Synthesis and characterization of (CH{double bond, long}CH)n-bridged (n = 1, 2, 3) heterobimetallic and trimetallic ferrocene-ruthenium complexes

Article abstract of DOI:10.1016/j.jorganchem.2009.12.019

A series of heterobinuclear ferrocene-ruthenium complexes Fc(CH{double bond, long}CH)_nRuCl(CO)(PMe₃)₃ (n = 1, 3; n = 2, 12), Fc(CH{double bond, long}CH)RuCl(CO)(Py)(PPh₃)₂ (4), and trimetallic Fc(CH{double bond, long}CH)RuCl(CO)(PPh₃)₂(Py-E-(CH{double bond, long}CH)Fc) (6) have been prepared. The length of the molecular rods is extended by successive insertion of CH{double bond, long}CH spacers in the bridging ligands or the ancillary ligands. The respective products have been fully characterized and the structures of 3 and 12 have been established by X-ray crystallography. Electrochemical studies have revealed that ethenyl heterobimetallic complexes display two successive one-electron processes, and that intermetallic electronic communication between the two endgroups is attenuated with the increase of the length of the conjugated bridge. The electrochemical behavior of the trimetallic complex reveals strong electronic communication between ruthenium and ferrocene transmitted through the ethenyl bridge, however, it also reveals a very weak interaction between ruthenium and ferrocene transmitted through the (E)-CH{double bond, long}CH-Py bridge.

Full text of DOI:10.1016/j.jorganchem.2009.12.019

Journal of Organometallic Chemistry 695 (2010) 809–815
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis and characterization of (CH@CH)n-bridged (n = 1, 2, 3)
heterobimetallic and trimetallic ferrocene–ruthenium complexes
*
Fang Liu, Xiang Hua Wu, Jian-Long Xia, Shan Jin, Guang-Ao Yu, Sheng Hua Liu
Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 27 October 2009
Received in revised form 16 December 2009
Accepted 17 December 2009
Available online 28 December 2009
A series of heterobinuclear ferrocene–ruthenium complexes Fc(CH@CH)nRuCl(CO)(PMe3)3 (n = 1, 3; n = 2,
12), Fc(CH@CH)RuCl(CO)(Py)(PPh3)2 (4), and trimetallic Fc(CH@CH)RuCl(CO)(PPh3)2(Py–E–(CH@CH)Fc)
(6) have been prepared. The length of the molecular rods is extended by successive insertion of CH@CH
spacers in the bridging ligands or the ancillary ligands. The respective products have been fully charac-
terized and the structures of 3 and 12 have been established by X-ray crystallography. Electrochemical
studies have revealed that ethenyl heterobimetallic complexes display two successive one-electron pro-
cesses, and that intermetallic electronic communication between the two endgroups is attenuated with
the increase of the length of the conjugated bridge. The electrochemical behavior of the trimetallic com-
plex reveals strong electronic communication between ruthenium and ferrocene transmitted through the
ethenyl bridge, however, it also reveals a very weak interaction between ruthenium and ferrocene trans-
mitted through the (E)–CH@CH–Py bridge.
Keywords:
Synthesis
Heterobinuclear
Ferrocene
Ruthenium vinyl complexes
Electrochemistry
Ó 2009 Elsevier B.V. All rights reserved.
1. Introduction
2. Results and discussion
Considerable attention has been paid to studying homobimetal-
lic complexes in which two equivalent metals are bonded through
unsaturated bridges and most of the information on electronic com-
munication comes from investigations on this class of compounds
[1–19]. Heterometallic complexes, however, are asymmetric sys-
tems. This asymmetry means that the heterometallic complexes
may have second-order NLO prosperities. Hetero-bimetallic com-
plexes may have second-order NLO properties [20]. In fact, het-
ero-bimetallic complexes related to (CH)x-bridged bimetallic
complexes such as [(CO)3M@C(OCH3)–(CH@CH)n–(C5H4)Fe(C5H5),
M = W, Cr, n = 1–4] have been synthesized, and they have high b val-
ues [21].
2.1. Synthesis of FcCH@CHC„CH (10)
The general synthetic route for the preparation of monometal-
lic, heterobimetallic and trimetallic complexes is outlined in
Scheme 1. The aldehyde FcCHO (7) underwent a Wittig reaction
with the triphenylphosphonium bromide 8 to give the compound
FcCH@CHC„CSiMe3 (9). The ferrocenyl-derived alkynyl compound
10 was obtained by reaction of 9 with Bu4NF, which can be purified
by chromatography on silica gel.
