Preparation, structural characterisation and electrochemical properties of iron(0) and tungsten(0) carbonyl complexes with 1-(diphenylphosphanyl)-1′-vinylferrocene and 1-(diphenylphosphanyl)-1′-(dimethylvinylsilyl)ferrocene as P-monodentate ligands

Article abstract of DOI:10.1016/j.jorganchem.2007.10.056

A new organometallic phosphanylalkene, 1-(diphenylphosphanyl)-1′-(dimethylvinylsilyl)ferrocene (2) was prepared and-together with 1-(diphenylphosphanyl)-1′-vinylferrocene (1)-studied as a ligand in iron- and tungsten-carbonyl complexes. The following complexes featuring the mentioned phosphanylalkenes as P-monodentate donors were isolated and characterised by spectral methods: [Fe(CO)₄(L-κP)] (4, L = 1; 5, L = 2) and trans-[W(CO)₄(L-κP)₂] (6, L = 1; 7, L = 2). In addition, the solid-state structures of 4 and 6 have been determined by single-crystal X-ray diffraction and the electrochemical properties of compounds 1, 2, 4 and 6 were studied by cyclic voltammetry at platinum electrode.

Full text of DOI:10.1016/j.jorganchem.2007.10.056

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 693 (2008) 297–306
www.elsevier.com/locate/jorganchem
Preparation, structural characterisation and electrochemical
properties of iron(0) and tungsten(0) carbonyl complexes with
1-(diphenylphosphanyl)-10-vinylferrocene and 1-(diphenylpho-
sphanyl)-10-(dimethylvinylsilyl)ferrocene as P-monodentate ligands
ˇ
*
ˇ
ˇ
Petr Stepnicka
Charles University in Prague, Faculty of Science, Department of Inorganic Chemistry, Hlavova 2030, 12840 Prague, Czech Republic
Received 13 September 2007; received in revised form 26 October 2007; accepted 31 October 2007
Available online 7 November 2007
Abstract
A new organometallic phosphanylalkene, 1-(diphenylphosphanyl)-10-(dimethylvinylsilyl)ferrocene (2) was prepared and—together
with 1-(diphenylphosphanyl)-10-vinylferrocene (1)—studied as a ligand in iron- and tungsten-carbonyl complexes. The following
complexes featuring the mentioned phosphanylalkenes as P-monodentate donors were isolated and characterised by spectral methods:
[Fe(CO)4(L-jP)] (4, L = 1; 5, L = 2) and trans-[W(CO)4(L-jP)2] (6, L = 1; 7, L = 2). In addition, the solid-state structures of 4 and 6
have been determined by single-crystal X-ray diffraction and the electrochemical properties of compounds 1, 2, 4 and 6 were studied
by cyclic voltammetry at platinum electrode.
ꢀ 2007 Elsevier B.V. All rights reserved.
Keywords: Ferrocene; Alkenylphosphanes; Iron; Tungsten; Electrochemistry; Structure elucidation
1. Introduction
the chiral representatives in enantioselective catalysis
(e.g., C [5] and D [6] in Scheme 1).
Phosphane donors are the most widely used ligands in
coordination chemistry and homogeneous catalysis [1].
The number of the known phosphane donors is enormous
and was markedly increased via introduced functional
groups that, in turn, offer a powerful tool for tuning elec-
tronic and steric properties of the resulting functionalised
phosphanes [2]. In addition to phosphanes modified with
polar donor groups (e.g., NR2, OR, CHO, CO2H, SR, het-
erocycles, PO3R2 and many other), a limited number of
compounds bearing potentially p-donating moieties has
been also reported. Phosphane A [3] and B [4] (Scheme 1)
that can be regarded as simple, alkenyl-modified triphenyl-
phosphane derivatives, represent archetypal examples of
such donors. Recently the interest in phosphanylalkenes
renewed, being stimulated by successful applications of
In previous work, we have focused on ferrocene-based
phosphanylalkenes that have not been studied in detail
before [7]. So far, we have studied the coordination proper-
ties of compound 1 [8] and also described the preparation
and use in catalysis of its planar chiral, 1,2-disubstituted
counterparts [9]. This contribution deals with the synthesis
of a SiMe2-spaced analogue of 1, viz. compound 2 [10], and
the preparation, structural characterisation and electro-
chemistry of iron- and tungsten-carbonyl complexes
involving compounds 1 and 2 as P-monodentate ligands.
2. Results and discussion
2.1. Preparation of the ligands
1-(Diphenylphosphanyl)-10-vinylferrocene (1) was pre-
pared by Wittig olefination of 10-(diphenylphosphanyl)
*
Fax: +420 221 951 253.
E-mail address: stepnic@natur.cuni.cz
0022-328X/$ - see front matter ꢀ 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.10.056

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P. Steˇpnicˇka / Journal of Organometallic Chemistry 693 (2008) 297–306
298
PPh2
CO
PR2
R
CO
CO
OC
Ph
PPh2
Fe
P
(
)
n
[Fe2 (CO)9 ]
Ph
Fe
*
R/OR
H
C
A (n = 0), B (n = 1)
PPh2
C
D
CH2
Y
4 (Y = void), 5 (Y = SiMe2 )
PPh2
PPh
2
Fe
Fe
Fe
H
C
H2C
Y
C
H
CH CH2
SiMe2CH CH2
Y
CH2
Fe
1
2
Ph
1 (Y = void)
2 (Y = SiMe2 )
CO
P
Scheme 1.
