Ruthenium(II) complexes with ferrocene-modified arene ligands: Synthesis and electrochemistry

Article abstract of DOI:10.1016/j.jorganchem.2004.03.047

A series of arene-ruthenium complexes of the general formula [RuCl₂{η⁶-C₆H₅ (CH₂)₂R}L] with R=OH, CH₂OH, OC(O)Fc, CH₂OC(O)Fc (Fc=ferrocenyl) and L=PPh₃, (diphenylphosphino)ferrocene, or bridging 1,1′-bis(diphenylphosphino)ferrocene, have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene-ruthenium complexes: (a) esterification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl₃ · n H₂O to afford [RuCl₂ {η⁶-C₆H₅ (CH₂)₂OC(O)Fc}]₂, and (b) esterification between ferrocene carboxylic acid and [RuCl₂{η⁶ -C₆H₅(CH₂)₃OH}L] to give [RuCl₂{η⁶-C₆H₅ (CH₂)₃OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by mass spectrometry. The single-crystal X-ray structure analysis of [RuCl₂{η⁶-C₆H₅ (CH₂)₃OH}(PPh₃)] shows that the presence of a CH₂CH₂CH₂OH side-arm allows [RuCl₂{η⁶-C₆H₅ (CH₂)₃OH}(PPh₃)] to form an intramolecular hydrogen bond with a chlorine atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system.

Full text of DOI:10.1016/j.jorganchem.2004.03.047

Journal of Organometallic Chemistry 689 (2004) 2456–2463
www.elsevier.com/locate/jorganchem
Ruthenium(II) complexes with ferrocene-modified arene
ligands: synthesis and electrochemistry
a,
Bruno Therrien , Ludovic Vieille-Petit , Julie Jeanneret-Gris , Petr Stepnicka
a
a
b,
*
*
ꢀ
ꢀ
ꢀ
,
a
€
Georg Suss-Fink
a
Institut de Chimie, Universitꢁe de Neuch^atel, Case postale 2, avenue de Bellevaux 51, CH-2007 Neuch^atel, Switzerland
Department of Inorganic Chemistry, Charles University, Hlavova 2030, 128 40 Prague 2, Czech Republic
b
Received 11 September 2003; accepted 22 March 2004
Abstract
A series of arene–ruthenium complexes of the general formula [RuCl2{g6-C6H5(CH2)2R}L] with R ¼ OH, CH2OH, OC(O)Fc,
CH2OC(O)Fc (Fc ¼ ferrocenyl) and L ¼ PPh3, (diphenylphosphino)ferrocene, or bridging 1,10-bis(diphenylphosphino)ferrocene,
have been synthesized. Two synthetic pathways have been used for these ferrocene-modified arene–ruthenium complexes: (a) es-
terification of ferrocene carboxylic acid with 2-(cyclohexa-1,4-dienyl)ethanol, followed by condensation with RuCl3 ꢀ nH2O to afford
[RuCl2{g6-C6H5(CH2)2OC(O)Fc}]2, and (b) esterification between ferrocene carboxylic acid and [RuCl2{g6-C6H5(CH2)3OH}L] to
give [RuCl2{g6-C6H5(CH2)3OC(O)Fc}L]. All new compounds have been characterized by NMR and IR spectroscopy as well as by
mass spectrometry. The single-crystal X-ray structure analysis of [RuCl2{g6-C6H5(CH2)3OH}(PPh3)] shows that the presence of a
CH2CH2CH2OH side-arm allows [RuCl2{g6-C6H5(CH2)3OH}(PPh3)] to form an intramolecular hydrogen bond with a chlorine
atom. The electrochemical behavior of selected representative compounds has been studied. Complexes with ferrocenylated side
arms display the expected cyclic voltammograms, two independent reversible one-electron waves of the Ru(II)/Ru(III) and Fe(II)/
Fe(III) redox couples. Introduction of a ferrocenylphosphine onto the ruthenium is reflected by an additonal reversible, one-electron
wave due to ferrocene/ferrocenium system which is, however, coupled with the Ru(II)/Ru(III) redox system.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Arene ligands; Ferrocene derivatives; Phosphine ligands; Ruthenium; Electrochemistry
1. Introduction
sulfido, a phosphido or an amido ferrocenyl derivative
(for recent examples see [3]), or reaction of terminal
ferrocenyl alkynes with the metal center (for recent ex-
amples see [4]). Nevertheless, the functionalization of an
g6-arene ligand by a ferrocenyl group has not received
great attention, and examples of such compounds are
still rare [5]. Among them we have to mention the work
of Hidai and co-workers [6], who have synthesised a
ruthenium complex containing a bidentate cyclopenta-
dienyl-modified ferrocenyl phosphine ligand (Scheme 1).