2.2. Synthesis and characterization of heterometallic complexes
Previously, we reported (CH@CH)3-bridged heterobimetallic
ferrocene–ruthenium complexes and found that the metals linked
through the (CH@CH)3 bridge interacted with each other [18]. In
this paper, we focus further on the (CH@CH)n-bridged (n = 1, 2,
3) ferrocene–ruthenium complexes and investigate how the length
of the bridge, the nature of the ancillary ligands bound to the me-
tal, and the coordination mode affect the intermetallic electronic
communication in the complexes.
The insertion products FcCH@CHRu(CO)Cl(PPh3)2 (2) and
FcCH@CHCH@CHRu(CO)Cl(PPh3)2 (11) are obtained by reaction of
RuH(CO)Cl(PPh3)3 with FcC„CH (1) [22], and FcCH@CHC„CH
(10), respectively. The two compounds were characterized by NMR
and elemental analysis. The 31P NMR spectrum (in CDCl3) of 2 dis-
played a signal at 31.68 ppm, as did compound 11 (32.18 ppm),
which is similar to compound 14 [18] and typical for RuCl(E)–
CH@CHR)(CO)(PPh3)2 [23].
Compounds 2 and 11 undergo a ligand-exchange reaction with
PMe3 to give the relevant six-coordinated complexes FcCH@CHRu-
(CO)Cl(PMe3)3 (3) and FcCH@CHCH@CHRu(CO)Cl(PMe3)3 (12),
respectively. The PMe3 ligands in 3 and 12 are meridionally
coordinated to ruthenium, as indicated by an AM2 pattern in the
31P{1H} NMR spectrum. The six-coordinated addition complex
* Corresponding author. Tel./fax: +86 27 67867725.
E-mail address: chshliu@mail.ccnu.edu.cn (S.H. Liu).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.12.019

810
F. Liu et al. / Journal of Organometallic Chemistry 695 (2010) 809–815
OC
PPh3
H
RuHCl(CO)(PPh3)3
Ru
Fe
Fe
Ph3P Cl
1
2
Fe
N
PMe3
5
N
OC
OC
OC
PMe3
PPh3
PPh3
Ru
Ru
Ph3P Cl
Ru
Ph3P Cl
PMe3
Fe
Fe
N
Fe
N
Me3P
Cl
Fe
6
3
4
TMS
CHO
Bu4NF
NaN(TMS)2
+
Fe
TMS
Fe
PPh3Br
9
7
8
OC
H
PMe3
OC
PPh3
Ru
RuHCl(CO)(PPh3)3
PMe3
Ru
Me3P
Fe
PMe3
Cl
Fe
Fe
Cl
Ph3P
11
12
10
OC PPh3
H
RuHCl(CO)(PPh3)3
Ru
Fe
Fe
Cl
Ph3P
13
14
OC
PMe3
PMe3
PMe3
Ru
Fe
Me3P Cl
15
CO
CO
Ph3P
Cl
Me3P
Ru
PMe3
RuHCl(CO)(PPh3)3
Me3P
Cl
Ru
PMe3
PPh3
17
16
N
CO
Ph3P
N
Ru
PPh3
Cl
18
Scheme 1.

F. Liu et al. / Journal of Organometallic Chemistry 695 (2010) 809–815
811
Table 2
FcCH@CHRu(CO)Cl(Py)(PPh3)2 (4) was obtained by reaction of
Selected bond lengths (Å) and angles (°) for 3 and 12.
compound 2 with pyridine (Py).
The compound Fc–(E)–CH@CH–Py (5) offers both a sp2–
p sys-
3
12
tem and a nitrogen-like lone pair for bonding to metal centers
and should be useful in the assembly of multi-metallic complexes.
Reaction of Fc–(E)–CH@CH–Py (5) with compound 2 gives the
corresponding six-coordinated three-center complex FcCH@CHRu
(CO)Cl(PPh3)2(Py–CH@CH–(E)–Fc) (6).
C(1)–C(11)
C(11)–C(12)
C(12)–C(13)
C(13)–C(14)
C(12)–Ru(1)
C(14)–Ru(1)
1.472(3)
1.337(3)
1.464(7)
1.330(7)
1.438(7)
1.326(6)
2.097(2)
125.1(2)
2.094(5)
The 1H NMR spectra (in CDCl3) of 3, 4, 10, 11, and 12 showed the
Fc–CH proton signal with a big J(HH)coupling constant, which are
15.0 Hz (3), 15.6 Hz (4), 15.6 Hz (10), 15.6 Hz (11), and 15.0 Hz
(12). The magnitude of the J(HH)coupling constant indicates that
the two vinylic protons (Fc–CH@CH) are in a trans geometry. The
1H NMR spectra (in CDCl3) of 3 and 12 showed the Ru–CH proton
signal with a big J(HH)coupling constant, which are 15.2 Hz (3)
and 15.2 Hz (12). The magnitude of the J(HH)coupling constant
indicates that the two vinylic protons (Ru–CH@CH) are in a trans
geometry and that the acetylene is cis-inserted into the Ru–H bond.