OC
Ph
Ph
CO
W
P
[W(cod)(CO)4 ]
CO
ferrocenecarboxaldehyde as previously described [8]. Its
silyl-spaced analogue, 1-(diphenylphosphanyl)-10-(dimethyl-
vinylsilyl)ferrocene (2), has been obtained by sequential
lithiation/functionalisation of 1,10-dibromoferrocene [11]:
the dibromide was first converted to bromide silane 3 and
then phosphanylated to yield the desired phosphane silane
2 (Scheme 2). Compound 2 resulted as a viscous, amber
brown oil, containing traces of side products co-eluting
during chromatography (see Section 4). Exhaustive purifi-
cation of 2 proved to be practically impossible due to very
similar retention characteristics of the impurities. Even so,
reversing the order of the reaction steps so that phosphany-
lation preceded the silylation led to the same product but
with a considerably higher amount of the side products.
Ph
Fe
H
C
CH2
Y
6 (Y = void), 7 (Y = SiMe2 )
Scheme 3. Preparation of iron and tungsten complexes with ligands 1
and 2.
soluble in common laboratory solvents, including hydro-
carbons, and thus prevents purification by crystallisation.
Consequently, complex 5 was isolated only by chromatog-
raphy and obtained as an orange glassy solid, showing a
strong tendency to retain traces of solvents.
Complexes 4 and 5 display characteristic carbonyl
stretching bands in IR spectra, the pattern being similar
to that of [Fe(CO)4(FcPPh2-jP)] (Fc = ferrocenyl) [12].
Their 1H and 13C{1H} NMR spectra fully support the
proposed formulation. The signals of the vinyl group shift
only slightly upon complexation, which clearly excludes
involvement of the vinyl moiety in coordination. For both
2.2. Complexation studies
Iron-carbonyl complexes involving ligands 1 and 2 as P-
monodentate donors (4 and 5 in Scheme 3) have been pre-
pared by reacting equimolar amounts of the appropriate
phosphane and [Fe2(CO)9] in refluxing toluene. After sol-
vent removal, the crude products were purified by column
chromatography. Compound 4 was further crystallised
from warm heptane and isolated as an air-stable, orange
microcrystalline solid. On the other hand, the presence of
the SiMe2 spacer makes 5 and its complexes much better
compounds, the carbonyl ligands give rise to a single
2
phosphorus-coupled doublet at dC ca. 213.3 with JPC
=
19–20 Hz. The 31P{1H} NMR resonances of the iron com-
plexes are shifted markedly downfield to dP ca. 67, which is
similar to [Fe(CO)4(dppf-jP)] (dppf = 1,10-bis(diphenyl-
phosphanyl)ferrocene; dP 68.4 [13] and 66.8 [14] for Fe-P)
and, particularly, to the mono-phosphane complex
[Fe(CO)4(Ph2PfcCONEt2-jP)] (dP 66.9; fc = ferrocene-
1,10-diyl) [15].
Br
Br
Br
i
. LiBu
Fe
Fe
The tungsten-carbonyl complexes trans-[W(CO)4(L-jP)2]
(L = 1, 6; L = 2, 7; Scheme 3) were synthesised by refluxing
the stoichiometric amounts of [W(CO)4(cod)] (cod =
g2:g2-cycloocta-1,5-diene) and the ligand in toluene. Simi-
larly to their iron-carbonyl counterparts, complex 6 was
isolated in a 75% yield by filtration of the reaction mixture
through a pad of silica gel, evaporation and subsequent
crystallisation from hot heptane whilst its SiMe2-homo-
logue 7 was isolated only by column chromatography as
a non-crystallising glassy solid owing to its high solubility.
The latter complex is typically contaminated by [W(CO)5-
(2-jP)] (9, around 10%), which co-elutes during chromato-
graphy.
ii. ClSiMe2CH CH2
SiMe2CH CH2
3
i
. LiBu
ii. ClPPh2
PPh2
Fe
SiMe2CH CH2
2
Scheme 2. Preparation of the phosphane–silane 2.

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299
Attempts to prepare a 1:1 (possibly chelating) complex
from [W(CO)4(cod)] and 1 failed. The reaction at 1:1 mole
ratio under conditions similar to the preparation of 6 affor-
ded only a mixture of the bis(phosphane) complex 6 and
unreacted 1, whereas, at room temperature, the educts
did not react at all (after 22 h in benzene-d6). Likewise, a
reaction between [W(CO)5(MeCN)] [16] and 1 (1:1 mole
ratio, in toluene at room temperature for 24 h) furnished
a mixture of 6 and another product tentatively formulated
as [W(CO)5(1-jP)] (8) on the basis of the NMR data (dP
1
11.3, s with 183W satellites, JWP = 246 Hz; cf. the data
1
for 9 and for [W(CO)5(Hdpf-jP)]: dP 10.9, JWP = 247 Hz;
Hdpf = 10-(diphenylphosphanyl)ferrocenecarboxylic acid
[17]).