In this compound, the cyclopentadienyl moiety is teth-
ered to a phosphine ferrocene derivative in four steps
before being activated and finally coordinated to the
ruthenium atom. This chiral-at-the-metal complex was
used in asymmetric catalysis, but no electrochemical
study was performed.
Heteronuclear ruthenium complexes with ferrocene-
containing ligands such as [Ru(NH3)5(NCFc)]2þ, are
known for more then 25 years [1]. However, arene–ru-
thenium complexes containing chelating bis(phosphi-
nyl)ferrocene ligands have been reported for the first
time by Bruce et al. [2]. Since then, other complexes
containing ferrocene and arene–ruthenium units have
been synthesized by either coordination to metal by a
* Corresponding authors. Tel.: +41-32-718-2499; fax: +41-32-718-
2511.
E-mail addresses: bruno.therrien@unine.ch (B. Therrien), stepnic@
ꢀ
natur.cuni.cz (P. Stepnicka).
ꢀ
ꢀ
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.03.047

B. Therrien et al. / Journal of Organometallic Chemistry 689 (2004) 2456–2463
Me
2457
H
Me
H
H
Me
Me2N
Ph2P
HCp
Ph2P
1) H2O2
2) MeI
3) CpNa
4) LiAlH4
5) sec-BuLi
Fe
Fe
Fe
P
Ru
Ph2
6) RuCl2(PPh3)3
Cl
PPh3
Scheme 1.
In this paper, we used two different strategies in order
to tether a ferrocenyl moiety to an arene ligand coordi-
nated to a ruthenium atom. Both imply a classical es-
terification reaction, in which the esterification is done
either prior to the coordination of the arene ligand (a), or
after the arene coordination (b), as lined out in Scheme 2.
From these two complementary approaches, a wide
variety of complexes can be synthesised. Starting from
the dinuclear ruthenium complex [RuCl2{g6-
C6H5(CH2)2OC(O)Fc}]2, route A, a phosphine ligand
(L) can be introduced by cleavage of the chloro bridge,
forming the corresponding [RuCl2{g6-C6H5(CH2)2
OC(O)Fc}L], where in route B, L is introduced prior to
the esterification. The use of (diphenylphosphino)ferro-
cene (FcPPh2) or 1,10-bis(diphenylphosphino)ferrocene
(fc(PPh2)2) as the ligands allow us to introduce an other
ferrocene moiety onto the ruthenium atom. This way,
we can form heteronuclear complexes possessing as
many as three different metallic cores, two different
ferrocene centers and one ruthenium.
2. Results and discussion
2.1. Synthesis and characterisation
The dinuclear ruthenium complex [RuCl2{g6-
C6H5(CH2)2O(CO)Fc}]2 [7] reacts with two equivalents
of PPh3, FcPPh2 or with one equivalent of fc(PPh2)2 in
dichloromethane to give quantitatively the heteronu-
clear complexes [RuCl2{g6-C6H5(CH2)2OC(O)Fc}-
(PPh3)] (1), [RuCl2{g6-C6H5(CH2)2OC(O)Fc}(FcPPh2)]
(2) and the ferrocene bridged, pentanuclear complex
[{RuCl2(g6-C6H5(CH2)2 OC(O)Fc)}2(l-fc(PPh2)2)] (3),
respectively (Scheme 3). The composition and structure
of the products have been determined by 1H and
31P{1H} NMR, infrared and mass spectrometry.
The formation of complexes 1, 2 and 3 is conveniently
monitored by 31P{1H} NMR spectroscopy. The 31P{1H}
NMR of 1 shows a singlet at 28.6 ppm, the chemical shift
being comparable to those observed for the analogous
triphenylphosphine (g6-arene)–ruthenium complexes
Fe
Fe
Fe
O
O
O
COOH
Ru
Ru
.
Cl
RuCl3 n H2O
Cl
Cl
Fe
+
(a)
Fe
Cl
OH
O
O
O
OH
+
COOH
O
(b)
Fe
O
Ru
Ru
Cl
L
Cl
L
Cl
Cl
Scheme 2.

2458
B. Therrien et al. / Journal of Organometallic Chemistry 689 (2004) 2456–2463
O
Fe
O
Fe
O
O
Ru
Cl
P
Ru
Ph2
Cl
Cl
Ph3P
Fe
Cl
1
2
O
Fe
O
Ru
P
Cl
Cl
Ph2
Ph2
P
Fe
Cl
Cl
Ru
O
Fe
O
3
Scheme 3.
