A facile synthesis of a wide variety of cationic ruthenium hydrido-arene complexes of binap (=1,1′-binaphthalene-2,2′-diylbis(diphenylphosphane)) and meo-biphep (=6,6′-dimethoxybiphenyl-2,2′-diylbis(diphenylphosphane))

Article abstract of DOI:10.1002/1522-2675(200211)85:11<3937::AID-HLCA3937>3.0.CO;2-X

A straightforward high-yield synthetic route to the cationic hydrido-arene complexes [RuH(η⁶-arene)(binap or MeO-biphep)](CF₃SO₃), with a variety of arenes containing both donor and acceptor substituents, is described. ¹³C-NMR Data for these complexes are reported. Several of these Ru-complexes have been used as transfer-hydrogenation catalysts in the reduction of acetophenone.

Full text of DOI:10.1002/1522-2675(200211)85:11<3937::AID-HLCA3937>3.0.CO;2-X

Helvetica Chimica Acta Vol. 85 (2002)
3937
A Facile Synthesis of a Wide Variety of Cationic Ruthenium Hydrido-Arene
Complexes of binap (ˆ1,1'-Binaphthalene-2,2'-diylbis(diphenylphosphane))
and MeOÀbiphep (ˆ6,6'-Dimethoxybiphenyl-2,2'-
diylbis(diphenylphosphane))
by Tilmann J. Geldbach and Paul S. Pregosin*
Laboratory of Inorganic Chemistry, ETHZ, HCI, Hˆnggerberg, CH-8093 Z¸rich
It is our pleasure to dedicate this contribution to Professor Dieter Seebach
A
straightforward high-yield synthetic route to the cationic hydrido-arene complexes [RuH(h6-
arene)(binap or MeOÀbiphep)](CF3SO3), with a variety of arenes containing both donor and acceptor
substituents, is described. 13C-NMR Data for these complexes are reported. Several of these Ru-complexes have
been used as transfer-hydrogenation catalysts in the reduction of acetophenone.
1. Introduction. There is increasing interest in the organometallic chemistry of
ruthenium, as a number of these compounds find application in organic synthesis [1
4]. Specifically, complexes of RuII have been shown to be excellent hydrogenation
[5][6] and transfer-hydrogenation [7 13] catalysts.
In many cases the Ru-catalyst precursor contains an h6-arene ligand [4][7][11][14
16], together with nitrogen or phosphorus ligands. These complexes can be prepared by
allowing commercially available Cl-bridged h6-arene (e.g., p-cymene) Ruthenium
complexes to react with monodentate or bidentate N- or P-donors to afford catalyst
precursors in good yield [17a] (see Scheme 1). Such complexes are often stable enough
to be characterized by X-ray diffraction methods [16][18 27]. The vast majority of
these h6-arene ligands stem from either alkyl benzenes (e.g., toluene, mesitylene or p-
cymene) or benzene itself. Interestingly, there is a dearth of literature concerned with
Ru(h6-arene) complexes with a variety of substituents on the complexed aromatic
moiety. As it is not certain that the h6-arene ligand remains complexed at the end of all
of the various catalytic reactions, it would be useful to have ready access to h6-arene
Ruthenium compounds with both strongly and weakly bound arenes.
Scheme 1
Ruthenium hydride complexes are stable [21][22][25][28][29] and often thought to
be involved in hydrogenation chemistry [30]. Several structures of Ru-complexes
containing both hydrides and h6-arene ligands are known [23][25][30 33]. We report

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Helvetica Chimica Acta Vol. 85 (2002)
here a general synthetic route to cationic phosphanyl-hydride complexes of the type
[RuH(h6-arene)(binap (1a) or MeOÀbiphep (1b))](CF3SO3) that allows the use of a
wide variety of arene ligands.
2. Syntheses. Many ruthenium(II) hydride complexes are prepared via addition of
H2 [34 40] to a suitable RuII compound or, occasionally, via oxidative addition with
Ruthenium(0) carbonyl complexes [20][41]. We have found it convenient to use i-
PrOH as the hydride source (although the synthesis can also be carried out with
MeOH), and there is precedence for the use of alcohols in this way [9][32][42].
Our synthetic approach involves alcohol complexation followed by b-H elimina-
tion; a summary of the new complexes prepared is given in Scheme 2. The starting six-
coordinate [Ru(OAc)2(binap or MeOÀbiphep)] complexes 2a and 2b are known
[5][43][44] and can be prepared in good yield. Protonation of the complexed acetate by
trifluoromethanesulfonic acid (TfOH) frees two equivalents of AcOH, thereby
allowing the solvent alcohol to coordinate. We presume that a labile cation of the
type [Ru(solvent)x(phosphanediyl)]2‡, x ˆ 3 or 4, exists after AcOH loss, and that this
complex can readily provide an open coordination position for the b-H elimination.
The hydride species that forms, [RuH(solvent)x(binap or MeOÀbiphep)](CF3SO3),
x ˆ 2 or 3, is relatively stable. A solid-state structure for a five-coordinate compound,
[RuH(i-PrOH)2(MeOÀbiphep-type)](BF4), [45] is known and [RuH((‡)binap)-
‡
(MeCN)3] and related derivatives [30] have been reported. The strong hydride ligand
labilizes the Ru-coordination sphere, thereby facilitating solvent dissociation and, thus,
allowing the arene to complex. The products, [RuH(h6-arene)(binap)](CF3SO3), and
[RuH(h6-arene)(MeOÀbiphep)] (CF3SO3), shown in Scheme 2, have been isolated
with yields on the order of 68 94%; however, all reactions proceed quantitatively with
the material losses arising during the workup.
Clearly, both electron-donating and electron-withdrawing groups on the arene can
be accommodated by this preparative route. It is worth noting that these complexes
need not have a classical ×piano-stool× structure, and that the plane defined by the two
P-atoms and the metal can be ca. perpendicular to the arene plane [33].

Helvetica Chimica Acta Vol. 85 (2002)
3939
Scheme 2
NMR Spectroscopy. The complexes were characterized by 1H-, 13C-, and 31P-NMR
spectroscopy. The hydride signals represent the X part of an ABX spin system and fall
in the range of ca. À8 to À11 ppm. The 31P-NMR spectra show AB spins systems and,
occasionally, only a broad singlet, due to the very similar (often separated by < 2 ppm)
31P chemical shifts. The complexed arene was identified via its expected [46] low
frequency 13C chemical shift (see Table 1). These data are best obtained via a 13C,1H
long-range correlation (see Fig. 1), in that all six nonequivalent C-atoms are readily
3
detected via their various J(13C,1H) values. There are two cross-peaks per C-atom
resonance, thus the assignment is unequivocal. The observed chemical shifts of ca. 85
123 ppm correspond to coordination chemical shifts (Dd ˆ d(arene complex) À d(free
arene) of ca. À15 to À35 ppm. Details of the Dd values for 4a and 6a are shown in
Table 2 and support an h6-structure, i.e., all six C-atoms are complexed. We do not find a
correlation of the C(14) resonance with literature Hammett constants.
