Homobinuclear Ru-Ru and heterobinuclear Ru-Rh complexes with alkynyl and vinylidene ligands as molecular units

Article abstract of DOI:10.1139/v00-170

The chelate complex [RuCl₂{Κ²(P,O)-i-Pr₂PCH₂CH ₂OMe}₂] (1) reacted, in the presence of CF₃SO₃Ag, with 1 equiv of C₆H₄(C≡CH)₂-p (4) to

Full text of DOI:10.1139/v00-170

519
Homobinuclear Ru–Ru and heterobinuclear Ru–Rh
complexes with alkynyl and vinylidene ligands as
molecular units
Helmut Werner, Petra Bachmann, and Marta Martin
Abstract: The chelate complex [RuCl2{κ2(P,O)-i-Pr2PCH2CH2OMe}2] (1) reacted, in the presence of CF3SO3Ag, with
1 equiv of C6H4(CϵCH)2-p (4) to afford the mononuclear vinylidene compound [RuCl(C=CHC6H4-p-CϵCH){κ2(P,O)-i-
Pr2PCH2CH2OMe}2](CF3SO3) (3). From 1 and 0.5 equiv of 4, the binuclear bis(vinylidene) complex [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-p-CH=C)RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3)2 (6) was obtained. The related
compound [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-m-CH=C)RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3)2 (7)
was prepared from 1, 0.5 equiv of C6H4(CϵCH)2-m (5), and silver triflate. The reaction of 2 or 3 with [RhCl(P-i-Pr3)2]2
(8) in the molar ratio of 2:1 yields, by addition of the 14-electron fragment [RhCl(P-i-Pr3)2] to the uncoordinated C—C
triple bond, the heterobinuclear complexes [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-m/p-CϵCH)RhCl(P-i-
Pr3)2](CF3SO3) (9, 10) which slowly rearrange at room temperature to give the bis(vinylidene) isomers [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-m/p-CH=C)RhCl(P-i-Pr3)2](CF3SO3) (11, 12).
Key words: ruthenium, rhodium, vinylidene complexes, alkyne complexes, phosphine complexes.
Résumé : En présence de CF3SO3Ag, le chélate complexe [RuCl2{κ2(P,O)-i-Pr2PCH2CH2OMe}2] (1) réagit avec un
équivalent de C6H4(CϵC)2-p (4) pour conduire à la formation du composé vinylidène mononucléaire
[RuCl(C=CHC6H4-p-CϵC){κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3)2 (3). À partir de 1 et d’un demi-équivalent de 4, on
obtient le complexe bis(vinylidène) binucléaire [RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-p-C=C)RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2] (CF3SO3)2 (6). On a préparé le composé apparenté [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-m-C=C)RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2] (CF3SO3)2 (7) en faisant réagir le com-
posé 1 un demi-équivalent de C6H4(CϵCH)2-m (5) en présence de triflate d’argent. Par le biais d’une addition du frag-
ment à quatorze électrons [RhCl(P-i-Pr3)2] à la triple liaison qui n’est pas coordinée, les réactions des composés 2 ou 3
avec le [RhCl(P-i-Pr3)2]2 (8), dans un rapport molaire de 2:1, conduisent aux complexes hétérobinucléaires
[RuCl{κ2(P,O)-i-Pr2PCH2CH2OMe}2(C=CHC6H4-m/p-CϵC)RhCl(P-i-Pr3)2] (CF3SO3)2 (9, 10) qui se réarrangement len-
tement à la température ambiante pour conduire aux isomères bis(vinylidènes) [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-m/p-C=C)RhCl(P-i-Pr3)2] (CF3SO3)2 (11, 12).
Mots clés : ruthénium, rhodium, complexes de vinylidènes, complexes d’alcynes, complexes de phosphines.