In their 31P{1H} NMR spectra, complexes 6 and 7 show
singlets that are shifted downfield as compared with the
free ligands (dP 16.3 and 16.5, respectively) and flanked
with 183W satellites (1JWP = 282 Hz). The presence of the
carbonyl ligands is manifested by a C-13 resonance at
around dC 204, which is split into a triplet due to the inter-
Fig. 1. Molecular structure of 4 showing the atom labeling scheme.
Carbon atoms within the aromatic rings are numbered consecutively and,
hence, only the pivotal and their adjacent carbon atoms are labelled for
clarity.
action with two equivalent phosphorus nuclei (2JPC
=
6 Hz). On the other hand, the carbons within to phospho-
rus-substituted cyclopentadienyl and phenyl rings give rise
to characteristic non-binomial triplets in the 13C{1H}
NMR spectra as typical for virtually coupled ABX spin
systems 12C–31P(A)–W–31P(B)–13C(X) with relatively large
Table 1
a
˚
Selected interatomic distances and angles for 4 (in A and ꢁ)
Fe(2)–P
2.237(1)
1.793(3)
1.798(4)
1.779(3)
1.756(4)
1.147(4)
1.150(5)
1.156(4)
1.172(4)
1.803(3)
1.815(4)
1.828(4)
1.451(6)
1.321(6)
178.6(1)
87.1(1)–89.8(1)
177.4(3)–179.6(3)
90.7(2)–92.6(2)
118.2(2)–122.7(2)
102.9(2)–105.8(2)
125.1(4)
1.655(2)
1.650(2)
4.1(2)
Fe(2)–C(31)
Fe(2)–C(32)
Fe(2)–C(33)
Fe(2)–C(34)
O(1)–C(31)
O(2)–C(32)
O(3)–C(33)
O(4)–C(34)
P–C(6)
2
JAB (or JPP) values [18]. Similar features have been
observed in the spectra of square-planar palladium(II)
complexes involving 10-functionalised ferrocene phos-
phanes as P-monodentate donors: trans-[PdCl2(Ph2PfcX-
jP)2], where X = CO2H (Hdpf) [19], PO3Et2 [20], and
CH=CH2 [8]. The NMR spectra clearly confirm the pres-
ence of uncoordinated double bonds (cf. the data for 6;
1H NMR: three double doublets at dH 4.93, 5.18, and
6.12 of an AMX spin system with characteristic coupling
constants; 13C NMR: two signals at dC 111.84 and 133.77).
P–C(11)
P–C(17)
C(1)–C(23)
C(23)–C(24)
P–Fe(2)–C(31)
P–Fe(2)–C(eq)b
Fe(2)–C–Oc
C(31)–Fe(2)–C(eq)d
C(eq)–Fe(2)–C(eq)e
C–P–Cf
C(1)–C(23)–C(24)
Fe(1)–Cg(1)
Fe(1)–Cg(2)
\Cp1,Cp2
a
2.3. The crystal structures of 4 and 6
View of the molecular structure of 4 is shown in Fig. 1
and the selected geometric data are listed in Table 1. The
coordination environment around the Fe(2) atom is regular
trigonal pyramidal as evidenced by the interligand angles
(Table 1) and also by the s parameter of 0.93 (the value
expected for ideal trigonal bipyramid is 1.0) [21]. The
Fe(2)-donor distances compare favourably to the respec-
tive distances reported for [Fe(CO)4(dppf-jP)] (Fe–P
The ring planes are defines as follows: Cp(1), C(1–5); and Cp(2),
C(6–10). Cg(1,2) denote the respective ring centroids.
b
The range of P–Fe(2)–C(32,33,34) angles.
The range of Fe(2)–C(n)–O(n) angles, where n = 31–34.
The range of C(31)–Fe(2)–C(32,33,34).
The range of C(32)–Fe(2)–C(33,34) and C(33)–Fe(2)–C(34) angles.
c
˚
˚
2.243(3) A, Fe–CO 1.75(1)–1.79(1) A [13]), [(l-dppf)-
d
˚
˚
e
{Fe(CO)4}2] (Fe–P 2.251(5) A, Fe–CO 1.78(2)–1.79(2) A
[13]), and [Fe(CO)4(Ph2PfcCONEt2-jP)] (Fe–P 2.2505(6) A,
Fe–CO 1.787(2)–1.800(2) A [15]).
f
˚
The range of C(6)–P–C(11,17) and C(11)–P–C(17) angles.
˚
The Fe(CO)4 fragment is located at the side of the ferro-
cene moiety so that the equatorial plane [FeC(n)O(n)]
(n = 2–4) is nearly perpendicular to the Cp(1) ring (the
dihedral angle is 85.3(2)ꢁ). Consequently, the Fe(2)–P vec-
tor deviates only by 3.4(2)ꢁ from the Cp(1) plane, with the
phosphorus and Fe(2) atoms being displaced by 0.159(1)
˚
and 0.289(1) A, respectively, above the Cp(1) plane (i.e.,
away from the ferrocene iron atom). To minimise steric
interactions, the Fe(2)(CO)3 and ‘PC3’ moieties are mutu-
ally staggered with the OC–Fe(2)–P–C(Ph) dihedral angles
close to 60ꢁ.