C(1)–C(11)–C(12)
C(11)–C(12)–C(13)
C(12)–C(13)–C(14)
C(11)–C(12)–Ru(1)
C(13)–C(14)–Ru(1)
126.8(5)
126.4(5)
125.2(5)
131.6(2)
131.6(4)
center, respectively. In the ferrocene moiety, the dihedral angle
of the substituted cyclopentadienyl ring and the unsubstituted
one in complex 3 is 3.64°, which is bigger than that of 0.42° in
complex 12. All of the olefinic double bonds in 3 and 12 are in a
trans geometry. The ruthenium center is a distorted octahedron
with three meridionally bound PMe3 ligands. The vinyl group is
trans to a PMe3 ligand and the CO group is trans to the chloride
group. The overall geometry around the ruthenium center is
2.3. X-ray structures of 3 and 12
The molecular structures of 3 and 12 were determined by X-ray
crystallography. The crystallographic details are given in Table 1.
Selected bond distances and angles for 3 and 12 are presented in
Table 2. The molecular structures of 3 and 12 are depicted in Figs.
1 and 2, respectively. The complexes 3 and 12 contain a ferrocenyl
moiety which has the cyclopentadienyl ring substituted with a
CH@CH group or a CH@CHCH@CH group linked to a ruthenium
closely related to the bimetallic ruthenium complex Fc(l–
CH@CHCH@CHCH@CH)RuCl(CO)(PMe3)3 [18].
Table 1
Crystal data, data collection, and refinement parameters for 3 and 12.
3
12
Formula
Formula weight
T (K)
C22H38ClFeOP3Ru
603.80
150(2)
C24H40ClFeOP3RuꢀCH2Cl2
714.77
298(2)
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Monoclinic
P2(1)/c
10.8484(12)
8.4672(9)
29.968(3)
90
Monoclinic
P2(1)/n
13.9345(3)
8.6398(2)
27.1934(6)
90
a
(°)
b (°)
94.394(2)
90
2744.7(5)
4
90.8120(10)
90
3273.52(13)
4
c
(°)
V (Åꢁ3
)
Z
Dcalcd (g cmꢁ3
)
1.461
1.450
Crystal size (mm)
F(0 0 0)
Diffractometer
Radiation
0.13 ꢂ 0.10 ꢂ 0.10 0.15 ꢂ 0.13 ꢂ 0.10
1240
1464
Fig. 1. Molecular structure of 3. For the disordered P(3)Me3, only one set of the
disordered atoms [C(20), C(21), and C(22)] are shown.
KappaCCD
MoK/a
1.362
KappaCCD
MoK/a
1.312
Absorption coefficient
(mmꢁ1
)
h range (°)
hkl range
1.36–27.00
ꢁ13 to 12
ꢁ10 to 10
ꢁ38 to 38
30054
1.63–26.00
ꢁ10 to 17
ꢁ10 to 10
ꢁ33 to 32
18910
Total number of reflections
Number of unique reflections 5961
6411
Number of observed
reflections [I > 2 (I)]
5437
4294
r
Number of restraints/
parameters
30/302
0/316
a, b for Wa
0.0385, 1.6383
0.0320
0.0467, 0.0000
0.0595
Final R
Rw
0.0720
0.1104
R (all date)
0.0355
0.0979
Rw (all date)
0.0735
1.050
0.1216
0.991
Goodness-of-fit (GOF) on F2
Largest difference in peak,
1.008 and ꢁ0.745 0.722 and ꢁ0.382
hole (e Åꢁ3
)
r
2(Fo)2 + (aP)2 + bP], where P ¼ ðFo2 þ F2c Þ=3.
a
W = 1/[
Fig. 2. Molecular structure of 12, solvent is omitted for clarity.

812
F. Liu et al. / Journal of Organometallic Chemistry 695 (2010) 809–815
2.4. Electrochemistry
the strong electronic communications between the iron end group
and the ruthenium end group [1c].
