Synthesis, characterization of (R)-2,2′-diamino-1,1′-binaphthyl mono-sulfonamide and its ruthenium complex and evaluation of the catalytic properties in transfer hydrogenation reactions

Article abstract of DOI:10.1016/S0022-328X(98)00796-7

(R)-2-amino-2′-(8-quinolinesulfonyl amino)-1,1′-binaphthyl is synthesized. Its ruthenium complex is shown to be an asymmetric catalyst for transfer hydrogenation reactions in high chemical yield and modest enantioselectivity. Single crystal diffraction studies of both the ligand and the ruthenium complex show strong π-stacking interactions between the quinoline ring and one of the naphthyl groups. The relationship between the structure and catalytic reactivity is also discussed.

Full text of DOI:10.1016/S0022-328X(98)00796-7

Journal of Organometallic Chemistry 568 (1998) 77–86
Synthesis, characterization of (R)-2,2%-diamino-1,1%-binaphthyl
mono-sulfonamide and its ruthenium complex and evaluation of the
catalytic properties in transfer hydrogenation reactions
Lisheng Cai *, Ying Han, Hussein Mahmoud, Brent M. Segal 1
The Department of Chemistry, The Uni6ersity of Illinois at Chicago, Chicago, IL 60607, USA
Received 19 February 1998; received in revised form 22 May 1998
Abstract
(R)-2-amino-2%-(8-quinolinesulfonyl amino)-1,1%-binaphthyl is synthesized. Its ruthenium complex is shown to be an asymmetric
catalyst for transfer hydrogenation reactions in high chemical yield and modest enantioselectivity. Single crystal diffraction studies
of both the ligand and the ruthenium complex show strong y-stacking interactions between the quinoline ring and one of the
naphthyl groups. The relationship between the structure and catalytic reactivity is also discussed. © 1998 Elsevier Science S.A. All
rights reserved.
Keywords: Asymmetric; Ruthenium; Sulfonamide; Binaphthyl; Transfer hydrogenation
1. Introduction
asymmetric transfer hydrogenation has remained quite
primitive [3]. It is only recently that some successful
examples have been reported for the reduction of some
activated olefins, aromatic ketones, and imines using
alcohols or formic acid as the hydrogen source [4]. Two
of the successful examples of the catalysts are shown in
Scheme 1.
A number of features have been discovered for these
series of catalysts: (a) the ligands accelerate the reac-
tion; (2) two equivalents of KOH are needed per cata-
lyst; (3) the presence of an NH moiety in each ligand is
crucially important. A mechanistic model based on
these observations has been proposed. Some of the key
features are that the hydrogen transfer occurs via
metal–ligand bifunctional catalysis, and the NH link-
age can stabilize a transition state by forming a hydro-
gen bond with the heteroatom. The six-membered cyclic
transition structure is schematically visualized by 3 in
Scheme 1. Scheme 2 illustrates the general sense of
asymmetric induction in transfer hydrogenation of
imines and aromatic ketones for one of the catalysts.
Here we want to report our initial efforts in this area of
research.
Asymmetric reduction of CꢀO and CꢀN bonds form-
ing chiral alcohols and amines, respectively, is among
the most fundamental molecular transformations [1]. In
nature, oxidoreductases, such as horse liver alcohol
dehydrogenase, catalyze transfer hydrogenation of car-
bonyl compounds to alcohols using cofactors like
NADH or NADPH [2]. Such biochemical reactions are
normally very stereoselective. However, organic synthe-
sis needs economically and technically more beneficial
methods that are very general. A reaction using non-
hazardous organic molecules provides a useful comple-
ment to catalytic reduction using molecular hydrogen,
particularly for small to medium scale reactions. Trans-
fer hydrogenation is operationally simple, and the selec-
tivities including functional group differentiation may
be different from those of hydrogenation. Catalytic
* Corresponding author. Tel.: +1 312 9963161; fax: +1 312
9960431; e-mail: cai@uic.edu
1 Present address: Department of Chemistry and Chemical Biology,
Harvard University, 12 Oxford Street, Cambridge, MA 02138, USA.
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00796-7

78
L. Cai et al. / Journal of Organometallic Chemistry 568 (1998) 77–86
Scheme 1. Some examples of catalysts for transfer hydrogenations and proposed key intermediate or transition state (X=O, NR).
2. Results and discussion
sulfonyl amide (C12–N2–S1) is 124°, typical for N-
arylsulphonamides, where the nitrogen is sp2 hybridized
[9]. The other bond distances and bond angles for each
individual atom for this molecule are within the range
for these types of compounds.
Compared with the asymmetric ligands based on
BINAP and 1,1%-bi-2-naphthol [5], asymmetric ligands
based on 1,1%-binaphthyl-2,2%-diamine, 1,1%-binaphthyl-
2-amino-2%-hydroxy, and 1,1%-binaphthyl-2-amino-2%-
thiol, are scarce [6]. However, promising results have
been obtained in the catalysis of Mukaiyama reactions
[7].
However, the arrangement of groups within the
molecule is quite interesting. The quinoline ring and
one of the naphthyl rings are slightly tilted toward each
other with a dihedral angle of 5.2°. The interplanar
˚
distance is about 3.3 A, which closely matches that of
2.1. Synthesis of the ligand
the graphite and other p-stacking systems. Importantly,
y-stacking may not be the only interaction to keep the
two rings close and parallel. We believe that they may
also interact through y-donor and y-acceptor bonds.
The quinoline ring is electronically poor and can act as
an electron acceptor, while the naphthyl group with
amine or amide substituent attached may act as an
electron donor. The magnitude of this interaction is
also reflected in the formation of the transition metal
complex as described below. The dihedral angle be-
tween the naphthyl rings toward the two nitrogen
atoms is 83°, as compared with 86° in 1,1%-binaphthyl-
2-amino-2%-hydroxy [10].
We set out to explore the asymmetric induction
based on the last three categories of 1,1%-binaphthyl
compounds. The synthesis of 8-quinolinesulfonyl amide
5 is shown in Scheme 3. Multiple trials, to select an
optimal condition to synthesize the sulfonamide, result
in finding that the reaction works best in a dilute
solution of acetonitrile with pyridine as base (8-quino-
line sulfonyl chloride is not very soluble in CH3CN).
The most common problem is the precipitate formation
between 2,2%-diamine-1,1%-binaphthyl or pyridine and
8-quinolinesulfonyl chloride in other solvents. Reac-
tions of sulfonyl chlorides and amines in DMF result in
our discovery of a new procedure for the synthesis of
formamidines [8].
2.2. Catalytic reacti6ity of the ligand 5 for a number
of in situ reactions
X-ray quality crystals for compound 5 were grown
from CH3CN/Et2O. The results of this study are shown
in Fig. 1 and Tables 1–3. The bond angle around the
No catalytic activity is observed for the reaction
between Zn(C2H5)2 and aldehydes such as benzalde-
hyde (PhCHO) and trans-PhCHꢀCHCHO. Pre-mixing
of 5 with Ti(OPri)4 did not improve the reaction. Cyclo-
propanation of styrene with ethyl diazoacetate in the
presence of the ligand 5 and CuOTf generates ethyl
1-phenyl-1-cyclopropanecarboxylate in high chemical
yield, however, no e.e. is observed.
2.3. Synthesis of the complex 6
The reaction of ligand 5 with RuCl2(Cumene) in
refluxing 2-isopropanol generates a half sandwich com-
plex 6. The complex is soluble in most common organic
solvents such as THF, ether, methanol, ethanol,
CH2Cl2, CHCl3, and slightly soluble in CH3CN,
toluene, benzene. Exchange of the anion chloride in 6
Scheme 2. General sense of selectivity by one of the asymmetric
transfer hydrogenation catalysts.

L. Cai et al. / Journal of Organometallic Chemistry 568 (1998) 77–86
79
Scheme 3. Synthesis of ligand 5 and its ruthenium complex 6.