[RuCl2(g6-C6H5Fc)(PPh3)] [7], and [RuCl2(g6-C6Et6)
(PPh3)] [8] which show signals at 28.6 and 24.0 ppm,
respectively. The presence of an electron donating fer-
rocene moiety in 2 and 3 results in an upfield shift of the
31P{1H} NMR signals by almost 10 ppm as compared to
complex 1.
In a similar reaction pathway, the dinuclear ruthe-
nium complex [RuCl2{g6-C6H5(CH2)3OH}]2 [9] reacts
with phosphine ligands in dichloromethane to give
quantitatively [RuCl2{g6-C6H5(CH2)3OH}(PPh3)] (4),
and the heteronuclear complexes [RuCl2{g6-C6H5
(CH2)3OH}(FcPPh2)] (5) and [{RuCl2(g6-C6H5(CH2)3
OH)}2(l-fc(PPh2)2)] (6), respectively (Scheme 4). Com-
pounds 4, 5 and 6 have been characterized by NMR and
IR spectroscopy, and by mass spectrometry. Complex 4
was first synthesised by Miyaki et al. [9] from the reac-
tion of [Ru{g6-C6H5(CH2)3OH}Cl2]2 with triphenyl-
phosphine in CH3CN. To study its electrochemical
behavior, using a slightly different synthetic route,
complex 4 was synthesized in excellent yield.
complexes exhibit signals at 29.4, 21.4 and 20.9 ppm
respectively. All attempts to crystallize complex 5 and 6
have failed, and only the single-crystal X-ray analysis of
complex 4 was obtained, see Fig. 1.
The ruthenium atom possesses a pseudo-octahedral
geometry, and the metrical parameters around the me-
tallic core compare well with those of similar three-leg-
ged piano-stool [Ru(g6-arene)(PPh3)Cl2] complexes [10].
A distortion at the arene ligand is present, the Ru–C
bond distance trans to the phosphorous atom, Ru(1)–
ꢂ
C(1) 2.280(5) A, is elongated as compared to the other
ꢂ
Ru–C bonds [ranging between 2.170(4) and 2.249(5) A].
In the solid state, an intramolecular hydrogen bond
between the hydroxy function and a chlorido ligand is
observed. The O–Cl distance of the hydrogen bond
ꢂ
[O(1)–Hꢀ ꢀ ꢀCl(1)] is 3.121(5) A with an angle of 159.2°.
Complexes 4, as well as 5 and 6 contain a hydroxy
function available for esterification by classical method
[11].
Complexes 4, 5 and 6 react with ferrocenecarb-
oxylic acid in dichloromethane, in the presence of
condensation agents, N,N-dicyclohexylcarbodiimine,
As for complexes 1 to 3, the formation of 4, 5 and 6 is
best monitored by 31P{1H} NMR spectroscopy. These
OH
HO
Ru
OH
Ru
OH
P
Cl
Cl
Ph2
Cl
P
Ph2
P
Fe
Ru
Cl
Cl
Ph2
Cl
Cl
Ph3P
Ru
Fe
Cl
4
5
6
Scheme 4.

B. Therrien et al. / Journal of Organometallic Chemistry 689 (2004) 2456–2463
2459
attempts to crystallize complexes 7, 8 and 9 were un-
1
successful. The H and 31P{1H} NMR spectra of com-
plexes 7, 8 and 9 show the expected signals, being in
agreement with the structures proposed in Scheme 5.
Complexes 3, 6, 7 and 9 give rise to the expected
molecular peaks m/z at 1568, 1171, 783 and 1595, re-
spectively, which in complexes 1, 4, 5 and 8 the frag-
ments [M–Cl]þ are observed as the most intense peaks.
The loss of chlorine atoms have been previously ob-
served for dichloro arene–ruthenium complexes [4c].
2.2. Electrochemistry
The representative and some model compounds (such
as ligands and precursors) have been studied by vol-
tammetry and cyclic voltammetry on platinum disc
electrode. The relevant data are summarized in Table 1.
As revealed by the separation of cyclovoltammetric
peaks (DEp 60–70 mV at 100 mV/s scan rate) and their
intensity ratios (ipa=ipc) close to unity, the ferrocene/
ferrocenium oxidations are in all cases one-electron,
reversible redox processes. The nature of Ru-centered
oxidations is generally more difficult to judge, as the
respective waves are sometimes located at the onset of
the base electrolyte decomposition. Nevertheless, where
both counter peaks are clearly detectable, the dEp and
(ipa=ipc) values also point to a normal one-electron, re-
versible processes.