The redox behavior of the mononuclear complexes (1, 10, 17,
and 18), binuclear complexes (3, 4, 12, and 15), and the trinuclear
complex (6) (1 mM in CH2Cl2) has been investigated by cyclic vol-
tammetric and square-wave voltammetric techniques with 0.1 M
n-Bu4NPF6 as the supporting electrolyte; pertinent data are com-
piled in Tables 3 and 4. Cyclic voltammograms of the related
monometallic iron (1) and ruthenium (17) complexes gave only
one oxidation. Heterobimetallic complex 3 undergoes two consec-
utive one-electron oxidation processes separated by 0.86 V (Fig. 3,
Table 3). The first oxidation wave at 0.00 V in the cyclic voltammo-
gram of complex 3 is tentatively ascribed to the ferrocene–ferroce-
nium couple. Substitution of the end hydrogen in the iron complex
1 by the ruthenium end group renders oxidation 0.44 V more
favorable. The second oxidation, which should have more ruthe-
nium character, is about 0.26 V less unfavorable than that of the
monometallic ruthenium complex 17. This can be attributed to
Heterobimetallic complexes 3, 12, and 15, in which PMe3 are
ancillary ligands bound to the metal, undergo two consecutive
one-electron oxidation processes, giving rise to redox waves A
and B (Fig. 4, Table 3). The first oxidation occurs at the iron center,
the second occurring at ruthenium, corresponding to oxidation of
FeIIRuII to FeIIIRuII and then of FeIIIRuII to FeIIIRuIII. The first oxida-
tion waves at 0.00, 0.04, and 0.09 V in the cyclic voltammogram
of complexes 3, 12, and 15 respectively, are ascribed to the ferro-
cene–ferrocenium couples. The second oxidation waves, which
are ascribed to the RuII–RuIII couples, are at 0.86 V for 3, 0.46 V
for 12, and 0.27 V for 15 (the ferrocene/ferrocenium redox couple
was located at 0.27 V under the experimental condition of Ref.
[19]). Comparing with complexes 12 and 15, complex 3 has the
highest second oxidation potential, which is attributed to the
shortest distance between ferrocene and the ruthenium atom.
The higher charge of ferrocenium transfers easily to the ruthenium
atom after the ferrocene in complex 3 is oxidized; therefore the
ruthenium atom is oxidized at a higher oxidation potential than
the ruthenium atoms in complexes 12 and 15. It is found that
the oxidation of the ruthenium atoms in the complexes occurs
more easily with the increased length of the bridge ligands. This
indicates that the interaction between ferrocene and the ruthe-
nium atom is reduced with the increasing length of the conjugated
bridge.
Table 3
Electrochemical data for PMe3-containing complexes.a
EA1=2 (V)
EB1=2 (V)
Compound
D
E1/2 (V)
1
3
10
12
15
17
0.44
0.00
0.31
0.04
0.09
–
–
0.86
–
0.46
0.27
0.58
–
0.86
–
0.42
0.18
–
Comparing the
further support the above conclusion. In complexes 3, 12, and 15
with ethenyl (CH@CH)n (n = 1, 2, 3) as a spacer, the E1/2 values
are 0.86, 0.42 and 0.18 V, respectively (Table 4). The large potential
separation ( E1/2 = 0.86 V) in complex 3 between the two one-
DE1/2 values of complexes 3, 12, and 15 could
D
D
a
Cyclic voltammograms recorded in 0.1 M Bu4NPF6 in CH2Cl2, 0.1 V sꢁ1
,
Pt
electrode, V vs. SCE (cf. Fc/Fc+ 0.270 V vs. SCE).
Table 4
Electrochemical data for Py-containing complexes.a
Compound
E1/2(A) (V)
E1/2(B) (V)
E1/2(C) (V)
E(C) ꢁ E(A)
4
5
6
18
ꢁ0.08
–
ꢁ0.09
–
0.26
0.27
0.76
–
0.78
0.51
0.84
–
0.87
a
Cyclic voltammograms recorded in 0.1 M Bu4NPF6 in CH2Cl2, 0.1 V sꢁ1
, Pt
electrode, V vs. SCE (cf. Fc/Fc+ 0.270 V vs. SCE).
1500
3
1
1000
17
500
0
-500
0.0
0.5
1.0
Potential (V)
Fig. 3. Cyclic voltammograms (CVs) of complexes 1, 3, and 17 in CH2Cl2/Bu4NPF6 at
= 0.1 V sꢁ1. Potentials are given relative to the Ag|Ag+ standard.
Fig. 4. Cyclic voltammograms (CVs) of complexes 3, 12, and 15 in CH2Cl2/Bu4NPF6
at
= 0.1 V sꢁ1. Potentials are given relative to the Ag|Ag+ standard.
t
t

F. Liu et al. / Journal of Organometallic Chemistry 695 (2010) 809–815
813
electron processes reflects a remarkable electronic delocalization
along the ethenyl bridge. By comparison of the above E1/2 values,
it can be seen that electronic communication is rapidly attenuated
with a successive insertion of two and three ethenyl units into the
bridge.