[Traduit par la Rédaction] Werner et al. 524
Introduction
Pr2PCH2CH2OMe}2] (1) using [(1.5-C8H12)RuCl2]n as the
starting material. Due to the hemilabile coordination mode
of the two phosphinoether ligands (for the term hemilabile
see ref. 2a; for reviews see ref. 2b), compound 1 is quite
reactive and affords with CO or PhCϵCH by cleavage of
one of the Ru—O bonds the corresponding carbonyl
and vinylidene complexes, [RuCl2(CO){κ1(P)-i-
Pr2PCH2CH2OMe}{κ2(P,O)-i-Pr2PCH2CH2OMe}] and
[RuCl2(C=CHPh){κ1(P)-i-Pr2PCH2CH2OMe}{κ2(P,O)-
i-Pr2PCH2CH2OMe}], respectively, (3). Moreover, treatment
of 1 with terminal alkynes RCϵCH, in the presence of silver
triflate, led to the formation of the cationic compounds
[RuCl(C=CHR){κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3)
which reacted with base by deprotonation of the vinylidene
ligand to give the alkynyl derivatives [RuCl(CϵCR){κ2-
(P,O)-i-Pr2PCH2CH2OMe}2] (1). Since we used in the
course of these studies apart from alkynes RCϵCH with R =
H, Ph, and C6H4Me-p also the diyne C6H4(CϵCH)2-m as a
substrate, we isolated a cationic complex with a ligand con-
taining an uncoordinated CϵCH unit in the side chain.
Recently, we (1) described an efficient method for the
preparation of the chelate complex [RuCl2{κ2(P,O)-i-
Received September 12, 2000. Published on the NRC
Research Press Web site at http://canjchem.nrc.ca on
May 29, 2001.
This paper is dedicated to Professor Brian R. James on the
occasion of his 65th birthday, in recognition of his manifold
contributions to organometallic chemistry and homogeneous
catalysis.
H. Werner,1 P. Bachmann, and M. Martin.2 Institut für
Anorganische Chemie der Universität, Am Hubland, D-97074
Würzburg, Germany.
1Corresponding author (fax: +49-931-888-4605;
e-mail: helmut.werner@mail.uni-wuerzburg.de
2Present adress: Departamento de Quimica Inorganica,
Universidad de Zaragoza, CSIC, E-50009 Zaragoza, Spain.
Can. J. Chem. 79: 519–524 (2001)
© 2001 NRC Canada
DOI: 10.1139/cjc-79-5/6-519

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Can. J. Chem. Vol. 79, 2001
Scheme 1.
Based on this result, the question arose whether this
ruthenium cation behaves like an ordinary terminal alkyne
and reacts with coordinatively unsaturated precursors to give
bimetallic products.
In answering this question, we report in the present paper
the synthesis of some homo- and hetero-binuclear Ru–Ru
and Ru–Rh complexes, the latter of which revealing different
coordination spheres around the two metal centers.
a small P—P coupling constant of 24.1 Hz. Further
characteristic features are the triplet resonance for the =CHR
1
proton in the H NMR spectrum at δ 5.09 and the low-field
signals at δ 355.5 and 117.2 in the 13C NMR spectrum
which, in agreement with DEPT measurements, are assigned
to the α- and β-C atoms of the vinylidene unit. The reso-
nances for the 13C NMR nuclei of the uncoordinated CϵC
bond appear as singlets at δ 83.8 and 77.4, respectively.
The reaction of 1 with an equimolar amount of CF3SO3Ag
but with 0.5 equiv instead of 1 equiv of the diyne 4 led, un-
der the same conditions as used for the preparation of 3, to
the binuclear complex 6 (see Scheme 1). Similarly to 3,
compound 6 is also an orange, only slightly air-sensitive
solid which is easily soluble in polar solvents such as ace-
tone or dichloromethane. In contrast to 3, the IR spectrum of
6 shows no stretching vibrations in the regions at about 3200
and 2100 cm–1, indicating that no CϵCH unit is present. The
13C NMR spectrum of 6 displays the signals for the
vinylidene carbon atoms at almost the same positions as
found for the mononuclear complex 3.