2.5. Catalytic reacti6ity of the complex for transfer
hydrogenations
by AgPF6 generates 7 (Scheme 3), showing that the
chloride is not in the immediate coordination sphere of
ruthenium. Other ruthenium starting materials such as
norbornene ruthenium dichloride or ruthenium trichlo-
ride do not generate any complexes. The free ligand is
un-changed under a variety of conditions such as differ-
ent solvents (DMF, isopropanol), and temperatures (r.t.
to 150°C).
As a start, ruthenium complex 6 (Scheme 4) catalyzes
the transfer hydrogenations of ketones in isopropanol
at 80°C to give the corresponding alcohols in high
yield, but with modest enantioselectivity at best. It
seems that the reduced reactivity of this complex comes
from the lack of an empty coordination site at r.t. The
most probable pre-dissociation is the weak ruthenium–
aniline bond, which may reduce the influence of the
chiral center on the incoming ketones or imines. The
presence of a base such as Na2CO3 destroys the cata-
lyst, no reaction is observed in isopropanol at 80°C
overnight. No intermediates were observed during the
2.4. Structure of the complex 6
Crystals suitable for X-ray single crystal study were
grown from CH3CN/Et2O system as detailed in the
experimental section. Two similar molecules exist in
each asymmetric unit. Structural information for only
one of them is given in Fig. 2 and Tables 4–6. The
ruthenium is a saturated diamagnetic 18-electron cen-
ter. The p6-coordination of the cumene is maintained
1
reaction by H-NMR. After the reaction, the catalyst
was recovered at 92%.
Transfer hydrogenation of h,i-unsaturated alde-
hydes or ketones such as chalone (trans-
PhCHꢀCHCOPh) generates a mixture of products
which originate from either CꢀC bond, or CꢀO bond,
or simultaneous reduction of CꢀC and CꢀO bonds.
Stronger reducing agents such as formic acid and tri-
ethylamine generate similar results under the same con-
ditions. However, no difference in e.e. values is
observed. Lowering temperature dramatically slows
down the reactions. h,i-Unsaturated acids or esters
such as methyl cinnamic ester (trans-PhCHꢀCHCO-
OCH3) or i-methyl cinnamic acid (trans-Ph(Me)
CꢀCHCOOH) cannot be reduced under the same con-
ditions. No reduction is observed for imines such as
trans-Ph(Me)CꢀN–Ph.
˚
with an average distance of 2.2090.04 A, comparable
with that of the neutral analog [11]. While the bond
lengths of Ru-amide (Ru–N2) and Ru-quinoline (Ru–
N3) are comparable with other Ru-analogs [11], the
˚
Ru-amine (Ru–N1) bond is longer by 0.1 A. This may
be the bond broken when the ruthenium center opens
its coordination for substrate binding. The dihedral
angle between the two naphthyl rings toward the two
nitrogen atoms is 71°, reduced from 83° in free ligand 5.
The bond angles around N2 are almost unchanged as
compared with free ligand, 12092°. Overlap of the
structure of the complex 6 with that of its free ligand 5
reveals minor changes in the ligand portion, except for
the decrease of the dihedral angle between the two
naphthyl rings toward the ruthenium center. The dihe-
dral angle of the quinoline ring, and one of the naph-
thyl rings, is 9.1°, only slightly larger than 5.2° observed
in free ligand 5. It appears that the ligand has a strong
tendency to maintain its own structure even after it
coordinates with the transition metal fragment. Amaz-
ingly, the ruthenium complex is the only one we can
make out of this ligand up to now. This may mean that
only the metal fragment, which matches the geometric
requirements of this multidentate ligand, can coordi-
nate. Substitution of the amino-group N1H2 with a
hydroxy group OH prevents formation of the ruthe-
nium complex at a variety of conditions [12].
2.6. Mechanistic implication
Since 6 and 7 are both 18-electron ruthenium com-
plexes, the catalysis may begin by predissociation of
one of the coordination sites. The ruthenium–amine
bond is longer or maybe weaker than the other two
ruthenium–nitrogen bonds, and it is the most probable
bond to break before the catalyst coordinates with the
substrate. Since the chirality of the ligand comes from
the chiral axis of the molecule, pre-dissociation of the
Ru–amine bond would make the catalyst lose its chiral
induction in the transfer hydrogenations. It may ac-

80
L. Cai et al. / Journal of Organometallic Chemistry 568 (1998) 77–86
Fig. 1. Molecular structure of ligand 5 with atomic numbering (ORTEP, 50% probability ellipsoids, hydrogen atoms omitted for clarity).
count for the low chiral induction of the reductions. The
Ru–amine bond is also difficult to break, and it may be
the reason that a high temperature is needed for the
catalysts to be functional.
It was discovered that the ruthenium complex catalyzes
the transfer hydrogenations between ketones and iso-
propanol at 80°C. The reaction gives high chemical yield,
but only modest enantioselectivity is observed. The
general harsh conditions needed to open one coordina-
tion site for the reaction, probably the dissociation of the
amino group, may render the reactive intermediate less
selective toward the substrates.
2.7. Catalytic reacti6ity of the complex 6 for other
reactions
Other hydrogen sources, such as H2 and NaBH4, have
been tested for the reduction of ketones and h,i-unsat-
urated aldehydes or ketones. The former reagent gives no
product, and no change in catalyst is observed. The latter
in methanol destroys the catalyst, free ligand is observed
as checked by TLC.
4. Experimental
4.1. General considerations
(R)-(+)-2,2%-diamine-1,1%-binaphthyl, 8-quinolinesul-
fonyl chloride, and [RuCl2(p6-cumene)]2 were purchased
from Aldrich. All manipulations were carried out using
either high-vacuum or glovebox techniques. 1H- and 13C-
NMR spectra were recorded on a Bruker AMX-400 spec-
trometer at 400.1 and 100.6 MHz, a Bruker AMX-200
spectrometer at 200.1 MHz, or Varian 300 spectrometer
at 299.949 MHz and 75.429 MHz, respectively. Enantio-
selectivity (e. e.) was measured on Chiralcel-OD column
at 254 nm with isopropanol/hexane (5:95) as eluents.
3. Conclusion
We have described a ligand based on the monosulfon-
amide of 2,2%-diamine-1,1%-binaphthyl and its complex
with ruthenium(II). The ligand has a strong tendency to
retain its original configuration. Evaluation of the cata-
lytic properties of both the free ligand under in situ
conditions and its ruthenium complex has been described.