Complexes 3 and 12 exhibit an irreversible wave at 0.21 and
0.24 V (C), respectively, which is dependent on the potential win-
dow: C disappeared when the potential sweep was limited to
0.4 V (Fig. 4). Similar phenomenon has been recently reported by
Ren and co-workers [24].
interaction between ruthenium and ferrocene is transmitted
through the (E)–CH@CH–Py bridge. The results indicate that the
complexes, which contain a conjugated bridge linking metal atoms
D
by
r metal–carbon bonds show much stronger electronic commu-
nication between metal atoms than the complexes in which a
bridge links the metal atoms by a dative bond. This is in good
agreement with the conclusion reported by Paul and Lapinte [25]
and Fillaut et al. [26].
3. Conclusions
The redox behavior of complex 4, in which PPh3 and Py are at-
tached to the metal center, is similar to complex 3 (Fig. 5, Table 4).
We have reported here the synthesis, characterization, and elec-
trochemical properties of a series of ferrocene–ruthenium com-
plexes. Electrochemical studies have revealed that ethenyl
heterobimetallic complexes display two successive one-electron
processes and that intermetallic electronic communication be-
tween the two end-groups is attenuated with the increase of the
length of the conjugated bridge. The electrochemical behavior of
the trimetallic complex reveals strong electronic communication
between ruthenium and ferrocene transmitted through the ethenyl
bridge and a very weak interaction between ruthenium and ferro-
cene transmitted through the (E)–CH@CH–Py bridge.
The
DE1/2 value in complex 4 is 0.84 V (Table 4). This rather large
D
E1/2 for 4 is indicative of strong electronic communication trans-
mitted through the ethenyl bridge. In order to gain an understand-
ing of the charge-transfer processes of the ferrocene–ruthenium
through different bonding modes, the redox behavior of the
three-center complex 6 has been investigated by cyclic voltamme-
try and square-wave voltammetry (Table 4). Complex Fc–(E)–
CH@CH–Py undergoes a reversible one-electron oxidation process
at 0.26 V, while complex 18 presents a irreversible one-electron re-
dox wave at 0.51 V. Complex 6 undergoes three consecutive one-
electron oxidation processes, giving rise to redox waves A0, B0,
and C0 (Table 4). In complex 6, the first oxidation wave lies at
ꢁ0.09 V, the second oxidation wave at 0.27 V, and the third oxida-
tion wave at 0.78 V (Fig. 4). Comparing the CV data (Table 4) with
those of the related species, the first oxidation occurs at the iron
center (A0), the second oxidation occurs at the iron center (B0) the
third oxidation occurs at the ruthenium (C0). It is found that the
second oxidation value is nearly equivalent with the value of com-
plex Fc–(E)–CH@CH–Py. The values of the first and the third oxida-
tion are nearly equivalent to the values of complex 4. This reveals
strong electronic communication between ruthenium and ferro-
cene transmitted through the ethenyl bridge, however, a very weak
4. Experimental section
4.1. General materials
All manipulations were carried out at room temperature under
a nitrogen atmosphere using standard Schlenk techniques, unless
otherwise stated. Solvents were pre-dried, distilled and degassed
prior to use, except those for spectroscopic measurements, which
were of spectroscopic grade. The starting materials RuHCl(-
CO)(PPh3)3 [27], TMS–C„CCH2PPh3Br [28], ethynylferrocene [22],
formylferrocene [29], and Fc–(E)–CH@CH–Py [30] were prepared
according to literature methods, and complex 15 [18] was also pre-
pared according to literature method.
4.2. Synthesis of FcCH@CHRuCl(CO)(PPh3)2 (2)
To suspension of RuHCl(CO)(PPh3)3 (0.44 g, 0.46 mmol) in
CH2Cl2 (30 mL) was slowly added
a solution of 1 (0.11 g,
0.52 mmol) in CH2Cl2 (10 mL). The reaction mixture was stirred
for 30 min to give a red solution. The reaction mixture was filtered
through a column of Celite. The volume of the filtrate was reduced
to ca. 5 mL under vacuum. Addition of hexane (50 mL) to the resi-
due produced a red solid, which was collected by filtration, washed
with hexane, and dried under vacuum. Yield: 0.36 g, 86%. Anal.