Results and discussion
The preparation of the mononuclear complex 3 (see
Scheme 1) followed the route which we had already used for
the analogous compound 2 (1). Stepwise treatment of the
starting material 1 in acetone with the diyne 4 and silver
triflate led, after separation of AgCl, to the formation of a
yellow solution from which 3 was isolated in 72% yield. The
proposed structure with the cis-disposed P-i-Pr2 groups is
supported by the 31P NMR spectrum which displays the typ-
ical pattern of an AB spin system showing two doublets with
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Werner et al.
521
Scheme 2.
The starting material 1 reacts not only with 4 but also
with the meta-isomer 5 of the diyne C6H4(CϵCH)2 in the
molar ratio of 2:1 to give the binuclear compound 7. Due to
the related structure of 6 and 7, it is not surprising that both
the chemical properties and the spectroscopic data of the two
isomers are in most respects quite similar. The slightly lower
symmetry of 7 compared to 6 is indicated, inter alia, by the
appearance of a broad multiplet instead of a singlet for the
protons of the C6H4 fragment and equally by the observation
of eight instead of two singlet resonances for the carbon at-
oms of the phenylene ring. We also note that apart from 6
and 7, three isomeric binuclear rhodium complexes with the
ortho-, meta-, and para-isomers of the bis(vinylidene) unit
C=CHC6H4CH=C have been prepared in our laboratory (4).
The uncoordinated alkyne functionality of both 2 and 3
can also be used for the preparation of the mixed-metal ru-
thenium–rhodium compounds 9–12 shown in Scheme 2. The
mononuclear precursors react, analogously as terminal al-
kynes RCϵCH (5), with the dimer [RhCl(P-i-Pr3)2]2 (8) un-
der mild conditions to give the Ru–Rh complexes 9 and 10
as orange microcrystalline solids in ca. 60% yield. In the IR
spectra of 9 and 10, the ν (ϵCH) and ν (CϵC) modes appear
at significantly lower wave numbers than in the spectra of 2
and 3 which is in agreement with the coordination of the tri-
ple bond to the rhodium center. The proposed trans-disposi-
tion of the two triisopropylphosphine ligands at Rh is
supported by the H NMR spectra of 9 and 10, each of
which displays two doublets of virtual triplets for the pro-
1
tons of the diastereotopic methyl groups of the P-i-Pr3 units.
Both 9 and 10 slowly rearrange, in toluene at room tem-
perature, to the isomeric species 11 and 12 which are iso-
lated as green, relatively air-stable solids in ca. 70% yield.
The 13C NMR spectra of 11 and 12 exhibit in the low-field
region two signals for the metal-bound carbon atoms at
about δ 355 and 292 which is consistent with the presence of
two different carbene-like vinylidene units in the molecule.
Another characteristic feature in the 31P NMR spectra of 11
and 12 is the appearance of two doublets for the phosphorus
atoms linked to ruthenium and of one doublet for the phos-
phorus atoms linked to rhodium, the latter showing a rather
large Rh—P coupling of ca. 135 Hz. With regard to the
course of the rearrangement of 9 and 10 to 11 and 12, we
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Can. J. Chem. Vol. 79, 2001
failed to find any evidence for the generation of an interme-
diate containing an alkynyl(hydrido)rhodium moiety
RhH(CϵCR)Cl(P-i-Pr3)2 as a building block, and therefore a
concerted mechanism is most likely (6). This result is
in contrast to that for the isomerization reaction of
trans-[RhCl(HCϵCtBu)(P-i-Pr3)2] to trans-[RhCl(=CϵCH-t-Bu)
(P-i-Pr3)2] for which a five-coordinate intermediate [RhH(C
ϵC-t-Bu)Cl(P-i-Pr3)2] could not only be detected but even
isolated (7).
tained. Yield: 298 mg (85%). IR (kBr) (cm–1): ν(C=C) 1600.