Aspects of the 3-D solution structure were determined by standard NOE methods.
Interestingly, for many of the complexes, the sterically more demanding substituent of
the arene is pointing towards the phosphane backbone. Fig. 2 shows a slice through the
hydride region of the NOESY spectrum of 9b. The strongest contacts stem from two P-
phenyls (one being dynamic on the NMR time scale) with additional substantial
contacts to HÀC(13) of the complexed arene and the tolyl Me group. Notably, there is
no contact to either the NH resonance or amide Me group. On the other hand, NOESY

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Helvetica Chimica Acta Vol. 85 (2002)
Table 1. Chemical Shifts of the Hydride and the Complexed Arenes in CD2Cl2
Complex
Hydride
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
3a
4a
5a
6a
À 8.99
À 9.16
À 8.74
À 8.80
À 9.12
À 8.85
À 9.47
À 9.24
À 8.73
À 9.03
À 10.36
À 10.71
À 10.24
À 10.64
À 10.16
95.5
111.4
113.3
97.2
121.3
119.5
118.6
119.8
97.0
95.1
96.5
99.0
87.8
91.3
93.6
89.0
101.2
101.8
87.2
86.7
85.1
85.2
86.4
98.1
97.2
93.9
101.3
98.1
97.6
101.3
96.5
96.2
99.6
99.6
85.6
85.8
94.4
91.8
91.8
99.1
98.2
92.3
95.4
95.4
95.3
95.2
93.9
94.0
93.2
92.9
85.6
85.8
99.6
94.1
94.3
95.7
90.1
92.5
91.7
90.7
94.1
93.1
86.6
87.2
85.1
85.2
86.4
95.0
94.2
94.1
94.0
94.5
98.3
98.0
102.0
101.8
116.3
116.4
86.2
7a (major)
7a (minor)
7b (major)
7b (minor)
8a
8b
9a
96.5
122.5
122.3
116.3
116.4
123.4
9b
10a
10b
11b
Fig. 1. Section of the C,H-long range spectrum of 5a in CD2Cl2 showing the cross-peaks from the complexed
3
arene due to J(C,H)

Helvetica Chimica Acta Vol. 85 (2002)
3941
Table 2. Coordination Chemical Shifts (Dd ˆ d (arene complex) d (free arene)) for the binap Complexes 4a
and 6a in CD2Cl2
Arene C-atom
Dd 4a
Dd 6a
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
À 26.3
À 34.1
À 30.3
À 33.7
À 29.3
À 35.1
À 37.1
À 26.6
À 33.9
À 36.2
À 35.7
À 30.9
data for the two diastereomeric complexes 7, reveal contacts from the hydride to the
methine and OH-signals of the arene side-chain. As H-bonding of TfOÀ to the alcohol
can be excluded from pulsed-gradient spin echo (PGSE) diffusion measurements1),
this difference in arene orientation might arise due to the greater steric bulk of a sp3-
hybridized substituent.
Fig. 2. Cross-section of the hydride region of the NOESY spectrum of 9b in CD2Cl2. The strongest cross-peaks
arise from interactions with P-phenyl protons HÀC(13) and HÀC(17).
Catalysis.
Several of the hydrido complexes were tested as catalysts in the
transfer-hydrogenation reduction of acetophenone (see Scheme 3).
The simple arene complexes with, e.g., benzene or toluene, were not active. Neither
was the acetophenone analogue 5, which might conceivably develop during the
The TfOÀ ion moves much faster than the cation, whereas, in the presence of H-bonding, similar rates of
diffusion are expected. Moreover, the diffusion constant for the cation is, as expected, only slightly faster
than that for [RuCl(h6-p-cymene)(binap)]OTf.
1
)

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Helvetica Chimica Acta Vol. 85 (2002)
Scheme 3
catalysis due to an arene-exchange reaction. Those arene compounds containing a
readily deprotonated group are relatively active (e.g., 7 11), and, for these complexes,
the reaction rates are basically independent of the nature of the arene. The
MeOÀbiphep derivatives showed faster rates than the analogous binap complexes.
Fig. 3 shows the formation of the alcohol product as a function of time for both 9b and
the known catalyst RuCl2(PPh3)3 13 [9]. Compound 13 should be a relatively good
catalyst, as it contains a monodentate phosphine that can dissociate, thereby facilitating
substrate complexation. Nevertheless, complex 9b is only ca. a factor of two slower than
13. This, together with a lack of arene influence, suggests that the active catalyst has a
structure that differs notably from the above compounds.
Fig. 3. Kinetic data for the transfer hydrogenation of acetophenone/i-PrOH at 908 andchange in ee over time
A solution containing complex 9a together with 2.5 equiv. of KOH in (D8)i-PrOH
was studied via NMR spectroscopy. Ca. 20 minutes after mixing, a new species is
formed quantitatively (see Table 3 for its 13C characteristics), which we believe arises
from deprotonation at the N-atom. After ca. 30 min, signals due to uncomplexed p-
methylacetanilide are observed, i.e., in a basic medium the arene ligandis lost .
Presumably, this arene loss results in exposure of three additional coordination
Table 3. Effect of Base on Chemical Shifts of 9a (in (D8)i-PrOH)
Hydride
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(18)
9a
À 10.26
À 11.23
121.1
136.8
88.1
91.9
97.9
97.4
103.7
99.6
93.7
93.6
86.8
91.3
170.8
178.7
9a ‡ base

Helvetica Chimica Acta Vol. 85 (2002)
3943
positions, which, then, are occupied by i-PrOH and/or substrate. It is likely that this
complex is the catalytically active species.
Fig. 3 also shows the observed enantiomeric excess as a function of time. Clearly,
the substantial observed decrease in enantiomeric excess with time makes this class of
complex unsuitable for enantioselective work. We believe that the loss of the arene
ligand gives rise to a labile (and, thus, relatively fast) catalyst capable of racemizing the
product PhCH(OH)CH3 via oxygen complexation and the usual b-H elimination
mechanism [9].
Summarizing, although our preparative route allows access to a wider variety of
arene complexes, these are not necessarily the most suitable precursors for transfer
hydrogenation.