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P. Steˇpnicˇka / Journal of Organometallic Chemistry 693 (2008) 297–306
300
Table 2
The ferrocene unit shows practically identical Fe-ring
a
˚
Selected interatomic distances and angles for 6 (in A and ꢁ)
centroid distances and a tilt of 4.1(2)ꢁ with the side proxi-
mal to the Fe(CO)4 unit being more opened for steric rea-
sons. The two ferrocene substituents are rotated with the
torsion angle C(1)–Cg(1)–Cg(2)–C(6) of 136ꢁ, which corre-
sponds to an intermediate conformation between anti-stag-
gered and anti-eclipsed (cf. the ideal values of 108ꢁ and
144ꢁ, respectively). The vinyl group is slightly rotated from
the plane of its bonding cyclopentadienyl ring: The angle
subtended by the Cp(2) plane and the C(23)–C(24) bond
is 11.8(3)ꢁ.
W–P
2.4816(8)
2.025(4)
2.029(4)
1.147(5)
1.147(5)
1.816(4)
1.838(4)
1.848(4)
1.43(1)
W–C(31)
W–C(32)
O(1)–C(31)
O(2)–C(32)
P–C(6)
P–C(11)
P–C(17)
C(1)–C(23)
P–W–C(31)
P–W–C(32)
W–C(31)–O(1)
W–C(32)–O(2)
W–P–Cb
C–P–Cc
Fe–Cg(1)
Fe–Cg(2)
\Cp1,Cp2
a
90.8(1)
84.4(1)
View of the molecular structure of 6 is presented in
Fig. 2 and the selected geometric data are given in Table
2. Complex 6 crystallises with the symmetry of the mono-
clinic P21/c space group with the tungsten atom residing
on the crystallographic inversion centers, which renders
only the half of the molecule symmetrically independent.
The interligand angles around the tungsten atom differ only
marginally from octahedral ones irrespective of the unlike
W-donor bond lengths (cf. P–W–C(31,32) angles in Table
178.8(3)
177.4(4)
112.2(1)–121.7(1)
100.0(2)–101.1(2)
1.652(3)
1.646(2)
3.2(3)
The ring planes are defines as follows: Cp(1), C(1–5); and Cp(2),
C(6–10). Cg(1,2) denote the respective ring centroids.
b
The range of W–P–C(6,11,17) angles.
The range of C(6)–P–C(11,17) and C(11)–P–C(17) angles.
c
˚
1). The observed W–P distance (2.4816(8) A) is noticeably
shorter than those reported for other structurally charac-
terised complexes with ferrocene ligands featuring either
terminal W(CO)5 units (e.g., [Cl2Pt{(l-dppf)W(CO)5}2],
The ferrocene Cp(2) and the {WC4} planes in 6 are
practically perpendicular (the dihedral angle is 88.9(2)ꢁ).
Owing to the imposed symmetry and the overall molecular
conformation, the ligand moieties are centrosymmetric
images (i.e., are anti to each other) and their ‘PC3’ motifs
appear mutually staggered (i.e., rotated by ca. 60ꢁ) when
looked upon along the P–P0 line. Similarly to 4, the ferro-
cene cyclopentadienyls exert a tilt of 3.2(2)ꢁ and adopt an
intermediate conformation between anti-staggered and
anti-eclipsed with the torsion angle C(1)–Cg(1)–Cg(2)–
C(6) = 130ꢁ.
˚
W–P 2.546(6) A [22]; [W(CO)4(L-jP)], where L = (Sp)-
1-(diphenylphosphanyl)-2-((E)-2-phenyethenyl)ferrocene,
˚
W–P 2.562(1) and 2.547(1) A [9]; and [(OC)5W@C(NEt2)-
˚
fcPPh2W(CO)5] W–P 2.545(1) A [15]) or chelated W(CO)4
moieties ([W(CO)4(L-g2:jP)], where L = (Sp)-1-(diphenyl-
˚
phosphanyl)-2-vinylferrocene, W–P 2.5328(9) A [9a];
2
0
˚
[W(CO)4(dppf-j P,P )], W–P 2.533(2) and 2.563(2) A [23];
2
1
˚
and [W(CO)4(Ph2PfcC(NEt2)-j C ,P)], W–P 2.5391(9) A
[15]). By contrast, the W–CO distances found in 6 do not
differ much from those in the mentioned complexes.
Fig. 2. View of the molecular structure of 6. For clarity, only labels for the pivotal and their adjacent carbon atoms with the consecutively numbered
aromatic rings are shown. The non-labeled part of the molecule is generated by the crystallographic inversion operation (symmetry operation: 1/2 ꢀ x,
3/2 ꢀ y, ꢀz).

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301
2.4. Electrochemistry
ence of electron-withdrawing substituents, the oxidation of
1 appears at more positive potentials than that of ferrocene
itself [Epa = 0.12 V vs. ferrocene/ferrocenium at the scan
rate 0.1 V sꢀ1; Epa (Epc) are the anodic (cathodic) peak
potentials]. The process is diffusion controlled as indicated
by the peak current ꢂ (scan rate)1/2 over the range 0.1–
5 V sꢀ1 but is associated with follow-up processes that con-
vert the electro-generated product into another (redox
active) species (see Fig. 4). Accordingly, a minor wave
was observed at higher potentials, which becomes more
pronounced during repeated cycling and is associated with
a reductive counterwave (Epa = 0.27 V, Epc = 0.20 V vs.
ferrocene/ferrocenium). The peak couple can be attributed
to oxidation of the corresponding phosphane oxide present
as a trace impurity in 1 or, more likely, formed by reaction
of the electrochemically generated cation radical 1+ꢀ with
traces of oxygen or water [24].
