Structural studies on novel Ru(II)-Binap complexes

Article abstract of DOI:10.1016/j.ica.2005.06.072

The solid-state structures for two complexes, 7 and 8, are reported. Complex 7 was prepared by treating Ru(OAc)₂(Binap) with two equivalents of HBArF in toluene solution, and represents only the second solid-state structure of a Binap complex, in which the Binap is a 6e donor to the Ru(II). The bonding is maintained in solution as shown via ¹³C NMR studies. The unusual cation 8, as an SbF6- salt, arises from prolonged reaction of Ru(OAc)₂(Binap) with wet HBF₄ (and, subsequently, added HSbF₆) in 1,2-dichloroethane.

Full text of DOI:10.1016/j.ica.2005.06.072

Inorganica Chimica Acta 359 (2006) 962–969
www.elsevier.com/locate/ica
Structural studies on novel Ru(II)–Binap complexes
a
a,
b
b,
*
Tilmann J. Geldbach , Paul S. Pregosin *, Silvia Rizzato , Alberto Albinati
a
Laboratory of Inorganic Chemistry, HCI ETH Ho¨nggerberg, 8093 Zu¨rich, Switzerland
Department of Structural Chemistry (DCSSI), and Faculty of Pharmacy University of Milan, 20133 Milan, Italy
b
Received 30 May 2005; accepted 23 June 2005
Available online 15 August 2005
Ruthenium and Osmium Chemistry Topical Issue
Abstract
The solid-state structures for two complexes, 7 and 8, are reported. Complex 7 was prepared by treating Ru(OAc)2(Binap) with
two equivalents of HBArF in toluene solution, and represents only the second solid-state structure of a Binap complex, in which the
Binap is a 6e donor to the Ru(II). The bonding is maintained in solution as shown via 13C NMR studies. The unusual cation 8, as an
ꢀ
SbF6 salt, arises from prolonged reaction of Ru(OAc)2(Binap) with wet HBF4 (and, subsequently, added HSbF6) in 1,2-
dichloroethane.
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: X-ray crystal structures; Ruthenium complexes; Binap
1. Introduction
coordinating the biaryl backbone to, e.g., Ru(II), via a
p-olefin bond [19–23]. Complexes 3–6, in Scheme 1, give
several examples. In these salts, the ligand is acting as a
six-electron donor to the Ru(II). The complexation of
the double bond adjacent to one of the P-donors was
unexpected, although White and co-workers [19] have
reported the structure of the [Ru(Cp)(Binap)]+cation
as having such a complexation mode. This represents
the only solid-state structure in which Binap adopts this
bonding mode; however, there are three further exam-
ples based on Ru–MeO–Biphep complexes [20,21]. It is
now clear [20–23] that 13C NMR and, to a lesser extent,
31P NMR, both can be used to recognize this bonding
mode in solution.
The atropisomeric chiral auxiliaries, Binap, 1 [1–13],
and MeO–Biphep, 2 [14–18], continue to
PPh2
PPh2
PPh2
MeO
MeO
PPh2
1
2
generate interest. Apart from their relevance to enantio-
selective homogeneous catalysis, it has been shown that
these bidentate aryl phosphine ligands are capable of
Recently, molecular structures with related bonding
modes for one Ru(Binapo) complex [24] (Binapo is the
mono-phosphine oxide of Binap), and for one Ru(Nu-
phos) derivative [25] (Nuphos is a butadiene derived
bidentate phosphine) have been reported.
*
Corresponding authors. Tel.: +41 44 632 2915; fax: +41 44 633
We report here the structure for a new Binap analog,
[Ru(g6-toluene)(Binap)](BArF)2, 7, as well as the struc-
1071.
E-mail address: pregosin@inorg.chem.ethz.ch (P.S. Pregosin).