L. Cai et al. / Journal of Organometallic Chemistry 568 (1998) 77–86
81
Table 2
4.2. Ligand 5
Atomic coordinates (×104) and equivalent isotropic displacement
parameters (A2×103) for 5
(R)-(+)-2,2%-diamine-1,1%-binaphthyl (120 mg, 0.423
Atom
x
y
z
Ueq
Table 1
Crystal data and structure refinement for 5
S(1)
O(1)
O(2)
N(1)
N(2)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
N(3)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
N(1S)
C(1S)
C(2S)
8511(1)
9497(2)
8158(2)
8958(2)
8568(2)
7307(3)
8112(3)
8085(3)
7282(3)
5625(4)
4837(4)
4834(3)
5622(3)
6457(3)
6442(3)
7310(2)
7880(2)
7841(3)
7261(3)
6154(3)
5634(3)
5636(3)
6166(3)
6731(2)
6707(3)
8508(2)
8594(3)
7905(3)
7072(3)
6082(3)
5968(3)
6713(3)
7554(3)
7689(3)
6932(3)
9348(5)
9059(4)
8646(5)
5503(1)
5998(2)
5075(2)
3688(3)
4611(2)
4299(3)
4307(3)
4975(3)
5607(3)
6337(3)
6369(3)
5702(3)
5025(3)
4976(3)
5645(3)
3586(2)
3767(2)
3106(3)
2258(3)
1079(3)
839(3)
1509(3)
2402(3)
2666(3)
1990(3)
6619(2)
7109(3)
7860(3)
8081(3)
7755(3)
7239(3)
6529(3)
6355(3)
6862(3)
7580(3)
1682(4)
957(5)
1757(1)
2115(2)
2452(2)
−911(3)
1020(2)
−1025(2)
−1330(3)
−2082(3)
−2509(3)
−2612(3)
−2301(4)
−1573(3)
−1165(3)
−1461(3)
−2213(3)
−250(3)
732(3)
1461(3)
1199(3)
−76(3)
−1041(3)
−1773(3)
−1525(3)
−528(3)
204(3)
37(1)
45(1)
45(1)
61(1)
35(1)
33(1)
37(1)
46(1)
52(1)
67(1)
73(2)
58(1)
43(1)
36(1)
47(1)
31(1)
31(1)
41(1)
42(1)
43(1)
46(1)
42(1)
37(1)
31(1)
36(1)
39(1)
47(1)
55(1)
57(1)
55(1)
50(1)
41(1)
34(1)
36(1)
42(1)
178(3)
80(2)
156(3)
Crystal data
Empirical for-
mula
C29H21N3O2S·CH3CN
Crystal habit
Crystal system
Space group
Unit cell dimen-
sions
White
Monoclinic
P2(1)/n
˚
a (A)
14.1083 (10)
13.2949 (10)
14.8700 (11)
113.6460 (10)
2555.0 (3)
4
˚
b (A)
˚
c (A)
i (°)
Volume (A )
3
˚
Z
Formula weight 516.60
Dcalc (Mg m−3
)
1.343
0.164
Absorption co-
efficient
(mm−1
)
F(000)
1080
Data collection
Diffractometer
used
Siemens SMART/CCD
12(2)
˚
Radiation (A)
0.71073
−723(3)
−1271(3)
−1074(3)
−57(3)
684(3)
1225(3)
1016(3)
236(3)
−304(3)
374(7)
445(4)
Temperature (K) 213(2)
2q Range
3.36B2qB45.00
Scan speed (°
1.2 in ꢀ
min−1
)
Index range
−125h518, −175k517, −195l515
Total reflections 10 585
Independent
reflections
3339 [Rint=0.0595]
Solution and
refinement
System used
Solution
Refinement
method
Shelx 93
8(5)
473(6)
Direct methods
Full-matrix least-squares on F2
Ueq is defined as one third of the trace of the orthogonalized Uij
tensor.
Weighting
scheme
ꢀ
−1=|2(F2o)+(0.0553P)2+0.93(P)
P=[max(F2o, 0)+2(F2c)]/3
Final R Indices R1=0.0530
[I\2|(I)]
mmol) and 8-quinolinesulfonyl chloride (110 mg, 0.486
mmol) were dissolved in 120 ml dried acetonitrile under
nitrogen. Pyridine (0.2 ml) was then added into the
flask. The reaction mixture was refluxed overnight or
until the reaction was finished as checked by TLC.
After the reaction, silica gel (1–2 g) was added into the
flask. The solvent was removed. The product was iso-
lated by column chromatography with hexane/ethyl
acetate (3:1) as eluant to afford 193 mg product. Yield
R1=SꢀFoꢁ−ꢁFcꢀ/SꢁFoꢁ
wR2=0.1093, where wR2={S[w(F2o−Fc2)2]/
S[w(F2o)2]}1/2
R Indices (all
data)
R1=0.0974, wR2=0.1321
Goodness-of-fit
1.054, where GOF=[S[w(F2o−F2c)2/(n−p)]1/2
and n and p denotes the number of data and
parameters.
on F2
Data/restraints/ 3336/0/344
parameters
Maximum and
1
96%. H-NMR (CD3CN at 400 MHz), l, 8.55 (brs, 1H,
3
amide NH); 8.13–8.02 (m, 5H, Ar–H); 7.92 (d, JHH
=
minimum
8.2 Hz, 1H, Ar–H); 7.86 (dd, 3JHH=8.2 Hz, 4JHH=1.2
Difference peaks 0.332 and −0.345
−3
˚
(e A
)
Hz, 1H, Ar–H); 7.48–7.36 (m, 4H, Ar–H); 7.31 (dd,
3
3JHH=8.2 Hz, JHH=4.3 Hz, 1H, Ar–H); 7.15 (ddd,

82
L. Cai et al. / Journal of Organometallic Chemistry 568 (1998) 77–86
3
4
3JHH=8.3 Hz, JHH=9.8 Hz, JHH=1.1 Hz, 1H, Ar–
129.7; 129.4; 128.8; 128.6; 128.4; 127.3; 126.7; 126.2;
125.9; 125.7; 124.2; 123.4; 123.0; 122.2; 121.5; 118.8;
108.5. GCMS, 475 (35%, M+); 458 (5%, M-NH3+); 283
(45%, M-SO2Q+); 267 (100%, M-NHSO2Q+); 129
(60%, Q+H+). High resolution MS: Found,
475.135898; Calcd, 475.135449530.
H); 6.94 (ddd, 3JHH=7.1 Hz, 3JHH=8.1 Hz, 4JHH=1.0
Hz, 1H, Ar–H); 6.82 (d, JHH=8.8 Hz, 1H, Ar–H);
6.74 (d, JHH=8.8 Hz, 1H, Ar–H); 6.61 (ddd, JHH
7.0 Hz, JHH=8.2 Hz, 1H, Ar–H); 6.03 (d, JHH=8.3
Hz, 1H, Ar–H); 3.80 (brs, 2H, NH2). 13C{1H}-
(DMSO-d6 at 300 MHz), d, 185.3; 151.1; 145.1; 142.3;
137.0; 136.5; 135.2; 134.9; 134.4; 133.2; 132.0; 130.6;
3
3
3
=
3
3
4.3. Ruthenium complex 6
Ligand 5 (500 mg, 1.052 mmol) and [RuCl2(p6-
cumene)]2 (354 mg, 0.579 mmol) were dissolved in
isopropanol. Triethylamine (3 mmol) was added. The
mixture was refluxed at 80°C for 1 h or until the
starting material disappeared on TLC plate. The sol-
vent was removed, and the solid was washed with
water, to afford product, 738 mg. Recrystallization
from methanol/ether gave the product (660 mg).
Table 3
˚
Bond lengths (A) and angles (°) for 5
S(1)–O(2)
S(1)–N(2)
N(1)–C(2)
C(1)–C(2)
C(1)ꢁC(11)
C(3)ꢁC(4)
C(5)ꢁC(6)
C(6)ꢁC(7)
C(8)ꢁC(9)
C(11)ꢁC(12)
C(12)ꢁC(13)
C(14)ꢁC(20)
C(15)ꢁC(20)
C(17)ꢁC(18)
C(19)ꢁC(20)
N(3)ꢁC(29)
C(23)ꢁC(24)
C(25)ꢁC(26)
C(26)ꢁC(27)
C(28)ꢁC(29)
1.433(3) S(1)–O(1)
1.434(2)
1.767(4)
1.432(4)
1.429(5)
1.416(5)
1.421(6)
1.406(6)
1.369(5)
1.422(5)
1.437(5)
1.355(5)
1.362(5)
1.407(5)
1.417(5)
1.318(5)
1.404(5)
1.406(5)
1.406(5)
1.363(5)
1.418(5)
1.639(3) S(1)–C(28)
1.376(4) N(2)–C(12)
1.383(5) C(1)ꢁC(9)
1.490(5) C(2)ꢁC(3)
1.348(5) C(4)ꢁC(10)
1.366(6) C(5)ꢁC(10)
1.400(6) C(7)ꢁC(8)
1.415(5 C(9)ꢁC(10)
1.376(5) C(11)ꢁC(19)
1.415(5) C(13)ꢁC(14)
1.413(5) C(15)ꢁC(16)
1.410(5) C(16)ꢁC(17)
1.372(5) C(18)ꢁC(19)
1.423(5) N(3)ꢁC(22)
1.365(4) C(22)ꢁC(23)
1.353(5) C(24)ꢁC(30)
1.361(5) C(25)ꢁC(30)
1.401(5) C(27)ꢁC(28)
1.418(5) C(29)ꢁC(30)
Alternatively, after the reaction was complete, the
solvent was removed under vacuum. The solid was
completely dissolved in CH3CN. After a few minutes,
pure yellow product precipitated out. Yield 92%.