Calc. for C49H41ClFeOP2Ru: C, 65.38; H, 4.59. Found: C, 65.53; H,
4.42%. 31P NMR (240 MHz, CDCl3): d 31.68 (s). 1H NMR (600 MHz,
CDCl3): d 3.79 (s, 5H, C5H5), 3.87 (s, 2H, C5H2H2C@), 3.96 (s, 2H,
C5H2H2C@), 5.41 (d, J = 13.2 Hz, 1H, FcCH@), 7.35–7.57 (m, 30H,
Ph), 7.72 (d, J = 13.2 Hz, 1H, Ru–CH).
4.3. Synthesis of FcCH@CHRuCl(CO)(PMe3)3 (3)
To a solution of complex 2 (0.18 g, 0.20 mmol) in CH2Cl2
(30 mL) was added
a 1.0 M THF solution of PMe3 (2.0 mL,
2.0 mmol). The reaction mixture was stirred for 15 h. The solvent
of the reaction mixture was removed under vacuum. The residue
was purified by column chromatography (silica gel, eluted with
20/80 acetone/petroleum ether) to give a yellow solid. Yield:
0.08 g, 70%. Anal. Calc. for C22H38ClFeOP3Ru: C, 43.76; H, 6.34.
Found: C, 43.38; H, 6.01%. 31P NMR (240 MHz, CDCl3): d ꢁ18.46
(t, J = 21.4 Hz, PMe3), ꢁ7.08 (d, J = 21.4 Hz, PMe3). 1H NMR (600
MHz, CDCl3): d 1.43 (t, J = 3.0 Hz, 18H, PMe3), 1.47 (d, J = 7.2 Hz,
Fig. 5. Cyclic voltammograms (CVs) of complexes 4, 5, and 6 in CH2Cl2/Bu4NPF6 at
t
= 0.1 V sꢁ1. Potentials are given relative to the Ag|Ag+ standard.

814
F. Liu et al. / Journal of Organometallic Chemistry 695 (2010) 809–815
9H, PMe3), 4.06 (s, 5H, C5H5), 4.09 (s, 2H, C5H2H2C@), 4.27 (s, 2H,
C5H2H2C@), 6.17 (d, J = 15.0 Hz, 1H, FcCH@), 7.35 (ddt,
JHH = 15.2 Hz, JPH = 7.0 Hz, JPH = 3.5 Hz, 1H, Ru–H). 13C NMR
2H, C5H2H2C@), 5.71 (d, J = 15.6 Hz, 1H, FcCH@CH), 6.84 (d,
J = 15.6 Hz, 1H, FcCH@CH). 13C NMR (150 MHz, CDCl3): d 66.96,
69.35, 69.65, 81.06 (s, C5H5, C5H4), 77.36, 83.61 (s, C„C), 103.47,
142.50 (s, CH@CH).
(150 MHz, CDCl3):
d 16.45 (t, J = 14.8 Hz, PMe3), 22.12 (d,
J = 20.2 Hz, PMe3), 64.30, 66.66, 68.04, 91.64 (s, C5H5, C5H4),
129.84 (s, FcCH@), 159.79 (s, Ru–CH), 202.42 (br, CO).
4.7. Synthesis of FcCH@CHCH@CHRuCl(CO)(PPh3)2 (11)
4.4. Synthesis of FcCH@CHRu(CO)Cl(PPh3)2(Py) (4)
The synthesis is similar to 2, with FcC„CH being replaced by
FcCH@CHC„CH (9). Yellow solid, yield: 0.34 g, 79%. Anal. Calc.
for C51H43ClFeOP2Ru: C, 66.14; H, 4.68. Found: C, 66.45; H, 4.91%.
31P NMR (240 MHz, CDCl3): d 32.18 (s). 1H NMR (600 MHz, CDCl3):
d 4.02 (s, 5H, C5H5), 4.12 (s, 2H, C5H2H2C@), 4.20 (s, 2H, C5H2H2C@),
5.25 (d, J = 15.6 Hz, 1H, FcCH@), 5.43 (m, 1H, FcCH@CHCH@), 6.08
(m, 1H, FcCH@ CHCH@), 7.34–7.67 (m, 31H, 30H Ph and Ru–CH).
A mixture of complex 2 (0.18 g, 0.20 mmol) and pyridine
(0.2 mL, 2.5 mmol) in CH2Cl2 (20 mL) was stirred for 30 min. The
solution was filtered through a column of Celite. The volume of
the filtrate was reduced to ca. 2 mL under vacuum. Addition of hex-
ane (15 mL) to the residue produced a yellow solid, which was col-
lected by filtration, washed with hexane, and dried under vacuum.