The redox potential of the RuII=III couples in com-
plexes 4 and 5 are higher than those observed in the
analogous complexes [RuCl2(g6-C6Me6)(PPh3)] (E0;
Ru: 0.48 V) and [RuCl2(g6-C6Me6)(FcPPh2)] (E0; Fe:
0.03, Ru: 0.66 V) [4c], which corresponds to a lower
electron donating ability of the g6-arene ligand in 4 and
Fig. 1. ORTEP view of 4, displacement ellipsoids are drawn at the 35%
probability level, hydrogen atoms are omitted for clarity. Selected
ꢂ
bond lengths (A) and angles (°): Ru(1)–P(1) 2.3446(14), Ru(1)–Cl(1)
2.4199(10), Ru(1)–Cl(2) 2.4105(12), Ru(1)–C(1) 2.280(5), Ru(1)–C(2)
2.249(5), Ru(1)–C(3) 2.170(4), Ru(1)–C(4) 2.176(5), Ru(1)–C(5)
2.193(6), Ru(1)–C(6) 2.171(5); P(1)–Ru(1)–Cl(1) 86.21(4), P(1)–Ru(1)–
Cl(2) 88.84(6), Cl(1)–Ru(1)–Cl(2) 90.21(4).
4-(dimethyl-amino) pyridine, and 4-pyrrolidinopyridine
to give the corresponding ferrocenoyl derivatives,
[RuCl2{g6-C6H5(CH2)3OC(O)Fc}(PPh3)] (7), [RuCl2
{g6-C6H5(CH2)3OC(O)Fc}(FcPPh2)] (8) and [{RuCl2
(g6-C6H5(CH2)3OC(O)Fc)}2(l-fc(PPh2)2)] (9), see Sch-
eme 5. These new complexes have been characterized
unambiguously by NMR, IR and mass spectroscopy.
The infrared spectrum of 7, 8 and 9 exhibit the
characteristic mCO absorption around 1710 cmꢁ1 of the
ester function and a set of bands around 1100 and
1000 cmꢁ1 due to the presence of ferrocene moieties. All
O
Fe
O
Fe
O
Ru
O
Cl
P
Ru
Ph2
Cl
Cl
Ph3P
Fe
Cl
7
8
O
Fe
Ru
O
P
Cl
Cl
Ph2
Ph2
P
Fe
Cl
Cl
Ru
O
Fe
O
9
Scheme 5.

2460
B. Therrien et al. / Journal of Organometallic Chemistry 689 (2004) 2456–2463
Table 1
Cyclovoltammetric dataa;b
Compound
Couplec
E0 (V)
dEp (mV)
1
FeC
Ru
FeP
FeC
Ru
Ru
FeP
Ru
FeP
Ru
Fe
0.23
0.79
60
70
60
60
70
60
70
70
70
70
70
60
2
0.11
0.23
0.90
0.76
4
5
0.10
0.88
6
0.10
0.80–0.83d;e
0.47
b
fc(C(O)O(CH2)2C6H8)2
FcCO2H
Fe
Fe
0.26
0.45d
0.11
b
fc(CO2H)2
FcPPh2
fc(PPh2)2
Fe
Fe
65
60
0.18
a The potentials are given relative to internal ferrocene/ferrocenium
E0 is redox potential determined by cyclic voltammetry as
E0 ¼ 1=2ðEpa þ EpcÞ, while dEp stands for the separation of the cy-
clovoltammetric counter peaks, DEp ¼ Epa ꢁ Epc. Epa and Epc are the
anodic and cathodic peak potentials, respectively. E0 values are iden-
tical with the respective half-wave potentials (E1=2) determined by
voltammetry. For conditions see Section 3.
b Fc ¼ ferrocenyl, fc ¼ ferrocene-1,10-diyl, fc(PPh2)2 ¼ 1,10-bis(diph-
enylphosphino)ferrocene.
c FeII/FeIII or RuII/RuIII redox couples. For compounds having
more ferrocenyl groups, indexes P and C indicate ferrocene/ferroce-
nium couples in the phosphine and carboxyl part, respectively.
d Epa given.
e The wave appears at the onset of base electrolyte decomposition;
counterwave not clearly detectable.
Fig. 2. Cyclic voltamograms of complexes 1 (top) and 2 (bottom).
5. A shift of the RuII=III redox potential to higher values
upon replacing a simple triphenylphosphine with a
ferrocenyl phosphine ligand also corresponds well to the
mentioned pair and can be accounted for by the pre-
ceding oxidation which changes the strongly electron-
donating ferrocene substituent at phosphorus into an
electron-withdrawing ferrocenium, thus lowering the
electron density at the ruthenium center and making the
Ru-oxidation more difficult. However, the mutual dif-
ference of the RuII=III potential is notably lower in the
present case (0.12 V) than for the mentioned g6-C6Me6
complexes (0.18 V).