3
1H-NMR (CD3OD at 400 MHz), l, 10.31 (d, JHH
=
3
5.4 Hz, 1H, Ar–H); 8.61 (d, JHH=7.5 Hz, 1H, Ar–
H); 8.15 (d, 3JHH=9.0 Hz, 1H, Ar–H); 8.06 (d,
3JHH=8.4 Hz, 1H, Ar–H); 7.97 (d, JHH=8.1 Hz, 1H,
3
3
3
Ar–H); 7.84 (dd, JHH=5.4 Hz, JHH=8.4 Hz, 1H,
Ar–H); 7.68 (d, 3JHH=8.4 Hz, 1H, Ar–H); 7.42 (t,
3JHH=7.5 Hz, 1H, Ar–H); 7.29 (d, JHH=7.5 Hz, 2H,
3
Ar–H); 7.18 (t, 3JHH=7.2 Hz, 1H, Ar–H); 7.11 (t,
3JHH=7.6 Hz, 1H, Ar–H); 7.02 (t, JHH=7.6 Hz, 1H,
3
N(1S)ꢁC(1S)
1.068(6) C(1S)ꢁC(2S)
1.398(7)
108.6(2)
3
O(2)ꢁS(1)ꢁO(1)
O(1)ꢁS(1)ꢁN(2)
O(1)ꢁS(1)ꢁC(28)
C(12)ꢁN(2)ꢁS(1)
C(2)ꢁC(1)ꢁC(11)
N(1)ꢁC(2)ꢁC(1)
C(1)ꢁC(2)ꢁC(3)
C(3)ꢁC(4)ꢁC(10)
C(5)ꢁC(6)ꢁC(7)
C(7)ꢁC(8)ꢁC(9)
C(8)ꢁC(9)ꢁC(1)
C(5)ꢁC(10)ꢁC(4)
C(4)ꢁC(10)ꢁC(9)
C(12)ꢁC(11)ꢁC(1)
118.7(2)
O(2)ꢁS(1)ꢁN(2)
O(2)ꢁS(1)ꢁC(28)
N(2)ꢁS(1)ꢁC(28)
C(2)ꢁC(1)ꢁC(9)
C(9)ꢁC(1)ꢁC(11)
N(1)ꢁC(2)ꢁC(3)
C(4)ꢁC(3)ꢁC(2)
C(6)ꢁC(5)ꢁC(10)
C(8)ꢁC(7)ꢁC(6)
C(8)ꢁC(9)ꢁC(10)
C(10)ꢁC(9)ꢁC(1)
C(5)ꢁC(10)ꢁC(9)
Ar–H); 6.79 (t, JHH=7.6 Hz, 1H, Ar–H); 6.63 (dd,
3JHH=3.9 Hz, 3JHH=8.4 Hz, 3H, Ar–H); 6.24 (d,
106.3(2)
108.8(2)
124.0(2)
120.7(3)
121.7(3)
119.9(3)
121.7(4)
119.8(4)
121.5(4)
122.7(3)
122.5(4)
118.0(4)
121.9(3)
107.7(2)
106.0(2)
119.7(3)
119.6(3)
118.4(3)
120.9(4)
121.2(4)
120.3(4)
117.6(3)
119.8(3)
119.5(4)
3JHH=6.0 Hz, 1H, Ar–H); 6.15 (d, JHH=3.6 Hz, 1H,
3
Ar–H); 6.14 (d, 3JHH=8.4 Hz, 1H, Ar-H); 6.03 (d,
3JHH=6.0 Hz, 1H, Ar–H); 5.87 (d, JHH=6.0 Hz, 1H,
3
3
Ar–H); 2.81 (hepta, JHH=6.9 Hz, 1H, CH); 2.02 (s,
3H, CH3); 1.06 (d, JHH=6.9 Hz, 3H, CH3); 0.89 (d,
3
3JHH=6.9 Hz, 3H, CH3). 13C{1H}- (DMSO-d6 at 300
MHz), l, 163.9; 144.6; 143.6; 142.9; 137.4; 136.3; 134.9;
134.0; 133.8; 133.6; 132.6; 132.5; 132.1; 131.2; 131.1;
129.3; 128.9; 128.7; 128.2; 127.5; 127.4; 127.1; 126.8;
126.7; 126.5; 126.1; 124.5; 118.7; 118.2; 108.5; 96.3;
96.1; 92.3; 89.6; 85.1; 31.7 (1C, CH); 22.9 (1C, CH3);
21.5 (1C, CH3); 17.7 (1C, CH3). FAB, 710 (22%, M-
Cl+); 512 (100%, M-Ru(cumene)+H+); 385 (77%,
M-Ru(cumene)-Q+H+). High resolution FAB for
C39H34N3O2SRu, the cationic portion of the complex:
Found, 710.142400; Calcd, 710.141522. Elemental anal-
ysis of C39H34N3O2SRuCl: Found, C, 61.89; H, 4.56; N,
5.82; Calcd, C, 62.87; H, 4.57; N, 5.63.
C(12)ꢁC(11)ꢁC(19) 118.5(3)
C(19)ꢁC(11)ꢁC(1)
C(11)ꢁC(12)ꢁN(2)
119.6(3)
119.5(3)
C(11)ꢁC(12)ꢁC(13) 121.3(3)
C(13)ꢁC(12)ꢁN(2) 119.2(3)
C(14)ꢁC(13)ꢁC(12) 120.1(3)
C(16)ꢁC(15)ꢁC(20) 120.9(4)
C(18)ꢁC(17)ꢁC(16) 120.7(4)
C(18)ꢁC(19)ꢁC(20) 118.0(3)
C(20)ꢁC(19)ꢁC(11) 120.1(3)
C(15)ꢁC(20)ꢁC(19) 119.7(3)
C(13)ꢁC(14)ꢁC(20) 121.9(4)
C(15)ꢁC(16)ꢁC(17) 119.9(4)
C(17)ꢁC(18)ꢁC(19) 120.8(4)
C(18)ꢁC(19)ꢁC(11) 121.9(3)
C(15)ꢁC(20)ꢁC(14) 122.3(4)
C(14)ꢁC(20)ꢁC(19) 118.0(3)
C(22)ꢁN(3)ꢁC(29)
117.0(3)
N(3)ꢁC(22)ꢁC(23)
124.1(4)
C(24)ꢁC(23)ꢁC(22) 119.2(4)
C(26)ꢁC(25)ꢁC(30) 121.2(4)
C(28)ꢁC(27)ꢁC(26) 120.3(4)
C(23)ꢁC(24)ꢁC(30) 119.5(4)
C(25)ꢁC(26)ꢁC(27) 120.0(4)
C(27)ꢁC(28)ꢁC(29) 121.3(3)
C(29)ꢁC(28)ꢁS(1)
N(3)ꢁC(29)ꢁC(30)
C(25)ꢁC(30)ꢁC(24) 123.2(4)
C(24)ꢁC(30)ꢁC(29) 117.4(4)
C(27)ꢁC(28)ꢁS(1)
N(3)ꢁC(29)ꢁC(28)
C(28)ꢁC(29)ꢁC(30) 117.8(3)
C(25)ꢁC(30)ꢁC(29) 119.4(4)
N(1S)ꢁC(1S)ꢁC(2S) 176.4(8)
119.0(3)
119.4(3)
4.4. Ruthenium complex 7
119.7(3)
122.7(3)
Ruthenium complex 6 was dissolved in acetone. Then
AgPF6 (one equivalent) in acetone was added. A white
precipitate came out immediately. After filtering the

L. Cai et al. / Journal of Organometallic Chemistry 568 (1998) 77–86
83
Fig. 2. Molecular structure of the ruthenium complex 6 with atomic numbering (ORTEP, 50% probability ellipsoids, hydrogen atoms omitted for
clarity).
solid through celite, the solvent of the clear solution
4.5. Catalytic reactions
was removed to generate the product 7 with exchanged
1
counterion. H-NMR (acetone-d6 at 400 MHz), l, 10.6
Typical procedure: acetophenone (12 mg, 0.1 mmol)
was dissolved in isopropanol or 1:1 mixture of iso-
propanol and other solvent (THF, ether, methylene
chloride). Ruthenium complex 6 (7 mg, 0.01 mmol) was
added. The reaction flask was put in an oil bath at
80°C. The reaction mixture was refluxed overnight. The
solvent was removed, and the product was purified by
TLC plate.