0020-1693/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2005.06.072

T.J. Geldbach et al. / Inorganica Chimica Acta 359 (2006) 962–969
963
Cl
Cl
R2
P
i-Pr2
P
i-Pr2
P
Cl
Cl
Cl
Cl
Ru
Ru
Ru
Ru
P
P
Cl
P
i-Pr2 Cl
R2
i-Pr2
316
4 16 R = cyclohexyl or
iso-propyl
+
(SbF6)2
Ru
BF4-
iPr2
R2P
P
MeO
MeO
PR2
Ru
P
iPr2
MeO
OMe
515
613 R = iso-propyl or phenyl
Scheme 1.
ture for a somewhat unusual Ru(II) Binap derivative, 8,
which developed during some P–C bond splitting/BF4
hydrolysis chemistry.
recrystallisation
from
dichloromethane/pentane
solution. We chose to prepare the BArF salt since,
as we will show, the BF4 salt can sometimes
hydrolyse.
F
H O
B
F
Ph2
P
2.1. Solid-state structure for 7
CH3
O
Ru
Ph2
P
P
(SbF6)
Ph2
Ru
(BArF)2
Crystals suitable for X-ray diffraction were grown
via slow diffusion of pentane into a CH2Cl2 solution
of 7. The molecular structure for 7 was determined
by X-ray diffraction and ORTEP views of the di-cat-
ion are shown in Fig. 1. Fig. 1(a) provides a clear
view of the complexation of the naphthyl double
bond. The structure for 7 represents the first example
of this mode of bonding for a Binap di-cationic
complex.
P
Ph2
7
8
2. Results and discussion
The local coordination sphere about ruthenium is
made up of the two Binap P-atoms, the complexed
naphthyl double bond and the g6-toluene ligand. The
complexation of the naphthyl double bond via carbons
C(1) and C(6) induces a distortion of the binaphthyl
moiety, such that the face of the naphthyl p-system is
opened toward the metal [21]. The angle between the
two lines, through atoms C(1)–C(4) and C(10)–C(40),
which should be ca. 0ꢁ in an undistorted binaphthyl
moiety, is ca. 32ꢁ. This bending, to accommodate the
new olefinic bond, is in keeping with our earlier observa-
tions [20,21]. Selected bond lengths and bond angles are
given in Table 1. The BArF anion is found fairly close to
the cation and one finds a number of short F–H con-
Complex 7 was prepared in excellent yield by treating
Ru(OAc)2(Binap) with two equivalents
F
15 16
(BAr4
)
2
14
CH3
11
13 12
Ru
PPh2
Ru(OAc)2
PPh2
toluene
RT
+ 2 HBArF
PPh25'
Ph2P
6
6'
5
1
1'
2'
4'
3'
10'
4
2
3
10
7
7'
9
8
8'
9'
ð1Þ
of the acid HBArF in toluene solution, see Eq. (1)
(BArF = tetrakis (3,5-bis(trifluoromethyl) phenyl)bo-
rate). The two equivalents of acetic acid set free are
removed by decantation of the solution from the red
oil that separates. A solid product was obtained by
˚
tacts, in the range 2.6–3.0 A, between the BarF anion
and either the binaphthyl moiety or the C atoms of
the P-bonded phenyl rings.

964
T.J. Geldbach et al. / Inorganica Chimica Acta 359 (2006) 962–969
Fig. 1. ORTEP plots of the di-cation from 7 showing (a) the g2-olefin complexation and (b) a view from the side showing a approximately parallel
arrangement of one naphthyl moiety with respect to the complexed g6-toluene. Ellipsoids drawn at 50% probability.
Table 1
2.2. Solution data for 7
˚
Selected bond lengths (A) and bond angles (ꢁ) for 7
The 31P NMR spectrum of 7 showed an AX spin sys-
tem, with the two different P-resonances observed at
d = 64.7 and d = 14.1, 2J(P,P) = 45 Hz. The latter
absorption appears at relatively low frequency and this
is recognized [20,21,40] to be due to the small ring
Ru–P(2)
Ru–C(1)
2.324(1)
2.340(5)
Ru–P(1)
Ru–C(6)
2.330(1)
2.265(5)
Ru–C(1L)
Ru–C(3L)
Ru–C(5L)
2.348(6)
2.260(6)
2.244(6)
Ru–C(2L)
Ru–C(4L)
Ru–C(6L)
2.267(5)
2.266(6)
2.267(6)
1
formed. The 2-D 13C, H long-range correlation reveals
P(1)–C(6)
1.782(5)
1.806(5)
1.829(5)
1.439(7)
P(1)–C(121)
P(2)–C(60)
P(2)–C(221)
1.796(5)
1.807(5)
1.826(5)
P(1)–C(111)
P(2)–C(211)
C(1)–C(6)
the two backbone carbons, C1 and C6 at d = 104.2 and
d = 71.1 ppm, respectively. These values correspond to
coordination chemical shifts, Dd, of more than
40 ppm, thus supporting a solution structure in which
the Binap is acting as a six-electron donor. The smaller
Dd for C1 is consistent with the observed longer
Ru–C(1) separation. The analogous chemical shift val-
ues for [Ru(Cp)(Binap)]+ are 88.2 and 56.9 ppm [21],
for C1 and C6, respectively. Obviously, these 13C values
are quite different from those for 7 perhaps due to its di-
cationic nature relative to the mono-cation,
[Ru(Cp)(Binap)]+.