1H NMR (400 MHz, CD2Cl2) δ: 7.21 (s, C6H4), 5.08, 5.06
(both t, J (PH) = 3.6 Hz, =CH), 4.19, 4.11, 4.04, 3.77 (all m,
CH2OCH3), 3.84, 3.82, 3.64 (all s, OCH3), 2.86, 2.48, 2.37,
2.32, 2.20, 2.01, 1.89 (all m, PCHCH3 and PCH2), 1.54–1.28
(br m, PCHCH3). 13C NMR (100.6 MHz, CD2Cl2) δ: 355.5
(dd, J (PC) = 18.1 and 15.1 Hz, Ru=C), 127.1, 126.3 (both s,
C6H4), 121.4 (q, J (FC) = 320.9 Hz, CF3), 117.8 (s, =CH),
72.7, 71.7 (both s, CH2OCH3), 63.2, 63.1, 61.8 (all s,
OCH3), 37.5 (d, J (PC) = 33.3 Hz, PCHCH3), 28.6, 28.5
(both d, J (PC) = 26.0 Hz, PCHCH3), 26.6 (d, J (PC) =
31.2 Hz, PCHCH3), 25.8 (d, J (PC) = 20.0 Hz, PCHCH3),
25.7 (d, J (PC) = 19.0 Hz, PCH2), 23.3 (d, J (PC) = 23.6 Hz,
PCH2), 20.1, 19.8, 19.75, 19.7, 19.6, 19.2, 19.1, 19.0 (all s,
PCHCH3). 31P NMR (162.0 MHz, CD2Cl2) δ: 68.1, 56.2
(both d, J (PP) = 24.3 Hz). 19F NMR (376.5 MHz, CD2Cl2)
δ: –78.6 (s). Anal. calcd. for C48H90Cl2F6O10P4Ru2S2: C
41.11, H 6.47, S 4.57; found: C 41.37, H 6.30, S 4.42.
Experimental
All experiments were carried out under an atmosphere of
argon by using standard Schlenk techniques. The starting
materials [RuCl2{κ2(P,O)-i-Pr2PCH2CH2OMe}2] (1) (1),
C6H4(CϵCH)2-p and -m (4, 5) (8), [RuCl-(C=CHC6H4CϵCH-
m){κ2(P,O)-i-Pr2PCH2CH2OMe}2](CF3SO3) (2) (1), and
[RhCl(P-i-Pr3)2]2 (8) (9) were prepared as described previ-
ously. IR spectra were recorded on a PerkinElmer 1420 IR
spectrometer and NMR spectra on Bruker AC 200 and WM
400 instruments. Melting points (dec. temp.) were deter-
mined by DTA.