3
3
(d, JHH=5.4 Hz, 1H, Ar–H); 8.67 (d, JHH=7.5 Hz,
3
1H, Ar–H); 8.16 (s, 2H, Ar–H); 8.00 (dd, JHH=8.1
Hz, 4JHH=0.9 Hz, 1H, Ar–H); 7.87 (dd, 3JHH=5.4
3
3
Hz, JHH=8.1 Hz, 1H, Ar-H); 7.72 (dd, JHH=8.1 Hz,
4JHH=1.8 Hz, 1H, Ar–H); 7.41 (td, 3JHH=7.5 Hz,
4JHH=1.5 Hz, 1H, Ar–H); 7.28 (td, 3JHH=7.2 Hz,
4JHH=1.5 Hz, 2H, Ar–H); 7.18 (td, 3JHH=7.2 Hz,
4JHH=1.5 Hz, 1H, Ar–H); 7.09 (td, 3JHH=7.6 Hz,
4JHH=1.2 Hz, 1H, Ar–H); 7.02 (td, 3JHH=7.6 Hz,
1
For sec-phenethyl alcohol, H-NMR in acetone-d6,
7.388–7.191 (m, 5H, Ar–H), 4.825 (m, 1H, CH), 4.157
4JHH=1.2 Hz, 1H, Ar–H); 6.79 (t, JHH=7.6 Hz, 1H,
3
3
3
(d, 1H, JHH=4.5 Hz, OH), 1.383 (d, 3H, JHH=6.6
3
Ar–H); 6.68 (d, JHH=9.0 Hz, 1H, Ar–H); 6.59 (d,
Hz, CH3).
3JHH=8.1 Hz, 1H, Ar–H); 6.52 (d, JHH=8.1 Hz, 1H,
3
1
For 1,2,3,4-tetrahydro-1-naphthol, H-NMR in ace-
tone-d6, 7.436–7.03 (m, 5H, Ar–H); 4.675 (vt, JHH
3
Ar–H); 6.33 (d, JHH=6.0 Hz, 1H, Ar–H); 6.28 (d,
3
=
3JHH=5.4 Hz, 1H, Ar–H); 6.18 (d, JHH=8.4 Hz, 1H,
3
3
4.2 Hz, 1H, CH); 4.008 (d, JHH=6.0 Hz, 1H, OH);
2.812–2.702 (m, 2H, CH2), 2.011–1.942 (m, 2H, CH2);
1.824–1.707 (m, 2H, CH2). MS, 148 (M+, 40%), 130
(M-H2O+, 100%), 120 (M-C2H4+, 100%), 105 (45%), 91
(80%), 77 (20%).
3
4
Ar–H); 6.14 (dd, JHH=5.4 Hz, JHH=0.9 Hz, 1H,
Ar–H); 6.05 (dd, 3JHH=5.7 Hz, 4JHH=0.9 Hz, 1H,
3
Ar–H); 3.00 (hepta, JHH=6.9 Hz, 1H, CH); 2.09 (s,
3
3H, CH3); 1.06 (d, JHH=6.9 Hz, 3H, CH3); 0.89 (d,
3JHH=6.9 Hz, 3H, CH3).

84
L. Cai et al. / Journal of Organometallic Chemistry 568 (1998) 77–86
Table 5
4.6. Collection and reduction of X-ray data for 5 and 6
Atomic coordinates (×104) and equivalent isotropic displacement
parameters (A2×103) for 6
The crystals of 5 were grown from CH3CN/ether.
For 6, a number of solvent systems have been tested for
generating X-ray quality crystals such as acetone–
ether, methanol–ether, acetonitrile–ether, and THF–
ether. Poor X-ray quality crystals are generated only in
acetonitrile–ether system, only powders are generated
in other combinations. Multiple sequential recrystalliza-
tions from acetonitrile/ether give crystals enough for
single crystal diffraction study.
Ru(1A)
Cl(1A)
S(1A)
2194(2)
3562(5)
2921(1)
3735(1)
2322(2)
1969(4)
2404(3)
2983(4)
2430(4)
3131(4)
2571(5)
2913(6)
3187(5)
3128(5)
2707(5)
2373(5)
2100(6)
2159(5)
2501(5)
2783(5)
2282(5)
2225(5)
1942(5)
1761(5)
1631(6)
1691(6)
1926(5)
2128(5)
2083(5)
1806(5)
3485(5)
3694(5)
3539(5)
3004(5)
2651(6)
2455(6)
2611(5)
2977(5)
3178(5)
3036(6)
3341(6)
3298(6)
2950(7)
2671(6)
2721(6)
3071(6)
2930(7)
3039(6)
3141(6)
4982(1)
4168(1)
5580(2)
5929(3)
5496(4)
4913(4)
5470(4)
4766(4)
5330(5)
5002(5)
4716(5)
4771(5)
5202(5)
5539(6)
5814(6)
5752(5)
5507(1)
3211(6)
4976(6)
27(1)
53(2)
43(2)
61(5)
47(4)
27(3)
30(3)
25(3)
24(3)
23(3)
24(3)
26(3)
37(3)
40(3)
39(3)
34(3)
24(3)
26(3)
30(3)
34(3)
45(4)
48(4)
50(4)
53(4)
49(4)
40(3)
35(3)
45(3)
34(3)
36(3)
38(3)
44(3)
48(4)
44(4)
30(3)
30(3)
36(3)
42(4)
35(3)
35(3)
34(3)
40(4)
43(4)
60(6)
39(3)
50(5)
63(5)
26(1)
49(2)
36(2)
50(4)
52(4)
22(3)
24(3)
25(3)
25(3)
22(3)
28(3)
28(3)
39(3)
44(4)
43(4)
34(3)
−239(6)
−649(16)
−268(15)
2444(13)
1309(15)
−9(14)
O(1A)
O(2A)
N(1A)
N(2A)
N(3A)
C(1A)
C(2A)
C(3A)
C(4A)
C(5A)
C(6A)
C(7A)
C(8A)
C(9A)
C(10A)
C(11A)
C(12A)
C(13A)
C(14A)
C(15A)
C(16A)
C(17A)
C(18A)
C(19A)
C(20A)
C(22A)
C(23A)
C(24A)
C(25A)
C(26A)
C(27A)
C(28A)
C(29A)
C(30A)
C(31A)
C(32A)
C(33A)
C(34A)
C(35A)
C(36A)
C(37A)
C(38A)
C(39A)
C(40A)
Ru(1B)
Cl(1B)
S(1B)
4518(15)
6206(12)
3672(12)
4832(14)
4699(13)
2260(16)
2631(14)
2057(16)
1073(16)
−182(18)
−478(18)
141(18)
983(18)
1356(16)
759(17)
2877(18)
4155(17)
4782(20)
4136(21)
2258(21)
1108(22)
449(21)
737(18)
1126(16)
283(17)
Table 4
−1073(18)
−2962(18)
−3473(19)
−2544(18)
−1184(18)
−622(17)
−1560(17)
1786(19)
2080(19)
3027(21)
3806(22)
4478(23)
4340(23)
3284(21)
2425(20)
2576(20)
3593(22)
−19(20)
−1279(19)
−2558(21)
−4006(20)
−4121(22)
−2939(22)
−1621(18)
−1418(18)
−2676(20)
4594(21)
3767(19)
2714(19)
2403(17)
3202(20)
4379(20)
5767(20)
1349(17)
2242(21)
−86(22)
3180(2)