P(2)–Ru–P(1)
P(2)–Ru–C(1)
C(6)–Ru–P(1)
89.74(5)
81.1(1)
45.6(1)
P(1)–Ru–C(1)
C(6) Ru–P(2)
71.2(1)
105.1(1)
The ruthenium–carbon bond distance, Ru–C(1), is
long, 2.340(5) A, relative to the Ru–C(6) separation,
2.265(5) A; however, this bond length is deceptive since
the p electrons in the C1–C6 bond are closer to the me-
˚
˚
tal. The analogous separations in the mono-cation
The presence of a distorted g6 toluene arene ligand in
7 (rather than an g4) is supported by the low frequency
13C positions of the six non-equivalent arene carbons:
C11, d = 121.2; C12, 16, d = 108.5, 112.2; C13, 15,
d = 91.1, 98.3; C14, d = 94.3. We have not distinguished
the two ortho and two meta 13C resonances. Five of
these resonances are easily detected in a conventional
[Ru(Cp)(Binap)]+ are 2.258(7) and 2.281(9) A [19]. The
˚
˚
C1–C6 bond distance in 7, 1.439(7) A, falls, coinciden-
tally, exactly between a single and double bond, in keep-
ing with a significant p interaction from the metal to the
olefin. The six Ru–C(arene) separations are normal [27–
39] and differ only in that the longer distance, Ru–
C(1L), from the ruthenium atom to the toluene ipso
carbon, at 2.348(6) A, hints at unsymmetrical p-com-
plexation. The values Ru–P(1), 2.330(1) A and Ru–
P(2), 2.324(1) A are normal [26].
1
one-bond 13C, H correlation, and the sixth (the ipso
˚
˚
carbon) via a correlation to the protons of the methyl
group.
˚
We note that two ortho proton resonances of the
complexed toluene, H12 and H16, appear at relatively
low frequency, 3.86 and 4.86 ppm. The toluene methyl
proton signal is also markedly shifted to low frequency,
Interestingly, the P–Ru–P angle, 89.74(5)ꢁ, is small
for a Binap complex, presumably due to the chelation.
This angle is often observed [2b,2c,8–11] to be between
92ꢁ and 94ꢁ.

T.J. Geldbach et al. / Inorganica Chimica Acta 359 (2006) 962–969
965
d = 0.64. We assign these rather large coordination
chemical shifts to a mixture of complexation and aniso-
tropic effects. The solid-state structure for 7 nicely
demonstrates that part of the toluene ligand lays over
the p-system of one of the naphthyl rings (with the
unexpected structure required this additional H-
bonding.
F
O
B
R2P
F
˚
O
shortest intra-ligand contacts in the range 3.1–3.3 A),
R2P
MeO
Ru
F
H
see Fig. 1(b). Consequently, local anisotropic effects
are expected to contribute to these low frequency proton
positions. However, as expected, the 13C chemical shifts
of the corresponding carbon resonances do not reflect
this anisotropic effect. We find no indication, in either
BF3
O
Me
10
1
the H or 31P spectra, for exchange [20] between the
two-naphthyl moieties in 7.
Despite some molecular distortion, due to the small
ring which forms when the backbone olefin complexes,
the Binap ligand readily accommodates this 6e-bonding
mode, both in the solid and solution states.