We thank P. G. Anil Kumar for the PGSE diffusion measurements. P. S. P. thanks the Swiss National Science
Foundation, the Bundesamt f¸r Bildung und Wissenschaft, and the ETH Zurich for financial support, F.
Hoffmann-La Roche AG Basel for the gift of chemicals, and Johnson Matthey for the loan of precious metal
salts.
Experimental Part
Catalysis: General procedure for the transfer hydrogenation of acetophenone: in an ampoule, a soln. of the
catalyst (0.01 mmol) in 10 ml degassed i-PrOH was treated with acetophenone (1.20 g, 10 mmol) and 0.1m
i-PrOK/i-PrOH (0.5 ml, 0.05 mmol) and stirred at 908. The conversion was monitored by NMR, and ee by
HPLC (Chiralcel OB-H).
Preparation of a Representative Complex: [1,1'-Binaphthalene-2,2'-diylbis(diphenylphosphane)-k2-P,P']hy-
drido[N-(h6-tol-4-yl)acetamide]ruthenium(II) Trifluoromethanesulfonate (9a). A suspension of [Ru(OAc)2(bi-
nap)] (150 mg, 0.178 mmol) and p-methylacetanilide (28 mg, 0.188 mmol) in i-PrOH (15 ml) was heated to 758
and subsequently treated with TfOH (35 ml, 0.399 mmol). Upon addition of the acid, the remaining solids
dissolved and the soln. color changed to pale yellow. The soln. was allowed to cool to r.t. and concentrated in
vacuo to ca. 1 ml. Addition of pentane led to precipitation of the product, which was collected by filtration. After
washing with Et2O and drying, 108 mg (89%) of complex 9a was obtained as a pale yellow solid (see below for
data).
(h6-Benzene)[1,1'-binaphthalene-2,2'-diylbis(diphenylphosphane)-k2P,P']-hydridoruthenium(II) Trifluoro-
methanesulfonate (3a): Yield: 94%. 1H-NMR (CD2Cl2, 300 MHz): 8.10 (m, HÀC(5')); 8.02 (br., 1 H); 7.81
7.43 (m, 15 H); 7.40 7.29 (m, 4 H); 7.26 (t, 3J(H,H) ˆ 7.3, HÀC(9)); 7.00 6.76 (m, 7 H); 6.72 (m, 1 H); 6.51 (br.,
3
3
1 H); 6.31 (d, J(H,H) ˆ 8.4, HÀC(7)); 6.22 (d, J(H,H) ˆ 8.4, HÀC(7')); 5.49 (s, 6 H, HÀC(11)); À8.99 (dd,
2J(P,H) ˆ 39.6, 2J(P,H) ˆ 29.5).13C-NMR (CD2Cl2, 75 MHz): 138.9 (m, C(1')); 138.2 (m, C(1)); 134.6 (d,
J(C,P) ˆ 9); 134.1 (d, J(C,P) ˆ 12); 133.7, 133.5 (C(3')); 133.4 (m, C(2'), C(3)); 132.9 (d, 3J(C,P) ˆ 8, C(2));
4
4
4
4
131.0 (d, J(C,P) ˆ 2); 130.7 (d, J(C,P) ˆ 2); 130.1 (d, J(C,P) ˆ 2); 129.8 (d, J(C,P) ˆ 2); 129.2 (C(4)); 129.1
(C(4')); 128.8 (d, J(C,P) ˆ 9); 128.6 (d, J(C,P) ˆ 9); 128.3, 128.2 (C(10')); 128.0 (C(7), C(10)); 127.7 (C(7'));
127.6 (C(9')); 127.5 (C(9)); 126.5 (C(8')); 126.4 (C(8)); 126.1 (d, 2J(C,P) ˆ 7, C(5')); 124.8 (d, 2J(C,P) ˆ 8, C(5));
95.5 (t, 2J(C,P) ˆ 2, C(11)). 31P-NMR (CD2Cl2, 202 MHz): 52.5 (d, 2J(P,P) ˆ 45); 51.9 (d, 2J(P,P) ˆ 45). ESI-MS:
‡
‡
803.2 (M ), 722.9 (100, [M À arene À H2] ). Anal. calc. for C51H39F3O3P2RuS: C 64.35, H 4.13; found: C 64.39,
H 4.25.
[1,1'-Binaphthalene-2,2-diylbis(diphenylphosphane)-k2P,P']hydrido(h6-toluene)ruthenium(II) Trifluoro-
methanesulfonate (4a): Yield: 95%. 1H-NMR (CD2Cl2, 400 MHz): 8.11 (m, C(5')); 7.99 (br.); 7.79 (m, 2 H);
3
7.74 7.47 (m, 14 H); 7.38 7.23 (m, 4 H); 6.96 6.76 (m, 7 H); 6.73 (t, J(H,H) ˆ 7.3, 1 H); 6.49 (br.); 6.33 (d,
3J(H,H) ˆ 8.7, HÀC(7)); 6.21 (d, 3J(H,H) ˆ 8.8, HÀC(7')); 6.04 (t, 3J(H,H) ˆ 6.0, HÀC(14)); 5.69 (t, 3J(H,H) ˆ
6.0, HÀC(15)); 5.27 (d, 3J(H,H) ˆ 6.0, HÀC(12)); 4.89 (t, 3J(H,H) ˆ 6.0, HÀC(13)); 4.70 (d, 3J(H,H) ˆ 6.4,
HÀC(16)); 2.14 (s, Me); À9.16 (dd, J(P,H) ˆ 39.3, J(P,H) ˆ 30.2). 13C-NMR (CD2Cl2, 100 MHz): 138.8 (m,
C(1')); 138.2 (m, C(1)); 134.7 (d, J(C,P) ˆ 9); 134.0 (d, J(C,P) ˆ 11); 133.7, 133.5 (C(3')); 133.4 (m, C(2'), C(3));
132.9 (d, 3J(C,P) ˆ 9, C(2)); 131.0 (d, 4J(C,P) ˆ 2); 130.7 (d, 4J(C,P) ˆ 2); 130.1 (d, 4J(C,P) ˆ 2); 129.8 (d,
4J(C,P) ˆ 2); 129.2 (C(4), C(4')); 128.8 (d, J(C,P) ˆ 9); 128.6 (d, J(C,P) ˆ 9); 128.3, 128.2 (C(10')); 128.0 (C(7));
127.7 (C(10)); 127.6 (C(9')); 127.5 (C(9)); 126.5 (C(8), C(8')); 126.1 (d, 2J(C,P) ˆ 8, C(5')); 124.8 (d, 2J(C,P) ˆ 8,
2
2

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Helvetica Chimica Acta Vol. 85 (2002)
C(5)); 111.4 (C(11)); 99.1 (C(15)); 98.1 (br., C(13)); 95.1 (d, 2J(C,P) ˆ 4, C(12)); 94.1 (m, C(16)); 91.8 (C(14));
2
21.0. 19F-NMR (CD2Cl2, 202 MHz): À79.21 (s). 31P-NMR (CD2Cl2, 162 MHz): 53.1 (d, J(P,P) ˆ 45); 52.6 (d,
‡
‡
‡
2J(P,P) ˆ 45). ESI-MS: 816.9 (100, M ), 723.1 ([M À arene À H2] ). Anal. calc. for C52H41F3O3P2RuS: C 64.66,
H 4.28; found: C 64.40, H 4.57.