Preparation of [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-m-CH=C)RuCl{κ2(P,O)-
i-Pr2PCH2CH2OMe}2](CF3SO3)2 (7)
The procedure was analogous to that described for 3, us-
ing 1 (262 mg, 0.50 mmol), 5 (31 mg, 0.25 mmol), and
CF3SO3Ag (128 mg, 0.50 mmol) in 20 mL of acetone as
starting materials. An orange microcrystalline solid was ob-
tained. Yield: 161 mg (46%). IR (KBr) (cm–1): ν(C=C) 1610,
1580. 1H NMR (400 MHz, CD2Cl2) δ: 7.22–6.95 (br m,
C6H4), 5.06, 5.05 (both t, J (PH) = 3.7 Hz, =CH), 4.20, 4.12,
4.04, 3.80 (all m, CH2OCH3), 3.87, 3.82, 3.65 (all s, OCH3),
2.88, 2.48, 2.42, 2.33, 2.22, 2.03, 1.91 (all m, PCHCH3 and
PCH2), 1.55–1.28 (br m, PCHCH3). 13C NMR (100.6 MHz,
CD2Cl2) δ: 357.4 (dd, J (PC) = 19.1 and 15.1 Hz, Ru=C),
129.5, 129.4, 129.3, 127.2, 125.7, 125.5, 123.0, 122.8 (all s,
C6H4), 121.4 (q, J (FC) = 319.9 Hz, CF3), 117.8, 117.7
(both s, =CH), 72.8, 72.7, 71.7 (all s, CH2OCH3), 63.2, 63.1,
61.7 (all s, OCH3), 37.5 (d, J (PC) = 31.2 Hz, PCHCH3),
29.6, 29.4 (both d, J (PC) = 26.3 Hz, PCHCH3), 26.7, 26.5
(both d, J (PC) = 28.8 Hz, PCHCH3), 25.7 (d, J (PC) =
20.2 Hz, PCHCH3), 25.6 (d, J (PC) = 19.6 Hz, PCH2), 23.3
(d, J (PC) = 23.0 Hz, PCH2), 20.2, 20.1, 19.7, 19.65, 19.6,
19.1, 19.0, 18.9 (all s, PCHCH3). 31P NMR (162.0 MHz,
CD2Cl2) δ: 68.0, 56.1 (both d, J (PP) = 24.3 Hz). 19F NMR
(376.5 MHz, CD2Cl2) δ: –78.6 (s). Anal. calcd. for
C48H90Cl2F6O10P4Ru2S2: C 41.11, H 6.47, S 4.57; found: C
41.49, H 6.21, S 4.49.
Preparation of [RuCl(C=CHC6H4-p-CϵCH){κ2(P,O)-i-
Pr2PCH2CH2OMe}2](CF3SO3) (3)
A solution of 1 (262 mg, 0.50 mmol) and 4 (63 mg,
0.50 mmol) in 10 mL of acetone was cooled to 0°C and then
treated with CF3SO3Ag (128 mg, 0.50 mmol). After the re-
action mixture was stirred for 20 min in the dark, the precip-
itate (AgCl) was separated by filtration through Kieselgur
and the filtrate concentrated to ca. 0.5 mL in vacuo. A yel-
low microcrystalline solid was formed which was washed
twice with ether and dried. Yield: 275 mg (72%). IR (KBr)
(cm–1): ν(ϵCH) 3200, ν(CϵC) 2080, ν(C=C) 1620, 1590. H
1
NMR (400 MHz, CD2Cl2) δ: 7.37, 7.30 (AB spin system, J
(HH) = 7.8 Hz, C6H4), 5.09 (t, J (PH) = 3.2 Hz, =CH), 4.18,
4.13, 4.04, 3.80 (all m, CH2OCH3), 3.84, 3.65, (both s,
OCH3), 3.10 (s, ϵCH), 2.88, 2.50, 2.40, 2.34, 2.30, 2.00,
1.85 (all m, PCHCH3 and PCH2), 1.53–1.29 (br m,
PCHCH3). 13C NMR (100.6 MHz, CD2Cl2) δ: 355.5 (dd,
J (PC) = 18.1 and 15.1 Hz, Ru=C), 132.7, 130.5, 126.5,
119.9 (all s, C6H4), 121.4 (q, J (FC) = 320.9 Hz, CF3), 117.2
(s, =CHR), 83.8 (s, CϵCH), 77.4 (s, CϵCH), 72.8, 71.7
(both s, CH2OCH3), 63.2, 63.1, 61.7, 61.6 (all s, OCH3),
37.7 (d, J (PC) = 33.2 Hz, PCHCH3), 29.5 (d, J (PC) =
26.0 Hz, PCHCH3), 26.6 (d, J (PC) = 28.6 Hz, PCHCH3),
25.8 (d, J (PC) = 20.0 Hz, PCHCH3), 25.4 (d, J (PC) =
22.0 Hz, PCH2), 23.2 (d, J (PC) = 24.0 Hz, PCH2), 20.1,
Preparation of [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-m-CϵCH)RhCl(P-i-
Pr3)2](CF3SO3) (9)
19.8, 19.7, 19.65, 19.6, 19.5, 19.1, 19.0 (all s, PCHCH3). 31
P
NMR (162.0 MHz, CD2Cl2) δ: 67.9, 56.3 (both d, J (PP) =
24.1 Hz). 19F NMR (376.5 MHz, CD2Cl2) δ: –78.6 (s). Anal.
calcd. for C29H48ClF3O5P2RuS: C 45.58, H 6.33, S 4.19;
found: C 45.19, H 6.22, S 4.22.