The redox behaviour of 2 is very similar except that the
oxidation shows signs of reversibility. At scan rates up to
5 V sꢀ1, the current ratio ipa/ipc is always lower than unity
but increases with the scan rate [ipa (ipc) denotes the anodic
(cathodic) peak current]. Compared to 1, the oxidation of 2
is shifted by ca. 100 mV more positive (Epa = 0.22 V vs. fer-
rocene/ferrocenium at scan rate 0.1 V sꢀ1; Fig. 3).
The electrochemical behaviour of 1, 2, 4 and 6 has been
studied by cyclic voltammetry on platinum disc electrode in
ca. 0.5 mM dichloromethane solutions containing 0.1 M
Bu4NPF6 as the supporting electrolyte. The electrochemi-
cal data are summarised in Table 3.
Compound 1 becomes oxidised in a single irreversible
step (Fig. 3), attributable to oxidation of the ferrocene moi-
ety to the corresponding ferrocenium. Because of the pres-
Table 3
Summary of the electrochemical dataa
Compound
Eꢁ0 [V]
+0.12b
1
2
4
6
a
+0.21
+0.28,c +0.58b
+0.17, +0.82,b ca. +1.27
The potentials are given relative to ferrocene/ferrocenium reference.
See Section 4 for details.
b
Irreversible oxidation. Oxidation peak potential (Epa
)
given
(0.1 V sꢀ1).
c
See text.
Fig. 3. Cyclic voltammograms of 0.5 mM dichloromethane solutions of 1 (left) and 2 (right) as recorded on platinum disc electrode at varying scan rate.
Fig. 4. Cyclic voltammograms of 1 recorded at different scan rates (left 0.1 V sꢀ1, right 0.5 V sꢀ1). The response obtained in the first cycle is shown in full
line while the second scan is indicated with a dotted line. Conditions: Pt disc electrode, 0.5 mM dichloromethane solution.

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P. Steˇpnicˇka / Journal of Organometallic Chemistry 693 (2008) 297–306
302
The oxidation of the dinuclear complex 4 occurs in two
(Fig. 5). As the overall reversibility increases at higher scan
rates, it is likely that the oxidation of 4 is accompanied by
some chemical complications and, probably, adsorption at
the electrode surface.
The redox response of compound 6 parallels the behav-
iour of [W(CO)4(FcPPh2-jP)2] [26] in that it undergoes two
successive, well-separated ferrocene oxidations followed by
a third, tungsten-centered one. The first ferrocene oxida-
tion is observed with full reversibility while the second
and third are essentially irreversible (Fig. 6). Similarly to
4, the redox steps are coupled with processes that result
in blocking of the electrode surface (Fig. 6).
The potential of the tungsten-centered oxidation in 6 is
markedly higher than that reported for [W(CO)4(PPh3)2]
(ca. 0.45 V vs. ferrocene/ferrocenium; irreversible wave)
[27]. This shift, apparently contrasting with the donor
ability of the ligands (ferrocenyl is a strong electron-
donating group), can be rationalised by the sequence of
the redox steps. Whereas the phosphane donors in
[W(CO)4(PPh3)2] are redox-silent, compound 6 undergoes
firstly two ferrocene-based oxidations that convert neutral
6 to a dicationic bis(ferrocenium) species. Thus, the spe-
cies to be oxidised in the last step is not only positively
charged but also contains two ligands whose donor ability
has been changed during the preceding redox steps (elec-
tron-donating ferrocene becomes electron-withdrawing
ferricinium; cf. the Hammett rp constants ꢀ0.18 and
0.29 for the ferrocenyl and ferrocenium groups, respec-
tively) [28], which naturally influences the redox response
of the ‘central’ atom.
separated one-electron steps. The first oxidation is reversible
and occurs most likely at the ferrocene ligand. The shift
towards more positive potentials can be accounted for
by an electron density lowering at the ferrocene unit con-
nected with coordination (Table 3). The following oxidation
is irreversible as well and can be tentatively attributed to
an oxidation of the Fe(CO)4 fragment (Fig. 5). A similar
two-step oxidative behaviour has been reported for
[Fe(CO)4(L-jP)], where L = [Fe(g5:g5-C5H4CH2CH2P-
(Ph)CH2CH2C5H4)] [25].
During scanning over both oxidative processes at rela-
tively slow scan rates (e.g., 0.1 V sꢀ1), a post-peak emerges
after the second wave while the reductive wave correspond-
ing to the first redox step occurs with a peak current lower
than for the respective oxidation counter wave. When the
scan rate is kept at 0.1 V sꢀ1 and the switching potential
is increased, an additional oxidation wave appears at
around +1.26 V during the second cycle while the original
peaks nearly disappear from the cyclic voltammogram
3. Conclusions
Organometallic phosphanylalkenes 1 and 2 readily coor-
dinate to ‘M(CO)4’ fragments (M = W and Fe) as P-mono-
dentate donors, while the alkenyl groups act as spectator
peripheral substituents. The reluctance of 1 and 2 to form
chelate complexes, already demonstrated in a series of pal-
ladium(II) and copper(I) complexes [8], stands against the
Fig. 5. Cyclic voltammograms of 4 as recorded on a platinum disc
electrode for 0.5 mM dichloromethane solutions and at 0.1 V sꢀ1 scan
rate. Note the difference between the first (solid line) and the second cycle
(dotted line).