[1,1'-Binaphthalene-2,2'-diylbis(diphenylphosphane)-k2P,P'](h6-chlorobenzene)hydridoruthenium(II) Tri-
fluoromethanesulfonate (5a): Yield: 91%. 1H-NMR (CD2Cl2, 500 MHz): 8.13 (dd, 3J(P,H) ˆ 8.8, 3J(H,H) ˆ
8.8, HÀC(5)); 8.01 (br., 1 H); 7.82 (m, HÀC(4), HÀC(5')); 7.75 (d, 3J(H,H) ˆ 8.7, HÀC(4')); 7.69 (m, 2 H); 7.66
(d, 3J(H,H) ˆ 7.8, HÀC(10)); 7.63 7.51 (m, 8 H); 7.35 (m, 3 H); 7.30 (t, 3J(H,H) ˆ 7.3, HÀC(9)); 6.97 (br., 1 H);
6.93 (m, HÀC(8), HÀC(8')); 6.84 (m, 3 H); 6.77 (m, 1 H); 6.52 (br., 1 H); 6.36 (d, 3J(H,H) ˆ 8.7, HÀC(7)); 6.25
(d, 3J(H,H) ˆ 8.7, HÀC(7')); 6.11 (t, 3J(H,H) ˆ 6.0, HÀC(14)); 5.63 (t, 3J(H,H) ˆ 6.0, HÀC(15)); 5.58 (d,
3J(H,H) ˆ 6.4, HÀC(12)); 5.11 (d, 3J(H,H) ˆ 6.8, HÀC(16)); 5.09 (t, 3J(H,H) ˆ 6.0, HÀC(13)); À8.74 (dd,
2J(P,H) ˆ 41.2, 29.7). 13C-NMR (CD2Cl2, 125 MHz): 139.0 (C(1')); 138.2 (C(1)); 134.8 (d, J(C,P) ˆ 9); 134.3
(C(6')); 134.1 (d, J(C,P) ˆ 12); 133.8 (C(3), C(3')); 133.5 (d, J(C,P) ˆ 10); 133.3 (C(2')); 133.0 (C(2)); 132.5
(C(61)); 131.3 (d, J(C,P) ˆ 3); 131.0 (d, J(C,P) ˆ 3); 130.3 (d, J(C,P) ˆ 3); 130.1 (d, J(C,P) ˆ 3); 129.5 (d,
J(C,P) ˆ 9, C(4)); 129.3 (d, J(C,P) ˆ 9, C(4')); 128.9 (d, J(C,P) ˆ 10); 128.7 (d, J(C,P) ˆ 10); 128.3 (C(10')); 128.0
(C(10)); 127.7 (C(9')); 127.6 (C(9)); 126.6 (C(8), C(8')); 126.2 (d, 2J(C,P) ˆ 8, C(5')); 124.7 (d, 2J(C,P) ˆ 8,
C(5)); 113.3 (br., C(11)); 98.2 (br., C(15)); 97.2 (br., C(13)); 96.5 (d, 2J(C,P) ˆ 3, C(12)); 94.4 (br., C(16)); 91.8
(d, 2J(C,P) ˆ 2, C(14)). 31P-NMR (CD2Cl2, 202 MHz): 51.4 (d, 2J(P,P) ˆ 43); 50.6 (d, 2J(P,P) ˆ 43). ESI-MS:
‡
‡
‡
837.0 (M ), 722.9 (100, [M À arene À H2] ). Anal. calc. for C51H38ClF3O3P2RuS: C 62.10, H 3.88; found:
C 61.47, H 4.27.
(h6-Benzamide)[1,1'-binaphthalene-2,2'-diylbis(diphenylphosphane)-k2P,P']hydridoruthenium(II) Trifluoro-
methanesulfonate (6a): Yield: 72%. 1H-NMR (CD2Cl2, 500 MHz): 8.13 (dd, 3J(P,H) ˆ 8.7, 3J(H,H) ˆ 8.7,
HÀC(5')); 7.83 7.49 (m); 7.37 7.30 (m); 7.28 (t, 3J(H,H) ˆ 7.3, HÀC(9)); 6.94 6.77 (m); 6.74 (m, 1 H); 6.68 (d,
3
3J(H,H) ˆ 6.0, HÀC(16)); 6.32 (m, HÀC(7), HÀC(14)); 6.26 (d, J(H,H) ˆ 8.2, HÀC(7')); 5.76 (t, 3J(H,H) ˆ
6.0, HÀC(13)); 5.36 (d, 3J(H,H) ˆ 6.4, HÀC(12)); 4.45 (t, 3J(H,H) ˆ 6.4, HÀC(15)); À8.80 (dd, 2J(P,H) ˆ 41.2,
2J(P,H) ˆ 28.9). 13C-NMR (CD2Cl2, 75 MHz): 164.5 (C(17)); 138.2 (br., C(1)); 137.5 (br., C(1')); 134.1 (d,
J(C,P) ˆ 9); 133.7 (C(3), C(3')); 133.4 (d, J(C,P) ˆ 12); 133.0 (C(2), C(2')); 132.9 (d, J(C,P) ˆ 2); 132.7 (C(6),
C(6')); 130.3 (d, J(C,P) ˆ 14); 129.5 (C(4)); 129.2 (C(4')); 128.8 (C(10), C(10')); 128.7 (d, J(C,P) ˆ 9); 128.4 (d,
J(C,P) ˆ 9); 128.1 (C(7)); 128.0 (C(7')); 127.7 (C(9')); 127.5 (C(9)); 126.9 (C(8')); 126.7 (C(8)); 125.6 (C(5'));
2
124.2 (C(5)); 99.0 (br., C(12)); 97.2 (d, J(C,P) ˆ 3, C(11)); 95.7 (C(16)); 95.0 (C(14)); 93.9 (C(13)); 92.3 (br.,
‡
C(15)). 31P-NMR (CD2Cl2, 202 MHz): 51.3 (d, 2J(P,P) ˆ 44); 50.5 (d, 2J(P,P) ˆ 44). ESI-MS: 846.0 (M ), 722.9
‡
‡
([M À arene À H2] ). Anal. calc. for C52H40F3NO4P2RuS: C 62.77, H 4.05; found: C 59.41, H 4.20.