The presence of a ferrocenyl phosphine in 5 and 6 is
naturally reflected by an additional wave due to the
ferrocene/ferrocenium couple. Similarly to [RuCl2(g6-
C6Me6)(FcPPh2)], the ferrocene/ferrocenium redox po-
tentials in 5 and 6 are nearly identical with those in the
corresponding uncoordinated phosphines, which con-
trasts with the expected behavior that an electron den-
sity decrease at phosphorus, due to the coordination to
ruthenium, would be relayed further onto the ferrocene
unit and result into an increase of its oxidation poten-
tial. As it is apparent that the ferrocene and (g6-arene)–
ruthenium units communicate electronically (see above),
the negligible potential shift is probably a result of an
efficient compensation of P ! Ru donation with P Ru
back bonding interactions [4c].
A formal introduction of a second ferrocenyl unit in
this type of complexes to give ferrocene-carbonyl-mod-
ified compounds 1 and 2 is reflected by the presence of
an additional, reversible ferrocene/ferrocenium wave,
see Fig. 2. The wave appears at the same position for
both compounds and is shifted by 30 mV cathodically
from the oxidation of FcCO2H. The ferrocenyl group is
separated from the g6-arene by a non-conjugated tether
and behaves as an independent redox system while the
ferrocene group within the coordinated phosphine part
communicates with the (g6-arene)–ruthenium unit sim-
ilarly as described for 5 and 6. The RuII=III and
Fe(phosphine)II=III potentials in the pairs of analogous
complexes 4–1 and 5–2 differ only insignificantly.
3. Experimental
3.1. General
All manipulations were carried out using freshly
distilled CH2Cl2. NMR spectra were recorded on a

B. Therrien et al. / Journal of Organometallic Chemistry 689 (2004) 2456–2463
2461
Varian 200 MHz spectrometer. IR spectra were re-
3.2.3. Spectroscopic data 2
corded on a Perkin–Elmer Spectrum One FT-IR
spectrometer (4000–400 cmꢁ1). Microanalyses were
carried out by the Laboratory of Pharmaceutical
Chemistry, University of Geneva (Switzerland). Elec-
tro-spray mass spectra were obtained in positive-ion
mode with an LCQ Finnigan mass spectrometer. The
starting dinuclear dichloro complexes [RuCl2{g6-C6H5
(CH2)2O(CO)Fc}]2 [7] and [Ru{g6-C6H5(CH2)3OH}
Cl2]2 [9] were prepared according to the published
methods. All other reagents were purchased (Fluka or
Aldrich) and used as received.
IR (KBr, cmꢁ1): m(CH) 3062 (w), 2925 (m); m(CO)
1710 (s); Fc 1106 (w), 1001 (m); PPh2 486 (w). 1H NMR
(200 MHz, CDCl3, ppm): d ¼ 7:76 (m, 4H, PPh2), 7.36
(m, 6H, PPh2), 5.15 (m, 5H, C6H5), 4.64 (s, 2H, C5H4),
4.42 (s, 4H, C5H4), 4.38 (m, 2H, –OCH2CH2–), 4.31 (s,
2H, C5H4), 4.01 (s, 5H, C5H5), 3.79 (s, 5H, C5H5), 2.88
(m, 2H, –OCH2CH2–). 31P{1H} NMR (81 MHz,
CDCl3): d ¼ 20:9 ppm. MS (EI mode, CHCl3): m/
z ¼ 899 [M + Na]. Anal. Calc. for C41H37Cl2Fe2
O2P1Ru1: C, 56.19; H, 4.26. Found: C, 56.02; H, 4.38%.
Electrochemical measurements were carried out with
a multipurpose polarograph PA3 interfaced to an XY
3.2.4. Spectroscopic data 3
IR (KBr, cmꢁ1): m(CH) 3053 (w), 2924 (m); m(CO)
1709 (s); Fc 1096 (w), 1027 (m); PPh2 485 (w). 1H NMR
(200 MHz, CDCl3, ppm): d ¼ 7:89 (m, 8H, PPh2), 6.99
(m, 12H, PPh2), 4.80 (m, 10H, C6H5), 4.78 (m, 4H,
C5H4), 4.70 (m, 4H, C5H4), 4.33 (m, 4H, –OCH2CH2–),
4.26 (m, 4H, C5H4), 4.02 (m, 4H, C5H4), 3.93 (s, 10H,
C5H5), 2.84 (m, 4H, –OCH2C H2–) 31P{1H} NMR (81
MHz, CDCl3): d ¼ 25:5 ppm. MS (EI mode, CHCl3): m/
z ¼ 1568 [M]. Anal. Calc. for C72H64Cl4Fe3O4P2Ru2: C,
55.19; H, 4.12. Found: C, 55.32; H, 4.60%.