Fig. 6. (left) Cyclic voltammograms of 6 as recorded on a platinum disc electrode for 0.5 mM dichloromethane solution at 0.1 V sꢀ1 scan rate. The dotted
line indicates the scan limited to the first oxidation. (right) Changes in cyclic voltammograms of 6 upon repeated cycling at 0.1 V sꢀ1 scan rate (the first
four scans, 1–4 are shown).

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P. Steˇpnicˇka / Journal of Organometallic Chemistry 693 (2008) 297–306
303
coordination behaviour of their 1,2-analogues [9a] and
4.2. Preparation of 10-dimethylvinylsilyl-1-bromoferrocene
(3)
organyls containing the 10-(diphenylphosphanyl)ferrocen-
1-yl group: 10-(diphenylphosphanyl)ferrocen-1-yl [29] and
[10-(diphenylphosphanyl)ferrocenyl]methylidene [15,30].
The structures of the resulting metal-carbonyl complexes
were established by spectral methods and, for crystalline
compounds, confirmed by X-ray diffraction analysis. In
addition, the redox behaviour of the selected representa-
tives has been studied by cyclic voltammetry on platinum
disc electrode.
Butyl lithium (2.0 mL of 2.5 M solution in hexanes,
5.0 mmol) was added to a solution of 1,10-dibromoferro-
cene (1.72 g, 5.0 mmol) in dry THF (20 mL) with cooling
to ꢀ78 ꢁC (dry ice/ethanol bath). The mixture was stirred
at this temperature for 10 min whereupon an orange pre-
cipitate formed. Chlorodimethyl(vinyl)silane (0.8 mL,
6 mmol) was slowly added causing the precipitate to dis-
solve, and the formed dark yellow-brown solution was stir-
red at ꢀ78 ꢁC for 15 min and then at room temperature for
90 min. Then, the reaction mixture was quenched by addi-
tion of saturated aqueous NaHCO3 solution. The organic
layer was separated, washed with brine, dried (MgSO4)
and evaporated, leaving the crude product as a dark amber
oil. Subsequent purification by flash column chromatogra-
phy (silica gel, hexane) afforded silane 3 as an amber
orange oil. Yield: 1.532 g (88%). The product is typically
contaminated by trace amounts of side products such as
FcSiMe2(CH@CH2), FcBr, and unreacted fcBr2, which
cannot be effectively removed by chromatography due to
similar retention characteristics. However, the side prod-
ucts do not hamper the following step and their amounts
are conveniently reduced by chromatography after the sub-
sequent phosphanylation (see the following section).
4. Experimental
4.1. Materials and methods
All syntheses were performed under argon atmosphere.
Tetrahydrofurane (THF) was distilled from potassium/
benzophenone ketyl. Toluene was dried over sodium metal
and distilled. Compounds 1 [18] and 1,10-dibromoferrocene
[11b] were prepared by the literature procedures. Other
chemicals and solvents for chromatography were obtained
from commercial sources and used without purification
(Fluka, Aldrich; solvents from Lach-Ner). The reported
yields are not optimised.
NMR spectra were recorded on a Varian UNITY
Inova 400 spectrometer (1H, 399.95; 13C, 100.58; 31P,
161.90 MHz) at 298 K. Chemical shifts (d/ppm) are given
relative to internal tetramethylsilane (1H and 13C) or an
external 85% aqueous H3PO4 (31P). The second-order mul-
tiplets due to the alkenyl- (AA0BB0 spin system) and phos-
phanyl-substituted (AA0BB0X spin system) ferrocene
cyclopentadienyl rings are labelled as apparent triplets
and quarterts (Fc = ferrocenyl, fc = ferrocene-1,10-diyl).
IR spectra were measured on an FT IR Nicolet Magna
760 instrument in the range of 400–4000 cmꢀ1. Mass spec-
tra in EI and FAB mode were recorded with a ZAB-EQ
(VG Analytical) spectrometer. The complexes notoriously
give erratic results in the standard combustion analysis
due to their limited stability and/or incomplete
combustion.
1H NMR (CDCl3): d 0.32 (s, 6H, SiMe2), 4.05, 4.10,
2
4.37, 4.40 (4 · apparent t, 2H, fc); 5.73 (dd, JHH = 3.7,
2
3JHH = 20.3 Hz, 1H, @CH2), 6.00 (dd, JHH = 3.7,
3
3JHH = 14.6 Hz, 1H, @CH2), 6.30 (dd, JHH = 14.6,
20.3 Hz, 1H, @CH). 13C{1H} NMR (CDCl3): d ꢀ2.03
(SiMe2), 67.33, 70.31 (2 · CH of fc); 71.62 (C–Si of fc),
74.09, 75.65 (2 · CH of fc); 77.70 (C–Br of fc), 131.87
(@CH2), 138.69 (@CH). EI MS: m/z (relative abundance)
350 (97), 348 (100) (M+ꢀ); 270 (12, [MꢀBr]+), 186 (11),
184 (10), 121 (16, C5H5Fe+), 85 (31, (CH2CH)Me2Si+).