A solution of 8 (101 mg, 0.11 mmol) in 15 mL of freshly
distilled THF was cooled to –60°C and then treated with 2
(160 mg, 0.21 mmol). A characteristic change of color from
violet to orange-yellow occurred. After the reaction mixture
was warmed to room temperature and stirred for 10 min, the
solvent was removed, the remaining orange solid washed
three times with 5 mL portions of pentane (–20°C), and
dried in vacuo. Yield: 159 mg (62%), mp 114°C (dec.). IR
(CH2Cl2) (cm–1): ν(ϵCH) 3070, ν(CϵC) 1790, ν(C=C) 1570.
1H NMR (200 MHz, CD2Cl2) δ: 7.59–6.75 (br m, C6H4),
5.10 (t, J (PH) = 3.1 Hz, =CH), 4.16, 4.14, 4.02, 3.83 (all m,
Preparation of [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-p-CH=C)RuCl{κ2(P,O)-
i-Pr2PCH2CH2OMe}2](CF3SO3)2 (6)
The procedure was analogous to that described for 3, us-
ing 1 (262 mg, 0.50 mmol), 4 (31 mg, 0.25 mmol), and
CF3SO3Ag (128 mg, 0.50 mmol) in 20 mL of acetone as
starting materials. An orange microcrystalline solid was ob-
© 2001 NRC Canada

Werner et al.
523
CH2OCH3), 3.81, 3.67 (both s, OCH3), 3.71 (d, J (RhH) =
2.8 Hz, ϵCH), 2.87, 2.51, 2.37, 2.33, 2.32, 2.10, 1.87 (all m,
RuPCHCH3 and PCH2), 2.74 (m, RhPCHCH3), 1.51–1.39
(br m, RuPCHCH3), 1.24 (dvt, N = 15.7, J (HH) = 7.5 Hz,
RhPCHCH3), 1.04 (dvt, N = 13.8, J (HH) = 6.7 Hz,
RhPCHCH3). 31P NMR (81.0 MHz, CD2Cl2) δ: 66.6, 55.7
(both d, J (PP) = 24.0 Hz, RuP), 31.3 (d, J (RhP) =
117.7 Hz, RhP). 19F NMR (376.5 MHz, CD2Cl2) δ: –78.4
(s). Anal. calcd. for C47H90Cl2F3O5P4RhRuS: C 46.16, H
7.42, S 2.62; found: C 46.09, H 7.35, S 2.26.
PCH2), 25.4 (d, J (PC) = 20.3 Hz, RuPCHCH3), 24.0 (vt,
N = 17.8 Hz, RhPCHCH3), 20.4 (s, RhPCHCH3), 20.2, 20.1,
19.8, 19.6, 19.5, 19.4, 19.3, 19.1 (all s, RuPCHCH3). 31P
NMR (81.0 MHz, CD2Cl2) δ: 68.6, 57.7 (both d, J (PP) =
24.7 Hz, RuP), 43.2 (d, J (RhP) = 135.1 Hz, RhP); 19F NMR
(376.5 MHz, CD2Cl2) δ: –77.5 (s). Anal. calcd. for
C47H90Cl2F3O5P4RhRuS: C 46.16, H 7.42, S 2.62; found: C
45.99, H 7.50, S 2.27.
