parameters,
bond distances and angles and an ORTEP figure showing the
full numbering scheme. This material is available free of
charge via the Internet at http://pubs.acs.org.
2
31P NMR (CD2Cl2, 162 MHz): 146.3 (d, J PP ) 42), 67.1 (d,
2J PP ) 42). MS (ESI): 604.9 (M+, -OTf, 100%). Anal. Calcd
for C34H41F6O7P2RuS2: C, 45.23; H, 4.58. Found: C, 44.70; H,
5.07.
Syn th esis of 18. A solution of 16 (15 mg, 0.017 mmol) in
1,2-dichloroethane (2 mL) was treated with triflic acid (4 µL,
OM0209778