HR MS: for C14H17 79Br56FeSi (M+) calc. 347.9632; found,
347.9642.
4.3. Preparation of 10-dimethylvinylsilyl-1-
(diphenylphosphanyl)ferrocene (2)
Electrochemical measurements were carried out with a
computer-controlled multipurpose polarograph lAUTO-
LAB III (Eco Chemie) at room temperature using a stan-
dard three-electrode cell with rotating platinum disc
electrode (AUTOLAB RDE; 3 mm diameter) as the work-
ing electrode, platinum sheet auxiliary electrode, and calo-
mel reference electrode (3 M KCl). The analysed
compounds were dissolved in dichloromethane (Fluka,
absolute, declared H2O content below 0.005%) to give
5 · 10ꢀ4 M concentration of the analyte and 0.1 M
Bu4NPF6 (Fluka, purissimum for electrochemistry). The
solutions were deaerated with argon prior to the measure-
ment and then kept under an argon blanket. The redox
potentials are given relative to the ferrocene/ferrocenium
reference and are reproducible within ca. 5 mV. The
potential of the ferrocene/ferrocenium couple under the
experiment conditions was +0.435 V.
Butyl lithium (1.7 mL of 2.5 M solution in hexanes,
4.3 mmol) was added to a solution of 3 (1.36 g, 3.9 mmol)
in dry THF (10 mL) while cooling to ꢀ78 ꢁC (dry ice/eth-
anol bath). After stirring for 15 min, neat chlorodiphenyl-
phosphane (0.9 mL, 4.9 mmol) was added dropwise and
the resulting mixture was stirred at ꢀ78 ꢁC for 15 min
and then at room temperature for 90 min. The reaction
was terminated by addition of saturated aqueous NaHCO3
solution and stirring for another 30 min. The reaction mix-
ture was diluted with diethyl ether, the organic layer was
separated, washed with brine, dried (MgSO4), and concen-
trated under vacuum. The brown residue was purified by
column chromatography on silica gel. First, elution with
hexane removed a minor orange band due to side products.
The following elution with hexane–diethyl ether (1:9 v/v)

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P. Steˇpnicˇka / Journal of Organometallic Chemistry 693 (2008) 297–306
304
afforded the major orange band of the product. Evapora-
tion of the second band under vacuum yielded 2 as an
orange brown oil. Yield: 1.21 g (68%, calculated for pure
3). Chromatographic purification markedly reduces the
amount of impurities mentioned above; another side prod-
uct formed during the phosphanylation step, detectable by
NMR and GC–MS is (diphenylphosphanyl)ferrocene.
1H NMR (CDCl3): d 0.25 (s, 6H, SiMe2), 4.01 (apparent
t, 2H), 4.07 (apparent q, 2H), 4.19 (apparent t, 2H), 4.33
[Mꢀ4CO]+ꢀ), 426 (20, [Mꢀ4COꢀC2H2]+ꢀ), 396 (100, 1+ꢀ),
370 (51, [1–C2H2]+ꢀ, isobaric with FcPPh2+ꢀ). HR MS: calc.
for C28H2156Fe2O4P (M+ꢀ), 563.9876; found, 563.9901.
4.5. Preparation of tetracarbonyl-[1-(diphenylphosphanyl-
jP)-10-(dimethylvinylsilyl)ferrocene]iron(0) (5)
A mixture of [Fe2(CO)9] (72 mg, 0.20 mmol), 2 (92 mg,
0.20 mmol) and toluene (8 mL) was heated at reflux for
1 h. The mixture was cooled, evaporated under vacuum
and the residue was purified by column chromatography
(silica gel, hexane–diethyl ether 5:1). Collecting the major
band followed by evaporation gave pure 6 as an orange
glassy solid. Yield: 88 mg (71%).
2
(apparent t, 2H) (4 · CH of fc); 5.68 (dd, JHH = 3.7,
2
3JHH = 20.3 Hz, 1H, @CH2), 5.96 (dd, JHH = 3.7,
3
3JHH = 14.6 Hz, 1H, @CH2), 6.23 (dd, JHH = 14.6,
20.3 Hz, 1H, @CH), 7.27–7.40 (m, 10H, PPh2). 13C{1H}
NMR (CDCl3): d ꢀ2.08 (SiMe2), 70.62 (C–Si of fc),
71.13 (d, JPC = 4 Hz), 72.37 (d, JPC ꢁ 1 Hz), 72.98 (d,
1H NMR (CDCl3): d 0.21 (s, 6H, SiMe2), 3.74 and 3.77
(2 · apparent t, 2H, fc); 4.48–4.51 (m, 4H, fc), 5.66 (dd,
1
JPC = 15 Hz), 74.03 (4 · CH of fc); 75.83 (d, JPC = 7 Hz,
2
3
C–P of fc), 128.08 (d, JPC = 7 Hz, CH of PPh2), 128.43
(CH of PPh2), 131.68 (@CH2), 133.46 (d, JPC = 20 Hz,
CH of PPh2), 138.85 (@CH), 139.09 (d, 1JPC = 10 Hz, Cipso
of PPh2). 31P{1H} NMR (CDCl3): d ꢀ16.3 (s). EI MS: m/z
(relative abundance) 454 (100, M+), 370 (35, [FcPPh2]+ꢀ),
242 (18), 240 (13), 199 (15), 183 (17). HR MS: for C26H27
56FePSi (M+) calc. 454.0969; found, 454.0980.