[1,1'-Binaphthalene-2,2'-diylbis(diphenylphosphane)-k2P,P']hydrido[1-(h6-phenyl)ethanol]ruthenium(II)
Trifluoromethanesulfonate (7a): Yield: 90%. 1H-NMR (CD2Cl2, 400 MHz): 8.15 (m); 8.05 (br.); 7.88 7.46 (m);
3
7.42 7.22 (m); 6.97 6.62 (m); 6.40 (m); 6.23 (m); 5.77 (HÀC(12), HÀC(13), minor); 5.46 (t, br., J(H,H) ˆ
5.5, HÀC(13), major); 5.18 (d, 3J(H,H) ˆ 5.9, HÀC(12), major); 5.00 (br., HÀC(15), major); 4.78 (d,
3J(H,H) ˆ 5.9, HÀC(16), major); 4.70 (br. m, HÀC(17), major); 4.44 (br. m, HÀC(17), minor); 4.40 4.33 (m,
HÀC(15), HÀC(16), minor); 3.80 (d, 3J(H,H) ˆ 4.2, OH, minor); 3.61 (d, 3J(H,H) ˆ 4.2, OH, major); 1.42 (d,
3J(H,H) ˆ 6.4, HÀC(18), major); 1.37 (d, 3J(H,H) ˆ 6.4, HÀC(18), minor); À8.85 (dd, 2J(P,H) ˆ 38.2,
2J(P,H) ˆ 30.4, major); À9.11 (dd, 2J(P,H) ˆ 39.2, 2J(P,H) ˆ 30.6, major). 31P-NMR (CD2Cl2, 162 MHz): 52.7 (d,
2J(P,P) ˆ 31, major); 52.6 (d, 2J(P,P) ˆ 31, major); 52.2 (d, 2J(P,P) ˆ 31, minor); 52.1 (d, 2J(P,P) ˆ 31, minor).
‡
‡
ESI-MS: 846.9 (M ), 722.8 (100, [M À arene À H2] ). Anal. calc. for C53H43F3O4P2RuS: C 63.91, H 4.35; found:
C 63.44, H 4.49.
[6,6'-Dimethoxybiphenyl-2,2'-diylbis(diphenylphosphane)-k2P,P']hydrido[1-(h6-phenyl)ethanol]ruthenium-
(II) Trifluoromethanesulfonate (7b): Yield: 91%. 1H-NMR (CD2Cl2, 400 MHz): 8.21 (br.); 7.59 7.31 (m); 7.15
7.04 (m); 6.99 (br.); 6.46 (t, 3J(H,H) ˆ 6.0, HÀC(14), minor); 6.36 6.29 (m, 4 H); 5.92 (d, 3J(H,H) ˆ 6.0,
HÀC(16), major); 5.83 (d, 3J(H,H) ˆ 6.0, HÀC(13), major); 5.47 (m, HÀC(13), minor); 4.96 (d, 3J(H,H) ˆ 6.0,
HÀC(12), minor); 4.92 (d, 3J(H,H) ˆ 6.0, HÀC(16), minor); 4.77 (m, HÀC(15), minor); 4.73 (q, 3J(H,H) ˆ 6.4,
HÀC(17), minor); 4.37 (q, 3J(H,H) ˆ 6.4, HÀC(17), major); 4.20 (t, 3J(H,H) ˆ 6.0, HÀC(15), major); 4.16 (d,
3J(H,H) ˆ 6.0, HÀC(12), major); 3.31 (s, Me, major); 3.29 (s, Me, minor); 3.25 (s, Me, minor); 3.24 (s, Me,
major); 1.41 (d, 3J(H,H) ˆ 6.4, HÀC(18), minor); 1.36 (d, 3J(H,H) ˆ 6.4, HÀC(18), major); À9.24 (dd, 2J(P,H)
ˆ 40.3, 2J(P,H) ˆ 30.2, minor); À9.47 (dd, 2J(P,H) ˆ 40.8, 2J(P,H) ˆ 29.8, major). 13C-NMR (CD2Cl2, 100 MHz):
119.8 (C(11), minor); 118.6 (C(11), major); 101.3 (C(13), minor); 97.6 (C(13), major); 95.3 (br., C(15), major);
95.2 (br., C(15), minor); 94.5 (C(14), minor); 94.0 (C(14), major); 93.6 (br., C(12), major); 91.7 (d, 2J(C,P) ˆ 4,
2
C(16), major); 90.7 (br., C(16), minor); 89.0 (d, J(C,P) ˆ 6, C(12), minor); 67.5 (C(17), major); 67.3 (C(17),
minor); 55.0 (C(7), C(7')); 54.9 (C(7), C(7')); 25.9 (C(18), major); 25.7 (C(18), minor). 31P-NMR (CD2Cl2,

Helvetica Chimica Acta Vol. 85 (2002)
3945
162 MHz): 50.8 (d, 2J(P,P) ˆ 46, major); 50.5 (d, 2J(P,P) ˆ 45, minor); 50.1 (d, 2J(P,P) ˆ 45, minor); 49.8 (d,
‡
‡
2J(P,P) ˆ 46, major). ESI-MS: 806.9 (M ), 682.8 (100, [M À arene À H2] ). Anal. calc. for C47H43F3O6P2RuS:
C 59.05, H 4.53; found: C 58.62, H 4.91.