Yield: 0.17 g, 87%. Anal. Calc. for C54H46ClFeNOP2Ru: C, 66.23; H,
4.73. Found: C, 66.16; H, 4.77%. 31P NMR (240 MHz, CDCl3): d
25.73 (s). 1H NMR (600 MHz, CDCl3): d 3.76 (s, 5H, C5H5), 3.80 (s,
2H, C5H2H2C@), 3.96 (s, 2H, C5H2H2C@), 5.56 (d, J = 15.6 Hz, 1H,
FcCH@), 6.59 (br, 2H, Py), 7.12–7.30 (m, 19H, 18H Ph and 1H Py),
7.62 (m, 13H, 12H Ph and Ru–H), 8.47 (br, 2H, Py).
4.8. Synthesis of FcCH@CHCH@CHRuCl(CO)(PMe3)3 (12)
The synthesis is similar to 3. Red solid, yield: 0.096 g, 76%. Anal.
Calc. for C24H40ClFeOP3Ru: C, 45.76; H, 6.40. Found: C, 45.90; H,
6.74%. 31P NMR (240 MHz, CDCl3): d ꢁ19.08 (t, J = 21.4 Hz, PMe3),
ꢁ7.54 (d, J = 21.4 Hz, PMe3). 1H NMR (600 MHz, CDCl3): d 1.40 (t,
J = 3.4 Hz, 18H, PMe3), 1.49 (d, J = 7.8 Hz, 9H, PMe3), 4.06 (s, 5H,
C5H5), 4.14 (s, 2H, C5H2H2C@), 4.30 (s, 2H, C5H2H2C@), 5.81 (d,
J = 15.0 Hz, 1H, FcCH@), 6.34 (m, 1H, FcCH@CHCH@), 6.43 (m, 1H,
FcCH@ CHCH@), 7.48 (ddt, JHH = 15.2 Hz, JPH = 7.2 Hz, JPH = 3.6 Hz,
1H, Ru–CH). 13C NMR (150 MHz, CDCl3): d 16.71 (t, J = 15.1 Hz,
PMe3), 20.07 (d, J = 20.1 Hz, PMe3), 65.92, 67.91, 69.13, 85.89 (s,
C5H5, C5H4), 128.47, 133.61, 137.71 (s, CH@CH), 170.37 (s, Ru–
CH), 202.29 (br, CO).
4.5. Synthesis of FcCH@CHRu(CO)Cl(PPh3)2(Fc–(E)–CH@CH–Py) (5)
A mixture of complex 2 (0.18 g, 0.20 mmol) and Fc–(E)–
CH@CH–Py (0.06 g, 0.21 mmol) in CH2Cl2 (20 mL) was stirred for
15 h. The solution was filtered through a column of Celite. The vol-
ume of the filtrate was reduced to ca. 5 mL under vacuum. Addition
of hexane (50 mL) to the residue produced a red solid, which was
collected by filtration, washed with hexane, and dried under vac-
uum. Yield: 0.21 g, 90%. Anal. Calc. for C66H56ClFe2NOP2Ru: C,
66.65; H, 4.75. Found: C, 66.73; H, 4.99%. 31P NMR (240 MHz,
CDCl3): d 25.47 (s). 1H NMR (600 MHz, CDCl3): d 3.75 (s, 5H,
C5H5), 3.94 (s, 4H, C5H4), 4.16 (s, 5H, C5H5), 4.39 (s, 2H, C5H2H2),
4.50 (s, 2H, C5H2H2), 5.59 (d, J = 15.2 Hz, 1H, FcCH@), 6.36 (d,
J = 15.6 Hz, 1H, PyCH@CH), 6.52 (br, 2H, Py), 6.93 (d, J = 15.6 Hz,
1H, PyCH@CH), 7.18–7.55 (m, 31H, 30H Ph and Ru–H), 8.29 (br,
2H, Py). 13C NMR (150 MHz, CDCl3): d 63.80, 66.36, 67.49, 69.39,
70.12, 80.96 (s, C5H5, C5H4), 121.80, 127.34, 128.99, 132.55,
132.75, 132.95, 133.12, 133.60, 134.30, 144.18 (s, Ph, Py, CH@CH),
153.50 (s, Ru–CH), 203.75 (br, CO).
4.9. Synthesis of C3H7CH@CHRuCl(CO)(PMe3)3 (17)
The synthesis is similar to 3. Yellow solid, yield: 0.11 g, 73%.