Although the reaction shown in Eq. (3) is most likely
quite complicated [43a], cation 8 can be thought of as
arising from a complex related to 9 (without triflate)
by successive phenyl migration, protonation and hydro-
lysis reactions involving water and a BF4 anion [43b].
Salts 8 and 10 represent the only examples of P,O-chelate
ligands with boron in their backbones, although boron
as a component of polydentate phosphine ligands is
now well known [44–47].
2.3. P–C bond cleavage and BF ꢀ4 hydrolysis
Use of wet triflic acid in 1,2-dichloroethane, instead
of HBArF, for the protonation reaction with
Ru(OAc)2(Binap), is known [40,41] to afford P–C bond
cleavage and the formation of 9 (see Eq. (2)). Although
the reaction takes place via a number of not obvious
steps [41], the product can be thought of as arising from
addition of water across the P–C bond.
The solid-state structure of 8 has been determined by
X-ray diffraction methods at low temperature, and two
views of this cation are shown in Fig. 2. The immediate
ruthenium coordination sphere of the cation consists of
the two P-donors, an oxygen donor from the OH–
B(F2)–O–P chelate ligand and the distorted p-complexed
arene (see Fig. 2(a)). For 10 there is no residual HBF4
and no water; however, there are many short contacts
between (a) the F atoms of the anion and the H atoms
OTf
Ph2
P
2 HOTf
Ru(OAc)2
P
C2H4Cl2
Ru
Ph2
PPh2
TfO
PPh2OH
˚
of the P-bonded phenyl rings (at c/a 2.4 A) and (b) be-
tween the F atoms of the BF2 moiety and the naphthyl
rings (at c/a 2.5 A). Moreover a short hydrogen bond is
9
˚
ð2Þ
present between the protonated O2 atom and a fluorine
atom of the SbF6 counter ion. The distance between
protonated O2 atom and the appropriate F-atom is ca.
Prolonged reaction of Ru(OAc)2(Binap) in 1,2-
dichloroethane, with wet HBF4/ether as the pꢀroton
source (see Eq. (3)) affords cation 8 as an SbF6 salt
(see Section 4). We have
˚
2.7 A (cf. Table 2).
The two Ru–P distances are markedly different, Ru–
˚
˚
F
P(1) = 2.3397(8) A and Ru–P(2) = 2.2713(8) A and the
Ru–O bond slightly long (see Table 2). The six Ru–
H O
B
F
Ph2
P
Ph2
P
˚
O
2 eq. HBF4 in Et2O
C2H4Cl2 363K
Ru
C(arene) bond lengths vary from ca. 2.14 to 2.43 A.
P
Ru(OAc)2
Ph2
The shortest separations are to C1 and C6 reflecting a
presumed intermediate along the reaction coordinate in
which a C1–C6 double bond was complexed to the ruthe-
nium [40]. The longest separations, Ru–C(30) = 2.419(3)
P
Ph2
8 as anSbF6 salt
0
˚
˚
A and Ru–C(2 ) = 2.431(3) A, are associated with the
fully substituted carbons and are rather long for Ru(II)
arene bonds [39a]. It would not be unreasonable to con-
sider these Ru–C(arene) distances as corresponding to an
g4 di-olefin complex. The two B–O bond lengths are sig-
nificantly different whereas the two B–F bond lengths are
the same within the experimental error.
ð3Þ
found [42] a related reaction starting from Ru(OAc)2
(MeO–Bipheꢀp), and the solid-state structure of cation,
10, as a BF4 salt, is known [42]. Increasing the water
content accelerates the formation of both 8 and 10.
The previously reported structure of 10 contains a BF4
anion that is hydrogen-bonded to a chelating hydroxyl
hydrogen atom, and it was possible that this rather
The three bond angles at ruthenium, P(2)–Ru–
P(1) = 92.72(3)ꢁ, O(2)–Ru–P(2) = 78.16(6)ꢁ and O(2)–

966
T.J. Geldbach et al. / Inorganica Chimica Acta 359 (2006) 962–969
Fig. 2. ORTEP plots of the cation of 8 showing (a) the O–B(F2)–O–P chelate ring and (b) the g-arene complexation. Ellipsoids drawn at 50%
probability.