[1,1'-Binaphthalene-2,2'-diylbis(diphenylphosphane)-k2P,P']hydrido[(h6-phenyl)acetone]ruthenium(II)
Trifluoromethanesulfonate (8a): Synthesis performed in MeOH. Yield: 68%. 1H-NMR (CD2Cl2, 500 MHz): 8.06
(dd, 3J(P,H) ˆ 9.2, 3J(H,H) ˆ 9.2, HÀC(5')); 7.81 7.26 (m, 19 H); 6.99 6.76 (m, 10 H); 6.66 (m, HÀC(14));
6.51 (d, 3J(H,H) ˆ 6.4, HÀC(16)); 6.35 (br., HÀC(13)); 6.29 (d, 3J(H,H) ˆ 8.7, HÀC(7)); 6.25 (d, 3J(H,H) ˆ 8.7,
3
HÀC(7')); 5.03 (d, J(H,H) ˆ 6.4, HÀC(12)); 4.28 (br., HÀC(15)); 2.08 (s, HÀC(18)); À8.73 (dd, 2J(P,H) ˆ
41.2, 2J(P,H) ˆ 28.0). 13C-NMR (CD2Cl2, 125 MHz): 195.6 (C(17)); 139.0 (C(1')); 138.0 (C(1)); 137.7 (d,
J(C,P) ˆ 46); 134.6 (d, J(C,P) ˆ 9); 134.1 (d, J(C,P) ˆ 13); 134.0 (d, J(C,P) ˆ 10); 133.8 (C(3), C(3')); 133.4 (d,
3
3J(C,P) ˆ 8, C(2')); 132.8 (d, J(C,P) ˆ 9, C(2)); 132.5 (C(6), C(6')); 131.1 (m); 130.3 (d, J(C,P) ˆ 2); 129.5 (d,
3J(C,P) ˆ 9, C(4')); 129.3 (d, 3J(C,P) ˆ 9, C(4)); 129.0 (d, J(C,P) ˆ 10); 128.8 (d, J(C,P) ˆ 10); 128.3 (d, J(C,P) ˆ
11); 128.0 (C(7), C(9')); 127,8 (C(7')); 127.7 (C(9)); 126.6 (C(8), C(8')); 126.1 (d, 2J(C,P) ˆ 8, C(5')); 124.6 (d,
2J(C,P) ˆ 9, C(5)); 101.2 (d, 2J(C,P) ˆ 4, C(12)); 98.3 (C(14)); 97.0 (d, 2J(C,P) ˆ 6, C(11)); 96.5 (C(13)); 94.1 (d,
2J(C,P) ˆ 3, C(16)); 93.9 (d, 2J(C,P) ˆ 5, C(15)); 26.1 (C(18)). 31P-NMR (CD2Cl2, 202 MHz): 50.9 (d, 2J(P,P) ˆ
‡
‡
44); 49.6 (d, 2J(P,P) ˆ 44). ESI-MS: 845.0 (M ), 722.9 ([M À arene À H2] ). Anal. calc. for C53H41F3O4P2RuS:
C 64.04, H 4.16; found: C 62.29, H 4.50.
[6,6'-Dimethoxybiphenyl-2,2'-diylbis(diphenylphosphane)-k2P,P']hydrido[h6-phenyl)acetone]ruthenium-
(II) Trifluoromethanesulfonate (8b): Yield: 81%. 1H-NMR (CD2Cl2 , 300 MHz): 7.92 (br., 1 H); 7.67 6.85 (m,
23 H); 6.63 (t, 3J(H,H) ˆ 6.0, HÀC(14)); 6.52 (d, 3J(H,H) ˆ 6.6, HÀC(16)); 6.40 (t, 3J(H,H) ˆ 6.0, HÀC(13));
6.31 (d, 3J(H,H) ˆ 8.2, HÀC(3), HÀC(3')); 4.88 (d, 3J(H,H) ˆ 6.0, HÀC(12)); 4.03 (t, 3J(H,H) ˆ 6.6,
HÀC(15)); 3.29 (s, MeO, HÀC(7)); 3.24 (s, MeO, HÀC(7')); 2.04 (s, Me, HÀC(18)); À9.03 (dd, 2J(P,H) ˆ
2
3
42.3, J(P,H) ˆ 29.1, 1 H). 13C-NMR (CD2Cl2, 75 MHz): 195.7 (C(17)); 157.9 (d, J(C,P) ˆ 12, C(2')); 157.7 (d,
3J(C,P) ˆ 12, C(2)); 137.6 (d, J(C,P) ˆ 46); 136.3 (d, J(C,P) ˆ 60); 134.5 (m); 134.2 (d, J(C,P) ˆ 9); 133.8 (d,
J(C,P) ˆ 10); 131.2 (m); 129.5 (d, 3J(C,P) ˆ 11, C(4), C(4')); 128.7 (m); 128.4 (d, 4J(C,P) ˆ 4, C(5), C(5')); 122.3
(d, J(C,P) ˆ 7); 120.4 (d, J(C,P) ˆ 7); 112.0 (d, 2J(C,P) ˆ 24, C(3), C(3')); 101.8 (d, 2J(C,P) ˆ 5, C(12)); 98.0
(C(14)); 96.2 (d, 2J(C,P) ˆ 1, C(13)); 94.0 (d, 2J(C,P) ˆ 6, C(15)); 93.7 (d, 2J(C,P) ˆ 4, C(16)); 55.1 (C(7)); 55.0
(C(7')); 26.1 (C(18)). 31P-NMR (CD2Cl2, 121 MHz): 49.0 (d, 2J(P,H) ˆ 46); 47.4 (d, 2J(P,H) ˆ 46). ESI-MS:
‡
‡
‡
805.0 (M ), 682.7 ([M À arene À H2] ), 604.8 (100, [M À arene À Ph] ). Anal. calc. for C47H41F3O6P2RuS ¥
MeOH: C 58.53, H 4.50; found: C 58.66, H 4.99.