Preparation of [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-p-CH=C)RhCl(P-i-
Pr3)2](CF3SO3) (12)
Preparation of [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-p-CϵCH)RhCl(P-i-
Pr3)2](CF3SO3) (10)
The procedure was analogous to that described for 11, us-
ing 10 (115 mg, 0.09 mmol) in 10 mL of toluene as starting
material. A green microcrystalline solid was obtained. Yield:
78 mg (71%), mp 108°C (dec.). IR (CH2Cl2) (cm–1): ν(C=C)
1610, 1570. 1H NMR (200 MHz, CD2Cl2) δ: 7.53–6.72
(br m, C6H4), 4.78 (t, J (PH) = 3.0 Hz, Ru=C=CH), 4.21,
4.17, 4.12, 3.97 (all m, CH2OCH3), 3.87, 3.67 (both s,
OCH3), 2.78, 2.45, 2.40, 2.36, 2.34, 2.16, 1.97 (all m,
RuPCHCH3 and PCH2), 2.80 (m, RhPCHCH3), 1.51–1.39
(br m, RuPCHCH3), 1.32 (dvt, N = 12.6, J (HH) = 6.2 Hz,
RhPCHCH3), the signal of Rh=C=CH could not be exactly
located. 13C NMR (100.6 MHz, CD2Cl2) δ: 355.2 (dd,
J (PC) = 18.2 and 15.1 Hz, Ru=C), 291.5 (dt, J (RhC) =
58.2, J (PC) = 15.9 Hz, Rh=C), 134.1, 129.7, 127.2, 122.3
(all s, C6H4), 120.2 (q, J (FC) = 321.1 Hz, CF3), 118.3 (s,
Ru=C=C), 112.4 (dt, J (RhC) = 15.4, J (PC) = 7.1 Hz,
Rh=C=C), 62.5, 61.6 (both s, OCH3), 37.1 (d, J (PC) =
31.6 Hz, RuPCHCH3), 29.3 (d, J (PC) = 24.1 Hz,
RuPCHCH3), 26.1 (d, J (PC) = 28.2 Hz, RuPCHCH3), 25.7
(d, J (PC) = 24.2 Hz, PCH2), 25.3 (d, J (PC) = 20.5 Hz,
PCH2), 25.2 (d, J (PC) = 20.1 Hz, RuPCHCH3), 23.7 (vt,
N = 17.5 Hz, RhPCHCH3), 20.3 (s, RhPCHCH3), 20.1, 19.9,
19.7, 19.6, 19.5, 19.4, 19.2, 19.1 (all s, RuPCHCH3). 31P
NMR (81.0 MHz, CD2Cl2) δ: 68.3, 57.6 (both d, J (PP) =
24.3 Hz, RuP), 43.7 (d, J (RhP) = 135.9 Hz, RhP). 19F NMR
(376.5 MHz, CD2Cl2) δ: –77.7 (s). Anal. calcd. for
C47H90Cl2F3O5P4RhRuS: C 46.16, H 7.42, S 2.62; found: C
46.29, H 7.45, S 2.67.
The procedure was analogous to that described for 9, us-
ing 3 (153 mg, 0.20 mmol) and 8 (94 mg, 0.10 mmol) as
starting materials. An orange microcrystalline solid was ob-
tained. Yield: 147 mg (60%), mp 120°C (dec.). IR (CH2Cl2)
(cm–1): ν(ϵCH) 3070, ν(CϵC) 1780, ν(C=C) 1570. H NMR
1
(200 MHz, CD2Cl2) δ: 7.65–6.78 (br m, C6H4), 5.08 (t, J
(PH) = 3.0 Hz, =CH), 4.13, 4.11, 4.01, 3.81 (all m,
CH2OCH3), 3.78, 3.68 (both s, OCH3), 3.67 (d, J (RhH) =
2.7 Hz, ϵCH), 2.87, 2.50, 2.35, 2.34, 2.31, 2.10, 1.88 (all m,
RuPCHCH3 and PCH2), 2.73 (m, RhPCHCH3), 1.49–1.37
(br m, RuPCHCH3), 1.23 (dvt, N = 15.8, J (HH) = 7.3 Hz,
RhPCHCH3), 1.02 (dvt, N = 13.7, J (HH) = 6.5 Hz,
RhPCHCH3). 31P NMR (81.0 MHz, CD2Cl2) δ: 66.2, 55.6
(both d, J (PP) = 24.3 Hz, RuP), 31.5 (d, J (RhP) =
116.8 Hz, RhP). 19F NMR (376.5 MHz, CD2Cl2) δ: –78.6
(s). Anal. calcd. for C47H90Cl2F3O5P4RhRuS: C 46.16, H
7.42, S 2.62; found: C 46.23, H 7.51, S 2.74.