d = 115.8 and d = 49.0, 2JPP = 52. The 19F NMR reveals
Table 2
˚
a broad resonance for the SbF6 anion, at d ca. ꢀ119.8
Selected bond lengths (A) and bond angles (ꢁ) for 8
and the non-equivalent BF2 signals as broad doublet res-
Ru–P(1)
Ru–O(2)
2.3397(8)
2.128(2)
Ru–P(2)
2.2713(8)
onances at d = ꢀ140.7 and d = ꢀ143.8. The observed
2
splitting is assigned to J(19F,19F). We believe that the
Ru–C(60)
Ru–C(40)
Ru–C(20)
2.177(3)
2.288(3)
2.431(3)
Ru–C(50)
Ru–C(30)
Ru–C(10)
2.284(3)
2.419(3)
2.137(3)
broadening arises due to the boron quadrupole so that
3
the spin–spin coupling J(31P,19F) is not observed.
The presence of a distorted p-arene ligand in 8 is
supported by the six low frequency 13C positions of the
p-arene carbons. Three of these resonances are easily
detected in a conventional one-bond 13C, 1H correlation,
and the remaining three via a long-range correlation.
Interestingly, the resonances for C6 and C1, in 8,
d = 73.0 and d = 102.4 are very similar to those found
in 7 (d = 71.1 and d = 104.2, respectively) supporting
the idea that these two carbons were bound early in the
reaction sequence leading to 8. The remaining four p-
arene resonances (C2, d = 113.2, C3, d = 109.6, C4,
d = 94.6, C5, d = 105.4) were complexed when the arene
fragment ‘‘shifted slightly’’ during the subsequent reac-
tions. We have not been able to locate the proton reso-
nance of the hydrogen bonded OH-group, described
above.
P(1)–C(6)
P(1)–C(111)
P(2)–C(211)
1.834(3)
1.838(3)
1.805(3)
P(1)–C(121)
P(2)–O(1)
P(2)–C(221)
1.832(3)
1.582(2)
1.816(3)
O(1)–B
B–F(2B)
O(2)–H(O2)
1.482(4)
1.379(4)
0.70(6)
O(2)–B
B–F(1B)
O(2)–F(3A)0
1.508(4)
1.389(4)
2.681(5)
P(2)–Ru–P(1)
O(2)–Ru–P(1)
92.72(3)
92.74(7)
O(2)–Ru–P(2)
78.16(6)
B–O(1)–P(2)
121.2(2)
110.0(3)
111.3(3)
108.8(3)
176(1)
B–O(2)–Ru
122.2(2)
109.6(3)
109.9(3)
107.1(2)
F(2B)–B–F(1B)
F(1B)–B–O(1)
F(1B)–B–O(2)
O(2)–H(O2)–F(3A)0
F(2B)–B–O(1)
F(2B)–B–O(2)
O(1)–B–O(2)
Primed atoms are generated by the symmetry operation: 1 ꢀ x; y ꢀ 1/
2; 1 ꢀ z.
Ru–P(1) = 92.74(7)ꢁ, are normal allowing for the small
bite angle of the O–B(F2)–O–P five membered ring che-
late ligand. The six bond angles about the boron atom
vary ca. 2ꢁ from 109ꢁ. For 8, the angle between the
two lines, C(1)–C(4) and C(10)–C(40), is now ca. 12ꢁ,
much less than that found for 7.
We note that there is a p-stacking interaction between
the second ring of the complexed naphthyl moiety (con-
taining C100) and a P-phenyl ring of the PPh2 group, see
Fig. 2(a). The shortest C–C separations are in the range
3. Comment
The Ru(II) chemistry of Binap is somewhat different
than that observed for other bidentate aryl phosphine li-
gands. There is a strong propensity for Binap (and
MeO–Biphep) to use electrons from the biaryl backbone
to stabilise reactive 16e cationic species, although very
few of these molecules have been characterized crystallo-
graphically. These cationic olefin complexes are mod-
estly stable; however, they can react with water under
acid conditions [41] to afford new arene complexes in
which a P–C bond has been split and a biaryl aromatic
moiety complexed in a strongly distorted g6 fashion.
˚
3.45–3.50 A.