[1,1'-Binaphthalene-2,2'-diylbis(diphenylphosphane)-k2P,P']hydrido[N-(h6-tol-4-yl)acetamide]ruthenium-
(II) Trifluoromethanesulfonate (9a): Yield: 89%. 1H-NMR (CD2Cl2, 500 MHz): 9.45 (s, NH); 8.22 (m,
HÀC(5)); 7.89 (br., 1 H); 7.79 (m, HÀC(4), HÀC(5')); 7.71 7.52 (m, 12 H); 7.32 (3 H); 7.24 (t, 3J(H,H) ˆ 7.3,
3
3
HÀC(9')); 6.92 6.84 (m, 7 H); 6.75 (t, J(H,H) ˆ 7.3, 1 H); 6.59 (m, 2 H); 6.23 (d, J(H,H) ˆ 8.3, HÀC(7'));
6.21 (d, 3J(H,H) ˆ 8.3, HÀC(7)); 5.76 (d, 3J(H,H) ˆ 6.9, HÀC(15)); 5.36 (d, 3J(H,H) ˆ 6.9, HÀC(16)); 3.85 (d,
3J(H,H) ˆ 6.9, HÀC(13)); 2.09 (s, Me, HÀC(19)); 1.81 (s, Me, HÀC(18)); À10.36 (1 H). 13C-NMR (CD2Cl2,
125 MHz): 170.5 (C(18)); 139.1 (m, C(1)); 137.7 (m, C(1')); 136.4 (d, 1J(C,P) ˆ 39, C(6')); 136.0 (C(6)); 134.8 (d,
4J(C,P) ˆ 3, C(3)); 134.7 (d, 4J(C,P) ˆ 3, C(3')); 134.4 (d, J(C,P) ˆ 3); 134.3 (d, J(C,P) ˆ 3); 133.8 (d, 3J(C,P) ˆ 3,
3
3
C(2)); 133.7 (d, J(C,P) ˆ 3, C(2')); 130.6 (d, J(C,P) ˆ 6); 129.8, 128.9 (m, C(5')); 128.8 (d, J(C,P) ˆ 3, C(4));
128.7 (d, 3J(C,P) ˆ 3, C(4')); 128.5 (d, J(C,P) ˆ 3); 128.4 (d, J(C,P) ˆ 3); 128.2 (C(10)); 128.1 (C(10')); 127.8
(C(7')); 127.7 (C(7)); 127.3 (C(9)); 127.1 (C(9')); 126.4 (m, C(5)); 126.2 (C(8)); 126.1 (C(8')); 122.5 (C(11));
102.0 (m, C(14)); 99.6 (m, C(13)); 93.2 (m, C(15)); 87.2 (C(12)); 86.6 (m, C(16)); 24.3 (C(19)); 20.5 (C(17)). 31P-
‡
‡
NMR (CD2Cl2, 162 MHz): 52.5 (s). ESI-MS: 873.4 (M ), 722.6 (100, [M À arene À H2] ). Anal. calc. for
C54H43F3NO4P2RuS: C 63.46, H 4.24, N 1.37; found: C 62.79, H 4.31, N 1.33.
[6,6'-Dimethoxybiphenyl-2,2'-diylbis(diphenylphosphane)-k2P,P']hydrido[N-(h6-tol-4-yl)acetamide]ruthe-
nium(II) Trifluoromethanesulfonate (9b): Yield: 93%. 1H-NMR (CD2Cl2, 500 MHz): 9.42 (s, NH); 8.02 (br.,
1 H); 7.60 (t, 3J(H,H) ˆ 7.3, 2 H); 7.56 7.32 (m, 16 H); 7.30 (br., 1 H); 7.15 (br., 1 H); 7.14 7.00 (m, 3 H); 6.62
(m, HÀC(16)); 6.32 (d, 3J(H,H) ˆ 8.4, HÀC(3')); 6.28 (d, 3J(H,H) ˆ 8.0, HÀC(3)); 5.76 (d, 3J(H,H) ˆ 7.3,
HÀC(15)); 5.20 (m, HÀC(12)); 3.75 (d, 3J(H,H) ˆ 6.5, HÀC(13)); 3.30 (s, MeO, HÀC(7')); 3.23 (s, MeO,
HÀC(7)); 2.14 (s, Me, HÀC(17)); 1.87 (s, Me, HÀC(19)); À10.71 (dd, 2J(P,H) ˆ 39.0, 2J(P,H) ˆ 31.7, 1 H).
13C-NMR (CD2Cl2, 125 MHz): 170.5 (C(18)); 157.8 (d, 3J(C,P) ˆ 1, C(2')); 157.6 (d, 3J(C,P) ˆ 1, C(2)); 139.0 (d,
1J(C,P) ˆ 45, C(6)); 134.9 (m); 134.4 (m); 133.6 (m); 130.7 (d, J(C,P) ˆ 1); 130.5, 130.4, 129.1 (m); 128.9 (m);
2
2
128.5 (m); 128.3 (m); 127.7 (m); 126.6 (m); 122.4 (d, J(C,P) ˆ 6, C(5')); 122.3 (C(11)); 120.3 (d, J(C,P) ˆ 7,
C(5)); 111.7 (d, 4J(C,P) ˆ 1, C(3')); 111.1 (d, 4J(C,P) ˆ 1, C(3)); 101.8 (m, C(14)); 99.6 (m, C(13)); 92.9 (m,
C(15)); 87.3 (C(16)); 86.7 (m, C(12)); 54.9 (C(7), C(7')); 24.4 (C(19)); 20.7 (C(17)). 31P-NMR (CD2Cl2,

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Helvetica Chimica Acta Vol. 85 (2002)
‡
‡
‡
202 MHz): 50.5 (s). ESI-MS: 833.9 (100, M ), 776.9 ([M À C2H3NO] ), 683.0 ([M À arene À H2] ). Anal. calc.
for C48H44F3NO6P2RuS: C 58.65, H 4.51, N 1.42; found: C 58.50, H 4.61, N 1.45.
{N-[4-(Acetylamino)-h6-phenyl]acetamide}[1,1'-binaphthalene-2,2'-diylbis(diphenylphosphane)-k2P,P']hy-
dridoruthenium(II) Trifluoromethanesulfonate (10a): Yield: 74%. 1H-NMR (CD2Cl2, 400 MHz): 9.20 (s, 2 NH);
8.08 (t, 3J(H,H) ˆ 7.3, HÀC(5)); 7.78 (br., 1 H); 7.73 7.64 (m, 3 H); 7.62 7.46 (m, 8 H); 7.39 7.31 (m, 3 H); 7.27
(m, HÀC(9)); 7.22 7.14 (m, 4 H); 6.94 6.80 (m, 4 H); 6.76 6.67 (m, 4 H); 6.50 (br., 1 H); 6.22 (m, 3 H); 6.16
(d, 3J(H,H) ˆ 8.6, HÀC(7)); 4.95 (d, 3J(H,H) ˆ 7.0, HÀC(12), HÀC(16)); 1.96 (s, 2 Me, HÀC(18)); À10.24 (dd,
2J(P,H) ˆ 41.2, 2J(P,H) ˆ 29.1, 1 H). 13C-NMR (CD2Cl2, 100 MHz): 170.3 (C(17)); 139.1 (m, C(1)); 137.7 (m,
C(1'), C(6)); 136.1 (C(6')); 134.0, 133.6, (C(3), C(3')); 133.4 (d, 3J(C,P) ˆ 8, C(2)); 132.9 (d, 3J(C,P) ˆ 10, C(2'));
130.5 (d, J(C,P) ˆ 11); 129.7 (d, J(C,P) ˆ 10); 129.0 (d, J(C,P) ˆ 10); 128.6 (C(4)); 128.3, 128.1, 128.0 (C(10));
129.7 (C(4'), C(7')); 127.7 (C(7), C(10)); 127.2 (C(9)); 127.0 (C(9')); 126.5 (C(5)); 126.1 (C(8')); 126.0 (C(8));
124.9 (C(5')); 116.3 (br., C(11), C(14)); 85.8 (br., C(13), C(15)); 85.4 (br., C(12), C(16)); 24.2 (C(15)). 31P-
‡
NMR (CD2Cl2, 162 MHz): 53.4 (d, 2J(P,P) ˆ 44); 52.5 (dd, 2J(P,P) ˆ 44). ESI-MS: 917.0 (100, M ), 814.9. Anal.
calc. for C55H45F3N2O5P2RuS: C 61.97, H 4.25, N 2.63; found: C 61.23, H 4.86, N 2.51.