Anal. Calc. for C15H36ClOP3Ru: C, 39.01; H, 7.86. Found: C, 39.13;
H, 7.99%. 31P NMR (240 MHz, CDCl3): d ꢁ18.94 (t, J = 21.4 Hz,
PMe3), ꢁ7.27 (d, J = 20.0 Hz, PMe3). 1H NMR (600 MHz, CDCl3): d
0.90 (t, J = 7.2 Hz, 3H, CH3), 1.39 (m, 20H, PMe3, CH3CH2CH2), 1.43
(d, J = 6.6 Hz, 9H, PMe3), 2.08 (m, 2H, CH3CH2CH2), 5.41 (m, 1H,
CH2CH@), 6.65 (ddt, JHH = 15.8 Hz, JPH = 7.2 Hz, JPH = 3.6 Hz, Ru–
H). 13C NMR (150 MHz, CDCl3):
d 13.96 (s, CH3), 16.15 (t,
J = 15.1 Hz, PMe3), 19.98 (d, J = 20.2 Hz, PMe3), 22.99, 41.17 (s,
CH3CH2CH2, CH3CH2CH2), 134.92 (s, CH2CH@), 155.31 (s, Ru–CH),
202.33 (s, CO).
4.6. Synthesis of FcCH@CHC„CH (10)
To a slurry of TMS–C„CCH2PPh3Br (0.5 g, 1.1 mmol) in THF
(20 mL) was added a 2.0 M THF solution of NaN(SiMe3)2 (0.7 mL,
1.4 mmol). The mixture was stirred for 30 min, and then a solution
of the formylferrocene (0.2 g, 0.9 mmol) in THF (10 mL) was added
slowly. The resulting solution was stirred for another 2 h, and then
water (50 mL) was added. The layers were separated, and the aque-
ous layer was extracted with diethyl ether (3 ꢂ 30 mL). The com-
bined organic layers were washed with a saturated aqueous
solution of sodium chloride (2 ꢂ 10 mL), dried over Na2SO4, fil-
tered, and then concentrated under rotary evaporation. The crude
product was purified by column chromatography (silica gel, eluted
with petroleum ether) to give compound 9. Yield: 0.22 g, 81%. 1H
NMR (600 MHz, CDCl3): d 0.21 (s, 9H, SiMe3), 4.14 (s, 5H, C5H5),
4.26 (s, 2H, C5H2H2C@), 4.34 (s, 2H, C5H2H2C@), 5.74 (d,
J = 15.4 Hz, 1H, FcCH@CH), 6.82 (d, J = 15.3 Hz, 1H, FcCH@CH).
To a solution of compound 9 (0.17 g, 0.55 mmol) in THF (10 mL)
was slowly added a 1.0 M THF solution of n-Bu4NF (0.6 mL,
0.6 mmol) with stirring. After 2 h, the solvent was removed and
the crude product was purified by column chromatography to give
complex 10. Yield: 0.11 g, 42%. Anal. Calc. for C14H12Fe: C, 71.22; H,
5.12. Found: C, 71.50; H, 5.01%. 1H NMR (600 MHz, CDCl3): d 2.99
(s, 1H, „CH), 4.15 (s, 5H, C5H5), 4.29 (s, 2H, C5H2H2C@), 4.37 (s,
4.10. Synthesis of C3H7CH@CHRuCl(CO)(PPh3)2(Py) (18)
The synthesis is similar to 4. Yellow solid, yield: 0.12 g, 68%.
Anal. Calc. for C47H44ClNOP2Ru: C, 67.42; H, 5.30. Found: C,
67.56; H, 5.73%. 31P NMR (240 MHz, CDCl3): d 26.69 (s). 1H NMR
(600 MHz, CDCl3): d 0.66 (t, J = 7.2 Hz, 3H, CH3), 1.05 (m, 2H,
CH3CH2CH2), 1.84 (m, 2H, CH3CH2CH2), 4.78 (m, 1H, CH2CH@),
6.58 (br, 2H, Py), 7.15–7.29 (m, 19H, 18H Ph and 1H Py), 7.59 (m,
13H, 12H Ph and Ru–H), 8.49 (br, 2H, Py).
4.11. Crystallographic details
Crystals suitable for X-ray diffraction were grown from a dichlo-
romethane of solution 3 and 12 layered with hexane. A crystal with
approximate dimensions of 0.13 ꢂ 0.10 ꢂ 0.10 mm3 for 3 and
0.15 ꢂ 0.13 ꢂ 0.10 mm3 for 12 was mounted on a glass fiber for
diffraction experiment. Intensity data were collected on a Nonius
Kappa CCD diffractometer with Mo Ka radiation (0.71073 Å) at
room temperature. The structures were solved by a combination
of direct methods (SHELXS-97 [31]) and Fourier difference tech-
niques and refined by full-matrix least squares (SHELXL-97 [32]).
All non-H atoms were refined anisotropically. The hydrogen atoms

F. Liu et al. / Journal of Organometallic Chemistry 695 (2010) 809–815
815
were placed in the ideal positions and refined as riding atoms. Fur-
References
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contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
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