2.4. Solution data for 8
The 31P NMR of 8 in CD2Cl2 reveals the expected AX
spin system with the two very different signals at,

T.J. Geldbach et al. / Inorganica Chimica Acta 359 (2006) 962–969
967
Some of these intermediate cationic complexes become
sufficiently electrophilic to assist in the hydrolysis of
the BF4 anion, affording the very unusual, but relatively
stable complexes 8 and 10. The structures of 8 and 10,
aqueous HBF4 (6 ll, 0.047 mmol) and HSbF6 Æ 6H2O
(16 mg, 0.047 mmol) stirred for 3 h at 90 ꢁC. The deci-
sion to addꢀHSbF6 arose after attempts to obtain crystals
of the BF4 salt proved fruitless. The solution was con-
centrated and the product precipitated via addition of
Et2O, affording the product as a yellow solid. Yield:
ꢀ
contain hydrogen bonded HX molecules (X ¼ SbF6
and BF4ꢀ, respectively), and these, presumably, help
to stabilise these novel complexes. Although the exact
mechanisms of all of these transformations remain
uncertain, there are indications that some of the reac-
tions proceed in a stereoselective fashion [44] and studies
designed to clarify these details are in progress.
1
40 mg (81%). H NMR (CD2Cl2, 400 MHz): 8.41 (d,
3
4
3JHH = 8.57, H10), 8.26 (dd, JHH = 8.8, JPH = 1.8,
0
0
H4 ), 8.21 (d, JHH = 7.9, H10 ), 7.97–7.89 (m, 3H), 7.83
3
0
0
(dd, JHH = 8.8, JPH = 7.0, H5 ), 7.72 (m, H8 ), 7.60–
7.53 (m, 6H), 7.34 (m, 1H), 7.27 (m, 1H), 7.23–7.16 (m,
4H), 7.09–7.00 (m, 4H), 6.92 (m, H8), 6.89–6.79 (m,
3
3
4H), 6.27(d, JHH = 8.5, H7), 5.88 (dd, JHH = 5.3,
3
3
4. Experimental
3JPH = 2.9, H6), 5.44 (br, 1H), 5.17 (m, H5). 13C NMR
1
(CD2Cl2, 1000 MHz): 142.7 (d, JPC = 60), 141.7 (d,
0
1
4.1. Preparation of 7
1JPC = 53, C6 ), 141.1 (d, JPC = 22, C1 ), 135.9 (C9),
0
134.7 (d, JPC = 2, C3 ), 134.4 (C8), 133.9 (m), 132.5 (d,
4
0
3
A mixture of Ru(OAc)2 (1) (30 mg, 0.036 mmol) and
HBArF Æ 2Et2O (76 mg, 0.075 mmol) was suspended in
toluene (10 ml) and stirred at RT for 10 min, during
which time, a red oil deposits. The supernatant was dec-
anted off and the residue washed with pentane and
recrystallized via slow diffusion of pentane into a
CH2Cl2 solution, affording red crystals of 7. Yield:
84 mg, 92%. 1H NMR (CD2Cl2, 500 MHz): 8.27 (d,
JPC = 11), 131.7 (d, JPC = 3), 131.5 (d, JPC = 14, C4 ),
0
131.4 (d, JPC = 7, C2 ), 131.0 (d, JPC = 3), 130.2 (d,
3
JPC = 3), 130.0 (C10), 129.7 (C9), 129.6 (d, JPC = 11,
2
0
0
C5 ), 129.4 (d, JPC = 12), 129.1 (C8 ), 128.7 (C10), 128.3
(d, JPC = 11), 128.0, 127.5 (d, JPC = 11), 127.4 (C7),
0
126.2, 126.1, 125.0 (C7 ), 113.2 (d, JPC = 9, C2), 109.6
(br, C3), 105.4 (d, JPC = 6, C5), 102.4 (d, JPC = 4, C1),
94.6 (d, JPC = 9, C4), 73.0 (C6). 9F NMR (CD2Cl2,
188 MHz): ꢀ119.8 (br, SbF6), ꢀ140.7 (m, BF2), ꢀ143.8
(m, BF2). 31P NMR (CD2Cl2, 162 MHz): 115.8 (d,
2JPP = 52), 49.0 (d, 2JPP = 52). Elemental analysis: Anal.