ꢁ ꢀꢃ
Recorder 4103 (both by Laboratornı prıstroje, Prague)
at room temperature using a standard three-electrode
system: platinum disc working, platinum wire auxiliary,
and Ag/AgCl (1 M KCl) reference electrode. The ana-
lyzed solutions contained ca. 4 ꢂ 10ꢁ4 M of the analyte
and 0.1 M Bu4NPF6 (Fluka, puriss for electrochemistry)
dissolved in dichloromethane (Merck p.a., used without
further purification) and were purged with argon. Cyclic
voltammograms were recorded on stationary disc elec-
trode at 100 mV/s while the voltammograms were
measured with rotating electrode (1000 minꢁ1) at a scan
rate of 20 mV/s. The potentials are given in volts relative
to the redox potential of the internal ferrocene/ferroce-
nium standard.
3.2.5. [RuCl2{g6-C6H5(CH2)3OH}(L)] (4: L ¼ PPh3,
5: L ¼ FcPPh2) and [{RuCl2(g6-C6H5(CH2)3OH)}2(l-
fc(PPh2)2)] (6)
To a solution of [RuCl2{g6-C6H5(CH2)3OH}]2 (300
mg, 0.5 mmol) in CH2Cl2 (20 ml) was added L {PPh3
(265 mg, 1.01 mmol), FcPPh2 (378 mg, 1.02 mmol),
fc(PPh2)2 (283 mg, 0.51 mmol)}, and the mixture was
stirred overnight. The orange–brown precipitate was
filtered through celite to eliminate insoluble degradation
materials. The solution is evaporated and the solid dried
under vacuum to give the product. Yield 465 mg (81%)
for 4: Yield 520 mg (75%) for 5: Yield 220 mg (38%)
for 6.
3.2. Syntheses
3.2.1. [RuCl2{g6-C6H5(CH2)2O(CO)Fc}L] (1: L ¼
PPh3, 2: L ¼ FcPPh2) and [{RuCl2(g6-C6H5(CH2)2
OC(O)Fc)}2(l-fc(PPh2)2)] (3)
To a solution of [RuCl2{g6-C6H5(CH2)2O(CO)Fc}]2
(200 mg, 0.2 mmol) in CH2Cl2 (20 ml) was added L
{PPh3 (114 mg, 0.43 mmol), FcPPh2 (155 mg,
0.42 mmol), fc(PPh2)2 (116 mg, 0.21 mmol)}, and the
mixture was stirred for 24 h. The orange–brown pre-
cipitate was filtered through celite to eliminate insoluble
degradation materials. The solution is evaporated and
the solid dried under vacuum to give the product. Yield
153 mg (50%) for 1: Yield 122 mg (35%) for 2: Yield 151
mg (48%) for 3.
3.2.6. Spectroscopic data 4
IR (KBr, cmꢁ1): m(OH) 3182 (s, br); m(CH) 3059 (w),
2927 (w); Fc 1093 (m), 999 (w); PPh3 527 (w). 1H NMR
(200 MHz, CDCl3): d ¼ 7:73 (m, 6H, PPh3), 7.40 (m,
9H, PPh3), 5.35 (m, 2H, C6H5), 5.13 (m, 2H, C6H5), 4.52
(m, 1H, C6H5), 3.77 (m, 2H, –CH2CH2CH2OH), 2.79
(m, 2H, –CH2CH2CH2OH), 1.96 (m, 2H, –CH2CH2
CH2OH). 31P{1H} NMR (81 MHz, CDCl3): d ¼ 29:4
ppm. MS (ESI, positive mode, acetone): m/z ¼ 535 [M–
Cl]. Anal. Calc. for C27H27Cl2O1P1Ru1: C, 56.8; H,
4.77. Found: C, 57.00; H, 4.70%.
3.2.2. Spectroscopic data 1
IR (KBr, cmꢁ1): m(CH) 3060 (w), 2923 (w); m(CO)
1698 (s); Fc 1095 (m), 999 (w); PPh3 526 (s). H NMR
1
(200 MHz, CDCl3, ppm): d ¼ 7:83 (m, 6H, PPh3), 7.44
(m, 9H, PPh3), 5.22 (m, 5H, C6H5), 4.74 (m, 2H, C5H4),
4.55 (m, 2H, C5H4), 4.43 (m, 2H, –OCH2CH2–), 4.15 (s,
5H, C5H5), 3.07 (m, 2H, –OCH2C H2–). 31P{1H} NMR
(81 MHz, CDCl3): d ¼ 28:6 ppm. MS (EI mode,
CHCl3): m/z ¼ 733 [M–Cl]. Anal. Calc. for
C37H33Cl2Fe1O2P1Ru1: C, 57.83; H, 4.33. Found: C,
58.07; H, 4.38%.