Preparation of [RuCl{κ2(P,O)-i-
Pr2PCH2CH2OMe}2(C=CHC6H4-m-CH=C)RhCl(P-i-
Pr3)2](CF3SO3) (11)
A solution of 9 (162 mg, 0.13 mmol) in 15 mL of toluene
was stirred for 4 h at room temperature. A change of colour
from orange to dark brown occurred. The solvent was re-
moved in vacuo, the remaining residue was dissolved in
2 mL of toluene, and the solution was chromatographed on
Al2O3 (neutral, activity grade V, height of column = 7 cm).
With toluene, a green fraction was eluted which was
evaporated to dryness in vacuo. The green solid was washed
twice with 2 mL portions of pentane (0°C) and dried in
vacuo. Yield: 113 mg (71%), mp 105°C (dec.). IR (CH2Cl2)
Acknowledgements
We thank the Deutsche Forschungsgemeinschaft (SFB
347), the European Community (Network ERBCHRXCT
930147) for financial support, and the Spanish Ministry of
Education for a scholarship (to M. M., EX94 25143294). We
also gratefully acknowledge support by Dr. W. Buchner and
Mrs. M.-L. Schäfer (NMR spectra), Mrs. R. Schedl and Mr.
C. P. Kneis (DTA measurements and elemental analyses),
and Degussa AG (chemicals).
1
(cm–1): ν(C=C) 1610, 1570. H NMR (200 MHz, CD2Cl2) δ:
7.55–6.74 (br m, C6H4), 4.80 (t, J (PH) = 3.1 Hz,
Ru=C=CH), 4.17, 4.15, 4.02, 3.85 (all m, CH2OCH3), 3.80,
3.63 (both s, OCH3), 2.88, 2.48, 2.39, 2.35, 2.31, 2.14, 1.92
(all m, RuPCHCH3 and PCH2), 2.74 (m, RhPCHCH3), 1.53–
1.42 (br m, RuPCHCH3), 1.30 (dvt, N = 12.8, J (HH) =
6.3 Hz, RhPCHCH3), the signal of Rh=C=CH could not be
exactly located. 13C NMR (100.6 MHz, CD2Cl2) δ: 355.3
(dd, J (PC) = 17.9 and 14.8 Hz, Ru=C), 292.7 (dt, J (RhC) =
59.6, J (PC) = 15.5 Hz, Rh=C), 133.8, 130.0 127.3, 122.2
(all s, C6H4), 119.6 (q, J (FC) = 319.1 Hz, CF3), 117.9 (s,
Ru=C=C), 112.2 (dt, J (RhC) = 15.3, J (PC) = 7.0 Hz,
Rh=C=C), 62.3, 61.3 (both s, OCH3), 36.9 (d, J (PC) =
31.8 Hz, RuPCHCH3), 29.0 (d, J (PC) = 24.2 Hz,
RuPCHCH3), 26.0 (d, J (PC) = 28.0 Hz, RuPCHCH3), 25.6
(d, J (PC) = 24.2 Hz, PCH2), 25.5 (d, J (PC) = 20.5 Hz,
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