Calc. for C44H33BF8O2P2RuSb (1041.31 g/mol): C,
50.75; H, 3.19. Found: C, 50.01; H, 3.55%.
3
3JHH = 9.2, H4), 8.19 (d, JHH = 7.9, H10), 8.02–7.96
(m, 4H), 7.90–7.68 (m, 8H), 7.62 (m, 2H), 7.59 (s, 8H),
3
3
7.49 (dd, JHH = 7.9, JPH = 12.6, 2H), 7.38 (dd,
0
3JHH = 7.5, J0HH = 8.3, H8 ), 7.28 (dd, JHH = 8.8,
3
3
3JHH = 8.8, H5 ), 7.04 (m, H16), 6.82 (m, 1H), 6.14 (m,
2H), 6.08 (m, 2H, H13, H15), 5.91 (dd, JHH = 8.3,
3
0
3JPH = 13.5, 2H), 5.82 (d, JHH = 8.3, H7 ), 4.86 (m,
4.3. X-ray crystallography
3
H14), 3.86 (d, JHH = 6.6, H12), 0.64 (s, CH3, 3H). 13C
3
1
NMR (CD2Cl2, 125 MHz): 162.1 (q, JCB = 50, ipso-
Air stable crystals of [Ru(g6-toluene)(Binap)]-
(BArF)2, 7, were obtained from pentane/dichlorometh-
ane solution. Yellow crystals of 8, suitable for X-ray
diffraction, were obtained by crystallization from
ether/dichloromethane and are air stable.
0
BArF), 145.4 (dd, JPC = 25, JPC = 2, C1 ), 142.1 (d,
2
3
3JPC = 9, C20), 137.3 (d, JPC = 8, C4), 136.2 (d,
3
4JPC = 2, C3 ), 135.7, 135.2 (ortho-BArF), 134.6 (d,
0
4JPC = 3, C3), 134.2 (d, JPC = 8, C2 ), 133.6, 133.1 (d,
3
JPC = 3), 132.8 (C8), 131.7 (m), 131.1 (C10), 131.0,
Prismatic single crystals of both compounds were
mounted, for the data collection, on a glass fiber, at a
random orientation, on a Bruker SMART CCD diffrac-
tometer at room temperature for 7 and on a Bruker
APEX CCD for 8. The latter crystal was then cooled
in a cold nitrogen gas stream to 90 K for the data collec-
tion. The space groups were determined from the sys-
tematic absences, while the cell constants were refined,
at the end of the data collection, with the data reduction
software SAINT [48]. An extended list of experimental
conditions for the data collection is given in the Supple-
mentary Data. The collected intensities were corrected
for Lorentz and polarization factors [48] and empirically
for absorption using the SADABS program [49].
0
0
130.6 (d, JPH = 11), 130.5 (C8 ), 130.4 (C9 ), 1290.4
0
(C10 ), 129.1 (meta-BArF), 129.8 (d, JPC = 02, C4 ),
3
1260. 3 (d, JPC = 6, C5), 125.3 (d, JPC = 2, C5 ), 125.1
2
2
(C7 ), 125.0 (q, JCF=272, CF3), 121.2 (d, JPC = 2,
1
C11), 117.9 (m, para-BArF), 112.2 (d, JPC = 4, C12),
108.5 (d, JPC = 3, C14), 104.2 (br, C1), 98.3 (d,
JPC = 3, C13), 94.3 (C16), 91.3 (C15), 71.1 (d, JPC = 34,
1
C6). 19F NMR (CD2Cl2, 282 MHz): ꢀ63.22 (s). 31P
2
NMR (CD2Cl2, 202 MHz): 64.7 (d, JPP = 45), 14.1 (d,
2JPP = 45). MS (Electrospray): 408.1 (M2+). Elemental
analysis: Anal. Calc. for C115H64B2F48P2Ru (2542.33 g/
mol): C, 54.33; H, 2.54. Found: C, 54.26; H, 2.66%.
4.2. Preparation of 8
Selected crystallographic and other relevant data are
listed in Table 3 and in the Supplementary Data. The
standard deviations on intensities were calculated in
terms of statistics alone.