Crystal data and structure refinement for 6
Crystal data
Empirical formula
Crystal habit
C39H34ClN3O2RuS·2CH3CN
Yellow
Crystal system
Space group
Monoclinic
P2(1)
Unit cell dimensions
˚
a (A)
9.3025 (5)
38.273 (2)
11.4226 (7)
108.263 (2)
3862.0(4)
4
˚
b (A)
˚
c (A)
i (°)
Volume (A )
Z
3
˚
990(21)
2206(19)
2871(21)
4683(18)
4061(18)
3408(18)
2641(18)
2607(20)
3259(20)
4025(17)
4031(15)
3351(18)
6252(19)
6420(17)
7065(18)
7527(15)
7261(18)
6719(18)
5596(19)
8277(15)
9614(18)
7818(21)
4447(1)
Formula weight
827.38
1.423
0.573
Dcalc (Mg m−3
)
Absorption coefficient (mm−1
)
F(000)
1704
Data collection
Diffractometer used
Radiation (A)
Siemens SMART/CCD
0.71073
˚
Temperature (K)
2q Range
213(2)
2.12B2qB48.00
1.2 in ꢀ
−125h512, −375k550,
−145l515
Scan speed (° min−1
Index range
)
Total reflections
19012
Independent reflections
9231 [Rint=0.1579]
Solution and refinement
System used
Shelx 93
Solution
Refinement method
Weighting scheme
Direct methods
Full-matrix least-squares on F2
ꢀ
−1=|2(F2o)+(0.0523P)2
P=[max(F2o, 0)+2(F2c)]/3
R1=0.0794
Final R Indices [I\2|(I)]
1816(5)
5620(6)
6727(6)
4975(5)
R1=SꢀFoꢁ−ꢁFcꢀ/SꢁFoꢁ
wR2=0.1261, where
wR2=[S[w(F2o−Fc2)2]/
S[w(F2o)2]]1/2
R1=0.1730, wR2=0.1830
0.997, where
O(1B)
O(2B)
N(1B)
N(2B)
N(3B)
C(1B)
C(2B)
C(3B)
C(4B)
C(5B)
6038(15)
5686(14)
2939(13)
4067(15)
5425(15)
4619(18)
4251(15)
5177(17)
6452(17)
8366(19)
8775(19)
7860(19)
6526(19)
5411(15)
3774(13)
6275(12)
5128(14)
5284(14)
7671(17)
7341(15)
8001(17)
8881(17)
10176(18)
10427(19)
9759(18)
8932(18)
R indices (all data)
Goodness-of-fit on F2
GOF=[S[w(F2o−F2c)2/(n−p)]1/2
and n and p denotes the
number of data and parameters
9218/601/960
Data/restraints/parameters
Maximum and minimum
difference peaks (e A
0.757 and −0.707
−3
˚
)
C(6B)
C(7B)
C(8B)
Absolute structure parameter
0.54(9)

L. Cai et al. / Journal of Organometallic Chemistry 568 (1998) 77–86
85
Table 5 (Continued)
Table 6
Selected bond lengths (A) and angles (°) for 6
˚
C(9B)
6030(18)
5404(5)
5118(5)
5626(5)
5683(5)
5937(5)
6148(5)
6277(5)
6215(6)
5955(5)
5770(5)
5824(5)
6083(5)
4411(5)
4199(6)
4345(5)
4871(5)
5226(6)
5438(6)
5296(5)
4918(5)
4729(5)
4858(5)
4583(5)
4608(5)
4932(5)
5229(5)
5195(5)
4819(5)
4961(7)
4887(6)
4758(6)
1640(8)
3701(8)
4199(8)
6243(8)
1414(10)
1162(8)
3797(9)
3906(8)
4107(10)
3990(8)
6498(9)
6839(7)
8651(17)
9252(17)
7026(17)
5817(17)
5224(19)
5758(18)
7639(20)
8865(21)
9538(20)
8998(19)
7674(18)
7017(19)
5302(18)
5897(19)
6533(19)
7366(17)
7424(19)
6692(19)
5954(17)
5899(15)
6623(18)
3681(18)
3444(17)
2903(17)
2447(15)
2647(17)
3296(18)
4286(19)
1721(16)
336(18)
29(3)
26(3)
28(3)
28(3)
35(3)
35(3)
42(3)
50(4)
42(3)
39(3)
30(3)
34(3)
35(3)
38(3)
41(3)
37(3)
43(4)
36(3)
27(3)
26(3)
32(3)
31(3)
31(3)
29(3)
26(3)
30(3)
32(3)
47(5)
38(3)
47(5)
57(5)
104(8)
125(10)
105(8)
97(7)
95(8)
113(9)
108(9)
106(9)
102(8)
101(8)
83(7)
101(8)
C(10B)
C(11B)
C(12B)
C(13B)
C(14B)
C(15B)
C(16B)
C(17B)
C(18B)
C(19B)
C(20B)
C(22B)
C(23B)
C(24B)
C(25B)
C(26B)
C(27B)
C(28B)
C(29B)
C(30B)
C(31B)
C(32B)
C(33B)
C(34B)
C(35B)
C(36B)
C(37B)
C(38B)
C(39B)
C(40B)
N(1S)
6912(17)
3525(18)
3370(18)
2358(19)
1559(20)
850(22)
Ru(1A)–N(2A)
Ru(1A)–C(35A)
Ru(1A)ꢁN(1A)
Ru(1A)ꢁC(36A)
Ru(1A)ꢁC(34A)
S(1A)ꢁO(1A)
S(1A)ꢁC(28A)
N(2A)ꢁC(12A)
N(3A)ꢁC(29A)
C(1A)ꢁC(9A)
2.10(2) Ru(1A)–N(3A)
2.15(2) Ru(1A)–C(31A)
2.194(12) Ru(1A)ꢁC(32A)
2.21(2) Ru(1A)ꢁC(33A)
2.26(2) S(1A)ꢁO(2A)
1.46(2) S(1A)ꢁN(2A)
1.78(2) N(1A)ꢁC(2A)
1.44(2) N(3A)ꢁC(22A)
1.42(2) C(1A)ꢁC(2A)
1.39(2) C(1A)ꢁC(11A)
1.35(2) C(3A)ꢁC(4A)
1.40(2) C(5A)ꢁC(6A)
1.44(2) C(6A)ꢁC(7A)
1.35(2) C(8A)ꢁC(9A)
1.42(2) C(11A)ꢁC(12A)
1.44(2) C(12A)ꢁC(13A)
1.37(3) C(14A)ꢁC(20A)
1.30(3) C(15A)ꢁC(20A)
1.37(3) C(17A)ꢁC(18A)
1.36(3) C(19A)ꢁC(20A)
1.41(2) C(23A)ꢁC(24A)
1.39(3) C(25A)ꢁC(26A)
1.41(3) C(26A)ꢁC(27A)
1.40(3) C(28A)ꢁC(29A)
1.41(3) C(31A)ꢁC(36A)
1.44(3) C(31A)ꢁC(37A)
1.41(2) C(33A)ꢁC(34A)
1.39(3) C(34A)ꢁC(38A)
1.43(2) C(38A)ꢁC(40A)
1.55(3)
2.125(14)
2.17(2)
2.20(2)
2.22(2)
1.449(13)
1.555(14)
1.44(2)
1.35(2)
1.39(2)
1.50(2)
1.42(2)