3.2.7. Spectroscopic data 5
IR (KBr, cmꢁ1): m(OH) 3431 (s, br); m(CH) 3056 (w),
2931 (w); Fc 1097 (s), 1027 (m); PPh2 487 (m). 1H NMR
(200 MHz, CDCl3): d ¼ 7:79 (m, 4H, PPh2), 7.41 (m,
6H, PPh2), 5.21 (m, 2H, C6H5), 5.07 (m, 3H, C6H5), 4.55
(m, 2H, C5H4), 4.38 (m, 2H, C5H4), 3.95 (s, 5H, C5H5),

2462
B. Therrien et al. / Journal of Organometallic Chemistry 689 (2004) 2456–2463
3.75 (m, 2H, –CH2CH2CH2OH), 2.70 (m, 2H,
–CH2CH2CH2OH), 1.91 (m, 2H, –CH2CH2CH2OH).
31P{1H} NMR (81 MHz, CDCl3): d ¼ 21:4 ppm. MS
(ESI, positive mode, acetone): m/z ¼ 643 [M–Cl]. Anal.
Calc. for C31H31Cl2Fe1O1P1 Ru1: C, 54.87; H, 4.60.
Found: C, 54.95; H, 4.69%.
4.44 (s, 4H, C5H4), 4.34 (s, 2H, C5H4), 4.18 (m, 2H,
–CH2CH2CH2O–), 4.03 (s, 5H, C5H5), 3.84 (s, 5H,
C5H5), 2.91 (m, 2H, –CH2CH2CH2O–), 1.83 (m, 2H,
–CH2CH2CH2O–). 31P{1H} NMR (81 MHz, CDCl3):
d ¼ 29:5 ppm. MS (EI mode, CHCl3): m/z ¼ 855 [M–Cl].
Anal. Calc. for C42H39Cl2Fe2O2P1Ru1: C, 56.66; H,
4.42. Found: C, 56.32; H, 4.35%.
3.2.8. Spectroscopic data 6
IR (KBr, cmꢁ1): m(OH) 3416 (s, br); m(CH) 3055 (w),
2923 (w); Fc 1095 (m), 1027 (m); PPh2 490 (w).1H NMR
(200 MHz, CDCl3): d ¼ 7:58 (m, 8H, PPh2), 7.44 (m,
12H, PPh2), 5.98 (t, 2H, C6H5), 5.75 (d, 4H, C6H5), 5.27
(m, 4H, C5H4), 5.17 (d, 4H, C6H5), 4.50 (m, 4H, C5H4),
3.43 (m, 4H, –CH2CH2CH2OH), 2.36 (t, 4H,
–CH2CH2CH2OH), 1.63 (m, 4H, –CH2CH2CH2OH).
31P{1H} NMR (81 MHz, CDCl3): d ¼ 20:9 ppm. MS
(ESI, positive mode, acetone) : m/z ¼ 1171 [M]. Anal.
Calc. for C52H52Cl4Fe1O2P2Ru2: C, 53.35; H, 4.48.
Found: C, 53.42; H, 4.55%.
3.2.12. Spectroscopic data 9
IR (KBr, cmꢁ1): m(CH) 3057 (w), 2927 (w); m(CO)
1708 (s); Fc 1095 (m), 1019 (m); PPh2 468 (m). 1H NMR
(200 MHz, CDCl3, ppm): d ¼ 7:87 (m, 8H, PPh2), 7.03
(m, 12H, PPh2), 4.82 (m, 10H, C6H5), 4.79 (m, 4H,
C5H4), 4.65 (m, 4H, C5H4), 4.28 (m, 4H,
–CH2CH2CH2O–), 4.24 (m, 4H, C5H4), 3.99 (m, 4H,
C5H4), 3.94 (s, 10H, C5H5), 2.99 (m, 4H,
–CH2CH2CH2O–), 1.79 (m, 4H, –CH2CH2CH2O–).
31P{1H} NMR (81 MHz, CDCl3): d ¼ 29:7 ppm. MS
(EI mode, CHCl3): m/z ¼ 1595 [M]. Anal. Calc. for
C74H68Cl4Fe3O4P2Ru2: C, 55.73; H, 4.30. Found: C,
55.42; H, 4.12%.