To
a
solution of Ru(OAc)2(BINAP) (40 mg,
0.047 mmol) in 1,2-dichloroethane (10 ml) was added

968
T.J. Geldbach et al. / Inorganica Chimica Acta 359 (2006) 962–969
Table 3
Experimental data for the X-ray diffraction study of compounds 7 and 8
Formula
C115H66B2F48P2Ru
2542.29
293(2)
C44H33BF8O2P2RuSb
1041.27
100(2)
Formula weight
Data collection T (K)
Diffractometer
Crystal system
Space group (No.)
Bruker SMART
monoclinic
P21/n (14)
14.274(1)
43.189(4)
18.694(2)
109.089(2)
10891(2)
4
Bruker APEX
monoclinic
P21 (4)
10.0436(8)
19.323(2)
11.1804(9)
111.686(2)
2016.2(3)
2
˚
a (A)
˚
b (A)
˚
c (A)
b (ꢁ)
3
˚
V (A )
Z
D(calcd) (g cmꢀ3
)
1.551
3.05
1.717
11.99
l (cmꢀ1
)
˚
Radiation
Mo Ka (graphite monochromated, k = 0.71073 A)
h range (ꢁ)
Data collected
1.25 6 h 6 26.43
83288
2.42 6 h 6 26.04
13661
Independent data
20066
7308
Observed reflections (no)
11393
7141
2
2
[jFoj > 2.0 r(jFj )]
No. of parameters (nv)
Rint
1273
536
0.0608
0.0700
0.1827
1.023
0.0259
0.0230
0.0538
0.992
R (observed reflections)
R2w ðobserved reflectionsÞ
Goodness-of-fit
P
P
R = (jFo ꢀ (1/k)Fcj)/ jFoj.
P
P
2
2
R2w ¼ ½ wðF 2o ꢀ ð1=kÞF c2Þ = wjF o2j ꢁ.
P
2
1=2
GOF ¼ ½ wðF 2o ꢀ ð1=kÞF c2Þ =ðno ꢀ nvÞꢁ
.
All calculations were carried out by using the PC ver-
sion of the programs WINGX [51], SHELX-97 [50] and OR-
TEP [52].
The scattering factors used, corrected for the real and
imaginary parts of the anomalous dispersion, were taken
from the literature [53].
wards the end of the refinement a peak was found (at
ca. 0.8 A) from atom O(2) with a geometry consistent
with the presence of an H atom, and this was included
in the refinement without constraints. All the other
˚
hydrogen atoms were placed in calculated positions
2
˚
˚
(C–H = 0.95(A), Biso(H) = 1.2 · B(Cbonded)(A )), and
included in the refinement using a riding model. Refin-
ing the Flackꢀs parameter [54] tested the handedness of
the structure.
4.4. Structural study of
[Ru(g6-toluene)(Binap)](BArF)2, 7
The structure was solved by direct and Fourier meth-
ods and refined by full matrix least squares [50], mini-
P
2
mizing the function ½ wðF 2o ꢀ ð1=kÞF c2Þ ꢁ and using
anisotropic displacement parameters for all atoms. As
usual, the ADPꢀs of some of the F atoms of the BArF
counter-ion are large suggesting the presence of disor-
der. However, a model with F atoms in split positions
did not improve the refinement, thus the previous model
was retained. No extinction correction was deemed nec-
essary. Upon convergence, the final Fourier difference
map showed no significant peaks. The contribution of
Acknowledgements
P.S.P. thanks the Swiss National Science
Foundation, the ETH Zurich and COST for financial
support as well as Johnson Matthey for the loan of
precious metals and F. Hoffmann-La Roche
AG, Basel, for the gift of MeO–Biphep precursors.
A.A. thanks M.I.U.R. for a research grant (PRIN
2004).
the hydrogen atoms, in their calculated position,
2
˚
˚
(C–H = 0.95(A),
B
iso(H) = 1.3/1.4 · B(Cbonded)(A )),
was included in the refinement using a riding model.
Appendix A. Supplementary data
4.5. Structural study of 8
Supplementary data associated with this article can
be found, in the online version, at doi:10.1016/
j.ica.2005.06.072.
The structure was solved and refined as above, using
anisotropic displacement parameters for all atoms. To-

T.J. Geldbach et al. / Inorganica Chimica Acta 359 (2006) 962–969
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