1.37(3)
1.40(3)
1.42(2)
1.41(2)
1.44(2)
1.41(3)
1.40(2)
1.39(2)
1.47(3)
1.33(3)
1.35(3)
1.35(3)
1.41(3)
1.36(3)
1.51(2)
1.49(3)
1.49(2)
1.51(3)
1059(22)
2078(21)
2950(20)
2746(20)
1695(20)
5410(20)
6622(20)
7946(21)
9419(19)
9531(20)
8332(19)
7030(17)
6768(17)
8055(19)
717(20)
1546(19)
2647(19)
2963(17)
2154(18)
1030(19)
−472(19)
4059(17)
3142(21)
5466(19)
−5656(33)
−3300(31)
−1352(28)
978(29)
C(2A)ꢁC(3A)
C(4A)ꢁC(10A)
C(5A)ꢁC(10A)
C(7A)ꢁC(8A)
C(9A)ꢁC(10A)
C(11A)ꢁC(19A)
C(13A)ꢁC(14A)
C(15A)ꢁC(16A)
C(16A)ꢁC(17A)
C(18A)ꢁC(19A)
C(22A)ꢁC(23A)
C(24A)ꢁC(30A)
C(25A)ꢁC(30A)
C(27A)ꢁC(28A)
C(29A)ꢁC(30A)
C(31A)ꢁC(32A)
C(32A)ꢁC(33A)
C(34A)ꢁC(35A)
C(35A)ꢁC(36A)
C(38A)ꢁC(39A)
N(2A)ꢁRu(1A)ꢁN(3A)
N(3A)ꢁRu(1A)ꢁC(35A)
N(3A)ꢁRu(1A)ꢁC(31A)
N(2A)ꢁRu(1A)ꢁN(1A)
C(35A)ꢁRu(1A)ꢁN(1A)
N(2A)ꢁRu(1A)ꢁC(32A)
2190(20)
−2098(26)
−1457(32)
1349(23)
2072(23)
−2408(33)
−2978(29)
−881(38)
−236(31)
812(31)
88.0(5) N(2A)ꢁRu(1A)ꢁC(35A)
130.8(6) N(2A)ꢁRu(1A)ꢁC(31A)
145.8(7) C(35A)ꢁRu(1A)ꢁC(31A) 68.3(8)
83.8(6) N(3A)ꢁRu(1A)ꢁN(1A)
142.4(6) C(31A)ꢁRu(1A)ꢁN(1A)
162.3(7) N(3A)ꢁRu(1A)ꢁC(32A)
87.2(7)
124.2(7)
N(2S)
N(3S)
N(4S)
C(1S)
C(2S)
C(3S)
C(4S)
C(5S)
85.4(5)
87.0(6)
109.6(6)
−6372(43)
−7494(36)
−4130(42)
−5042(34)
−532(40)
513(31)
C(35A)ꢁRu(1A)ꢁC(32A) 81.5(8) C(31A)ꢁRu(1A)ꢁC(32A) 38.5(7)
N(1A)ꢁRu(1A)ꢁC(32A)
N(3A)ꢁRu(1A)ꢁC(36A)
96.9(6) N(2A)ꢁRu(1A)ꢁC(36A)
167.8(6) C(35A)ꢁRu(1A)ꢁC(36A) 38.3(6)
95.7(7)
C(6S)
C(7S)
C(8S)
213(27)
2380(29)
2836(27)
C(31A)ꢁRu(1A)ꢁC(36A) 36.1(7) N(1A)ꢁRu(1A)ꢁC(36A)
C(32A)ꢁRu(1A)ꢁC(36A) 67.1(8) N(2A)ꢁRu(1A)ꢁC(33A)
106.5(6)
146.9(6)
1427(37)
2247(32)
N(3A)ꢁRu(1A)ꢁC(33A)
92.3(6) C(35A)ꢁRu(1A)ꢁC(33A) 67.7(8)
C(31A)ꢁRu(1A)ꢁC(33A) 67.4(7) N(1A)ꢁRu(1A)ꢁC(33A)
129.3(7)
Ueq is defined as one third of the trace of the orthogonalized Uij
tensor.
C(32A)ꢁRu(1A)ꢁC(33A) 37.1(6) C(36A)ꢁRu(1A)ꢁC(33A) 78.2(7)
N(2A)ꢁRu(1A)ꢁC(34A) 108.6(7) N(3A)ꢁRu(1A)ꢁC(34A) 100.8(6)
C(35A)ꢁRu(1A)ꢁC(34A) 36.6(7) C(31A)ꢁRu(1A)ꢁC(34A) 80.8(7)
N(1A)ꢁRu(1A)ꢁC(34A) 166.1(7) C(32A)ꢁRu(1A)ꢁC(34A) 69.4(7)
C(36A)ꢁRu(1A)ꢁC(34A) 66.9(6) C(33A)ꢁRu(1A)ꢁC(34A) 38.9(7)
The crystals of 5 and 6 were transferred to a Siemens
SMART/CCD three circle ( fixed at 54.65°) diffrac-
tometer equipped with a cold stream of N2 gas and a
graphite-monochromated Mo–Kh radiation source.
Data collection was performed at −60°C with an
X-ray power of 2.2 kW. A total of 1321 frames of
two-dimensional diffraction images were collected, each
of which was measured for 10 s. Crystallographic data
for 5 and 6 are summarized in Tables 1 and 4,
respectively.
The raw data frames were processed to produce
conventional intensity data by the program SAINT. An
initial background was determined from the first 12° of
data. Integration was performed with constant spot
sizes of 1.75° in the detector plane and 0.9° in omega.
O(2A)ꢁS(1A)ꢁO(1A)
O(1A)ꢁS(1A)ꢁN(2A)
O(1A)ꢁS(1A)ꢁC(28A)
C(2A)ꢁN(1A)ꢁRu(1A)
C(12A)ꢁN(2A)ꢁRu(1A)
C(22A)ꢁN(3A)ꢁC(29A)
C(29A)ꢁN(3A)ꢁRu(1A)
C(2A)ꢁC(1A)ꢁC(11A)
C(3A)ꢁC(2A)ꢁC(1A)
C(1A)ꢁC(2A)ꢁN(1A)
C(10A)ꢁC(4A)ꢁC(3A)
C(5A)ꢁC(6A)ꢁC(7A)
C(7A)ꢁC(8A)ꢁC(9A)
C(1A)ꢁC(9A)ꢁC(8A)
C(4A)ꢁC(10A)ꢁC(9A)
C(9A)ꢁC(10A)ꢁC(5A)
117.8(8) O(2A)ꢁS(1A)ꢁN(2A)
110.9(8) O(2A)ꢁS(1A)ꢁC(28A)
107.4(9) N(2A)ꢁS(1A)ꢁC(28A)
116.8(8) C(12A)ꢁN(2A)ꢁS(1A)
118.8(10) S(1A)ꢁN(2A)ꢁRu(1A)
114(2) C(22A)ꢁN(3A)ꢁRu(1A)
132.6(12) C(2A)ꢁC(1A)ꢁC(9A)
119(2) C(9A)ꢁC(1A)ꢁC(11A)
122(2) C(3A)ꢁC(2A)ꢁN(1A)
120(2) C(2A)ꢁC(3A)ꢁC(4A)
119(2) C(6A)ꢁC(5A)ꢁC(10A)
117(2) C(8A)ꢁC(7A)ꢁC(6A)
123(2) C(1A)ꢁC(9A)ꢁC(10A)
125(2) C(10A)ꢁC(9A)ꢁC(8A)
119(2) C(4A)ꢁC(10A)ꢁC(5A)
110.1(8)
103.1(8)
106.6(8)
123.0(13)
117.9(8)
112.7(11)
120(2)
121(2)
118(2)
120(2)
123(2)
122(2)
119(2)
116(2)
122(2)
119(2) C(12A)ꢁC(11A)ꢁC(19A) 120(2)

86
L. Cai et al. / Journal of Organometallic Chemistry 568 (1998) 77–86
Table 6 (Continued)
atom atomic positional and equivalent isotropic ther-
mal parameters, selected bond distances and angles for
5 and 6 are provided in Tables 2, 3, 5 and 6. Final
anisotropic temperature factors and hydrogen posi-
tional parameters are given in Tables S1–S5.