3.2.9. [RuCl2{g6-C6H5(CH2)3OC(O)Fc}(L)] (7: L ¼
PPh3, 8: L ¼ FcPPh2) and [{RuCl2(g6-C6H5(CH2)3
OC(O)Fc)}2(l-fc(PPh2)2)] (9)
3.3. Structure determinations
A solution of ferrocene carboxylic acid (100 mg,
0.43 mmol), N,N-dicyclohexylcarbodiimide (93 mg,
0.45 mmol), 4-(dimethylamino)pyridine (37 mg, 0.3
mmol), 4-pyrrolidinopyridine (45 mg, 0.3 mmol), and
[RuCl2{g6-C6H5(CH2)3OH}(L)] (0.4 mmol of 4 and 5;
0.2 mmol of 6) in CH2Cl2 (20 ml) was stirred under
nitrogen at room temperature during 3 days. The
resulting solution was filtered through celite to remove
N,N-dicyclohexylurea, and the solid dried under
vacuum to give the product. Yield 135 mg (43%)
for 7: Yield 188 mg (53%) for 8: Yield 88 mg (28%)
for 9.
X-ray data for [4]; C27H27Cl2OPRu, M ¼ 570:43
g/mol, monoclinic, P21=c (no. 14), a ¼ 16:7409ð8Þ,
ꢂ
b ¼ 7:8989ð3Þ, c ¼ 18:0745ð10Þ A, b ¼ 93:469ð6Þ°,
3
ꢂ
U ¼ 2385:7ð2Þ A , T ¼ 153 K, Z ¼ 4,
l
(Mo
Ka) ¼ 0.967 mmꢁ1, 4622 reflections measured, 3145
unique (Rint ¼ 0.0370) which were used in all calcula-
tions. The final wR(F2) was 0.1168 (all data). The data
were measured using a Stoe Image Plate Diffraction
system equipped with a / circle, using Mo Ka graphite
ꢂ
monochromated radiation (k ¼ 0:71073 A) with / range
0–180°, increment of 0.7°, 3 min per frame, 2h range
ꢂ
from 2.0° to 26°, Dmax ꢁ Dmin ¼ 12:45 ꢁ 0:81 A. The
structure was solved by direct methods using the pro-
gram SHELXS-97 [12]. The refinement and all further
calculations were carried out using SHELXL-97 [13]. The
H-atoms were included in calculated positions and
treated as riding atoms using the SHELXL default pa-
rameters. The non-H atoms were refined anisotropically,
using weighted full-matrix least-square on F2. Fig. 2 was
drawn with ORTEP [14].
3.2.10. Spectroscopic data 7
IR (KBr, cmꢁ1): m(CH) 3057 (w), 2927 (w); m(CO)
1708 (s); Fc 1096 (m), 1002 (w); PPh3 529 (s). d ¼ 7:87
(m, 6H, PPh3), 7.50 (m, 9H, PPh3), 5.25 (m, 5H, C6H5),
4.69 (m, 2H, C5H4), 4.53 (m, 2H, C5H4), 4.23 (m, 2H,
–CH2CH2CH2O–), 4.11 (s, 5H, C5H5), 2.95 (m, 2H,
–CH2CH2CH2O–), 1.78 (m, 2H, –CH2CH2CH2O–).
31P{1H}5 NMR (81 MHz, CDCl3): d ¼ 28:3 ppm. MS
(EI mode, CHCl3): m/z ¼ 783 [M]. Anal. Calc. for
C38H35Cl2Fe1O2P1Ru1: C, 58.33; H, 4.51. Found: C,
58.56; H, 4.78%.
4. Supplementary material
CCDC-216104 4 contains the supplementary crys-
tallographic data for this paper. These data can be ob-
tained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [or from the Cambridge Crystallo-
graphic Data Centre, 12, Union Road, Cambridge CB2
1EZ, UK; fax: (internat.) +44-1223/336-033; e-mail:
deposit@ccdc.cam.ac.uk].
3.2.11. Spectroscopic data 8
IR (KBr, cmꢁ1): m(CH) 3066 (w), 2920 (m); m(CO)
1706 (s); Fc 1111 (w), 1008 (m); PPh2 478 (w). 1H NMR
(200 MHz, CDCl3, ppm): d ¼ 7:82 (m, 4H, PPh2), 7.40
(m, 6H, PPh2), 5.17 (m, 5H, C6H5), 4.67 (s, 2H, C5H4),

B. Therrien et al. / Journal of Organometallic Chemistry 689 (2004) 2456–2463
2463
(j) C. Standfest-Hauser, C. Slugovc, K. Mereiter, R. Schmid, K.
Kirchner, L. Xiao, W. Weissensteiner, J. Chem. Soc., Dalton
Trans. (2001) 2989–2995;
Acknowledgements
The authors are grateful to the Fonds National Suisse
de la Recherche Scientifique for financial support. A
generous loan of ruthenium chloride hydrate from
the Johnson Matthey Technology Centre is gratefully
acknowledged.
ꢀ
ꢀ
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