{N-[4-(N-Acetylamino)-h6-phenyl]acetamide}[6,6'-dimethoxybiphenyl-2,2'-diylbis(diphenylphosphane)-k2P,P']-
hydridoruthenium(II) Trifluoromethanesulfonate (10b): Yield: 74%. 1H-NMR (CD2Cl2, 500 MHz): 9.32 (s,
NH); 7.88 (br., 1 H); 7.47 7.21 (m); 7.11 6.95 (m); 6.28 (m, HÀC(3), HÀC(3')); 6.22 (d, 3J(H,H) ˆ 6.4,
HÀC(15), HÀC(13)); 4.83 (d, 3J(H,H) ˆ 6.4, HÀC(12), HÀC(16)); 3.28 (s, HÀC(7), MeO); 3.23 (s, HÀC(7'),
MeO); 2.03 (s, HÀC(18)); À10.64 (dd, 2J(P,H) ˆ 42.2, 2J(P,H) ˆ 29.8, 1 H). 13C-NMR (CD2Cl2, 125 MHz):
170.3 (C(17)); 157.8 (d, 3J(C,P) ˆ 11, C(2)); 157.6 (d, 3J(C,P) ˆ 12, C(2')); 138.5 (d, 1J(C,P) ˆ 58); 137.8 (d,
1J(C,P) ˆ 45); 136.1 (d, 1J(C,P) ˆ 50); 134.8 (d, J(C,P) ˆ 13); 134.3 (C(6), C(6')); 134.1 (d, J(C,P) ˆ 9); 133.9 (d,
J(C,P) ˆ 10); 132.7 (d, 1J(C,P) ˆ 58); 130.5 (d, J(C,P) ˆ 20); 130.4 (d, J(C,P) ˆ 9); 129.1 (d, 3J(C,P) ˆ 10, C(4'));
128.9 (d, 3J(C,P) ˆ 10, C(4)); 128.1 (d, J(C,P) ˆ 10); 128.0 (d, J(C,P) ˆ 10); 122.5 (d, 2J(C,P) ˆ 6, C(5')); 120.4 (d,
2J(C,P) ˆ 7, C(5)); 116.4 (br., C(11), C(14)); 111.6 (C(3)); 111.1 (C(3')); 85.8 (C(13), C(15)); 85.2 (C(12),
C(16)); 54.9 (C(7), C(7')); 24.3 (C(18)). 31P-NMR (CD2Cl2, 162 MHz): 53.4 (d, 2J(P,H) ˆ 44); 52.5 (d, 2J(P,H) ˆ
‡
‡
44). ESI-MS: 877.0 (100, M ), 684.7 ([M À arene À H2] ). Anal. calc. for C49H45N2O7P2RuS: C 57.36, H 4.42,
N 2.73; found: C 56.90, H 4.68, N 2.62.
[6,6'-Dimethoxybiphenyl-2,2'-diylbis(diphenylphosphane)-k2P,P']hydrido[N-(h6-phenyl)benzamide]ruthe-
nium(II) Trifluoromethanesulfonate (11b): Synthesis performed in MeOH. Yield: 78%. 1H-NMR (CD2Cl2,
400 MHz): 9.33 (s, NH); 8.18 (br., 1 H); 7.79 (m, 2 H); 7.57 7.22 (m, 21 H); 7.14 6.98 (m, 5 H); 6.83 (m,
HÀC(16)); 6.30 (d, 3J(H,H) ˆ 6.4, HÀC(3), HÀC(3')); 5.84 (m, HÀC(13)); 5.77 (d, 3J(H,H) ˆ 6.4, HÀC(12));
5.46 (t, 3J(H,H) ˆ 5.7, HÀC(14)); 4.60 (t, 3J(H,H) ˆ 6.4, HÀC(15)); 3.29 (s, MeO); 3.26 (s, MeO); À10.16 (dd,
2J(P,H) ˆ 40.6, 2J(P,H) ˆ 29.6, 1 H). 13C-NMR (CD2Cl2, 100 MHz): 166.8 (C(17)); 157.8 (d, 3J(C,P) ˆ 11, C(2'));
157.7 (d, 3J(C,P) ˆ 11, C(2)); 138.2 (dd, 1J(C,P) ˆ 42, 3J(C,P) ˆ 3, C(6)); 136.6 (dd, 1J(C,P) ˆ 47, 3J(C,P) ˆ 5);
134.8 (d, J(C,P) ˆ 12); 134.4 (d, J(C,P) ˆ 9); 133.4 (d, J(C,P) ˆ 10); 133.2, 132.6, 130.6 (dd, J(C,P) ˆ 10, J(C,P) ˆ
2); 130.4 (dd, J(C,P) ˆ 8, J(C,P) ˆ 2); 129.3 (d, 3J(C,P) ˆ 9, C(4)); 129.1 (m); 128.7, 128.5, 128.4, 128.3 (C(4'));
2
2
4
123.4 (C(11)); 122.8 (d, J(C,P) ˆ 7, C(5')); 120.6 (d, J(C,P) ˆ 7, C(5)); 111.6 (d, J(C,P) ˆ 2, C(3)); 111.3 (d,
4J(C,P) ˆ 2, C(3')); 99.6 (br., C(15)); 94.4 (br., C(13)); 86.5 (C(16)); 86.4 (d, 2J(C,P) ˆ 4, C(12)); 86.2 (d,
2J(C,P) ˆ 4, C(14)); 54.9 (C(7), C(7')). 31P-NMR (CD2Cl2, 162 MHz): 51.5 (d, 2J(P,H) ˆ 45); 51.0 (d, 2J(P,H) ˆ
‡
‡
45). ESI-MS: 882.0 (100, M ), 682.8 ([M À arene À H2] ). Anal. calc. for C52H44F3NO6P2RuS ¥ MeOH: C 59.88,
H 4.55, N 1.32; found: C 59.89, H 4.86, N 1.12.
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ReceivedJune 15, 2002