C(12A)ꢁC(11A)ꢁC(1A)
C(11A)ꢁC(12A)ꢁC(13A) 122(2) C(11A)ꢁC(12A)ꢁN(2A)
C(13A)ꢁC(12A)ꢁN(2A)
C(13A)ꢁC(14A)ꢁC(20A) 124(2) C(16A)ꢁC(15A)ꢁC(20A) 122(2)
C(15A)ꢁC(16A)ꢁC(17A) 120(2) C(16A)ꢁC(17A)ꢁC(18A) 122(2)
C(19A)ꢁC(18A)ꢁC(17A) 120(2) C(18A)ꢁC(19A)ꢁC(11A) 125(2)
C(18A)ꢁC(19A)ꢁC(20A) 118(2) C(11A)ꢁC(19A)ꢁC(20A) 118(2)
C(15A)ꢁC(20A)ꢁC(14A) 123(2) C(15A)ꢁC(20A)ꢁC(19A) 118(2)
119(2) C(19A)ꢁC(11A)ꢁC(1A)
121(2)
120(2)
118(2) C(14A)ꢁC(13A)ꢁC(12A) 117(2)
5. Supplementary material
C(14A)ꢁC(20A)ꢁC(19A) 119(2) N(3A)ꢁC(22A)ꢁC(23A)
125(2)
C(24A)ꢁC(23A)ꢁC(22A) 119(2) C(23A)ꢁC(24A)ꢁC(30A) 121(2)
C(26A)ꢁC(25A)ꢁC(30A) 122(2) C(27A)ꢁC(26A)ꢁC(25A) 120(2)
C(26A)ꢁC(27A)ꢁC(28A) 121(2) C(27A)ꢁC(28A)ꢁC(29A) 121(2)
Tables of atom coordinates, anisotropic thermal
parameters of 5 and 6 (22 pages) are available from the
author (L.C.).
C(27A)ꢁC(28A)ꢁS(1A)
C(30A)ꢁC(29A)ꢁC(28A) 117(2) C(30A)ꢁC(29A)ꢁN(3A)
C(28A)ꢁC(29A)ꢁN(3A)
116(2) C(29A)ꢁC(28A)ꢁS(1A)
122.8(13)
122(2)
121(2) C(24A)ꢁC(30A)ꢁC(29A) 119(2)
C(24A)ꢁC(30A)ꢁC(25A) 123(2) C(29A)ꢁC(30A)ꢁC(25A) 119(2)
C(36A)ꢁC(31A)ꢁC(32A) 121(2) C(36A)ꢁC(31A)ꢁC(37A) 120(2)
C(32A)ꢁC(31A)ꢁC(37A) 120(2) C(36A)ꢁC(31A)ꢁRu(1A) 73.4(13)
C(32A)ꢁC(31A)ꢁRu(1A) 72.0(11) C(37A)ꢁC(31A)ꢁRu(1A) 129.7(14)
C(33A)ꢁC(32A)ꢁC(31A) 118(2) C(33A)ꢁC(32A)ꢁRu(1A) 72.2(10)
C(31A)ꢁC(32A)ꢁRu(1A) 69.5(12) C(32A)ꢁC(33A)ꢁC(34A) 122(2)
C(332A)ꢁC(33A)ꢁRu(1A) 70.7(10) C(34A)ꢁC(33A)ꢁRu(1A) 71.7(10)
C(35A)ꢁC(34A)ꢁC(38A) 125(2) C(35A)ꢁC(34A)ꢁC(33A) 116(2)
C(38A)ꢁC(34A)ꢁC(33A) 119(2) C(35A)ꢁC(34A)ꢁRu(1A) 67.6(10)
C(38A)ꢁC(34A)ꢁRu(1A) 136.3(12) C(33A)ꢁC(34A)ꢁRu(1A) 69.3(10)
C(34A)ꢁC(35A)ꢁC(36A) 122(2) C(34A)ꢁC(35A)ꢁRu(1A) 75.8(11)
C(36A)ꢁC(35A)ꢁRu(1A) 73.0(11) C(31A)ꢁC(36A)ꢁC(35A) 121(2)
C(31A)ꢁC(36A)ꢁRu(1A) 70.5(13) C(35A)ꢁC(36A)ꢁRu(1A) 68.7(10)
C(34A)ꢁC(38A)ꢁC(40A) 116(2) C(34A)ꢁC(38A)ꢁC(39A) 107.8(14)
C(40A)ꢁC(38A)ꢁC(39A) 110(2)
Acknowledgements
We are grateful to The University of Illinois at
Chicago for financial support.
References
[1] R. Noyori, Asymmetric Catalysis in Organic Synthesis, Wiley,
New York, 1994, Chapter 2.
[2] (a) J.B. Jones, Tetrahedron 42 (1986) 3351. (b) E. Schoffers, A.
Golebiowski, C.R. Johnson, Tetrahedron 52 (1996) 3769.
[3] (a) G. Zassinovich, G. Mestroni, S. Gladiali, Chem. Rev. 92
(1992) 1051. (b) C.F. de Graauw, J.A. Peters, H. van Bekkum, J.
Huskens, J. Synth. (1994) 1007.
[4] (a) M. Saburi, M. Ohnuki, M. Ogasawara, T. Takahashi, Y.
Uchida, Tetrahedron Lett. 33 (1992) 5783. (b) W. Leitner, J.M.
Brown, H.J. Brunner, J. Am. Chem. Soc. 115 (1993) 152. (c) R.
Noyori, S. Hashiguchi, Acc. Chem. Res. 30 (1997) 97.
[5] (a) I. Ojima (Ed.) Catalytic Asymmetric Synthesis, VCH, New
York, 1993. (b) R. Noyori, Asymmetric Catalysis in Organic
Synthesis, Wiley, New York, 1994.
[6] (a) K. Kabuto, T. Yoshida, S. Yamaguchi, S. Miyano, H.
Hashimoto, J. Org. Chem. 50 (1985) 3013. (b) C.-W. Ho, W.-C.
Cheng, M.-C. Cheng, S.-M. Peng, K.-F. Cheng, C.-M. Che, J.
Chem. Soc. Dalton Trans. (1996) 405. (c) E.M. Carreira, R.A.
Singer, W.J. Lee, J. Am. Chem. Soc. 116 (1994) 8837. (d) J.-H.
Lin, C.-M. Che, T.-F. Lai, C.-K. Poon, Y.X. Cui, J. Chem. Soc.
Chem. Commun. (1991) 468.
Scheme 4. Asymmetric transfer hydrogenations by ruthenium com-
plex 6.
[7] (a) K. Kabuto, T. Yoshida, S. Yamaguchi, S. Miyano, H.J.
Hashimoto, Org. Chem. 50 (1985) 3013. (b) C.-W. Ho, W.-C.
Cheng, M.-C. Cheng, S.-M. Peng, K.-F. Cheng, C.-M. Che, J.
Chem. Soc. Dalton Trans. (1996) 405. (c) E.M. Carreira, R.A.
Singer, W. Lee, J. Am. Chem. Soc. 116 (1994) 8837. (d) J.-H.
Lin, C.-M. Che, T.-F. Lai, C.-K. Poon, Y.X. Cui, J. Chem. Soc.
Chem. Commun. (1991) 468.
[8] Y. Han, L. Cai, Tetrahedron Lett. 38 (1997) 5423–5426.
[9] K.K. Andersen, Sulphonic acids and their derivatives, in:
D.H.R. Barton, W.D. Ollis (Eds.), Comprehensive Organic
Chemistry, vol. 3, Pergamon Press, Oxford, 1979.
The intensity data were corrected for Lorentz, polariza-
tion effects, and absorption corrections.
4.7. Solution and refinement of structures 5 and 6
The structures were solved by direct methods and
standard difference Fourier techniques. Two indepen-
dent molecules were found in the asymmetric unit cell.
All final refinements were completed using SHELXL-
93. This was carried out on F2 for all reflections except
for those with either very negative F or reflections
flagged for potential systematic errors, normally for
reflections besides strong ones. Final non-hydrogen
[10] H. Mahmoud, Y. Han, B.M. Segal, L. Cai, Tetrahedron Asym-
metry 9 (1998) 2035.
[11] K.-J. Haack, S. Hashiguchi, A. Fujii, T. Ikariya, R. Noyori,
Angew. Chem. Int. Ed. Engl. 36 (1997) 285.
[12] L. Cai, Y. Han, unpublished results.
.