3JHH = 20.2, JHH = 3.8 Hz, 1H, @CH2), 5.97 (dd, JHH
=
2
3
14.6, JHH = 3.8 Hz, 1H, @CH2), 6.18 (dd, JHH = 20.2,
14.6 Hz, 1H, @CH), 7.39–7.57 (m, 10H, PPh2). 13C{1H}
NMR (CDCl3): d ꢀ2.18 (SiMe2), 71.39 (CSi of fc), 72.08
(d, JPC = 9 Hz), 73.86, 74.11, 74.73 (d, JPC = 12 Hz)
(4 · CH of fc); 128.10 (d, JPC = 10 Hz), 130.37 (d,
JPC = 2 Hz) (2 · CH of PPh2); 132.05 (@CH2), 132.53 (d,
JPC = 10 Hz, CH of PPh2), 137.43 (@CH), 138.12 (d,
2
4.4. Preparation of tetracarbonyl-[1-(diphenylphosphanyl-
jP)-10-vinylferrocene]iron(0) (4)
1JPC = 33 Hz, Cipso of PPh2), 213.27 (d, JPC = 20 Hz,
C„O); the signal due to CP of fc is probably obscured
by the solvent resonance. 31P{1H} NMR (CDCl3): d
+67.0 (s). IR (RAS): m/cmꢀ1 m(C„O) 2050 (vs), 2012 (w),
1975 (vs), 1952 (vs), 1913 (m). EI MS: m/z (relative abun-
dance) 622 (4, M+ꢀ), 510 (58, [Mꢀ4CO]+ꢀ), 454 (100, 2+ꢀ),
370 (13, [1–SiMe2(C2H2)]+ꢀ, isobaric with FcPPh2+ꢀ). HR
MS: calc. for C30H2756Fe2O4PSi (M+ꢀ), 622.0115; found,
622.0105.
A mixture of [Fe2(CO)9] (73 mg, 0.20 mmol), 1 (80 mg,
0.20 mmol) and toluene (1 mL) was brought to boiling
whereupon the solid carbonyl quickly dissolved to give a
turbid orange solution. After refluxing for 1 h, the reaction
mixture was cooled to room temperature and passed
trough a short silica gel column (elution with toluene) to
remove dark decomposition products. The orange eluate
was evaporated under vacuum and the residue immediately
dissolved in hot heptane (4 mL). The solution was filtered
while hot and the filtrate was allowed to crystallise at room
temperature and then 0 ꢁC overnight. The formed crystals
were isolated by suction, washed with cold pentane and
dried under vacuum to give 4 as an orange crystalline solid
(fine needles). Yield: 94 mg, 83%.
4.6. Preparation of trans-tetracarbonylbis[1-(diphenyl-
phosphanyl-jP)-10-vinylferrocene]tungsten(0) (6)
[W(cod)(CO)4] (41 mg, 0.10 mmol) and
1 (80 mg,
0.20 mmol) were dissolved in toluene (8 mL) and the solu-
tion was heated at gentle reflux for 3 h. Then, it was cooled
to room temperature and filtered through a short silica gel
column. The column was washed with toluene and the
orange eluate was concentrated under vacuum. The glassy
residue was immediately dissolved in hot heptane, the solu-
tion was filtered while hot and allowed to crystallise at
room temperature and then at 0 ꢁC. The separated crystal-
line product was filtered off, washed with hexane and dried
under vacuum to give 6 as an orange microcrystalline solid.
Yield: 82 mg (75%).
1H NMR (CDCl3): d 3.73, 4.02 (2 · apparent t, 2H),
4.42 (m, 2H), 4.46 (apparent q, 2H) (4 · CH of fc); 4.95
3
2
(dd, JHH = 10.8, JHH = 1.3 Hz, 1H, @CH2), 5.18 (dd,
2
3JHH = 17.5, JHH = 1.3 Hz, 1H, @CH2), 6.02 (dd,
3JHH = 17.5, 10.8 Hz, 1H, @CH), 7.38–7.59 (m, 10H,
PPh2). 13C{1H} NMR (CDCl3): d 67.91, 71.32, 74.05 (d,
JPC = 9 Hz), 75.38 (d, JPC = 12 Hz) (4 · CH of fc); 84.68
(CCH@CH2 of fc), 112.41 (@CH2), 128.13 (d, JPC
=
10 Hz), 130.36 (d, JPC = 2 Hz), 132.52 (d, JPC = 10 Hz)
1H NMR (CDCl3): d 3.94, 4.08 (2 · apparent t, 2H),
4.29 (br m, 2H), 4.35 (apparent t, 2H) (4 · CH of fc);
1
(3 · CH of PPh2); 133.33 (@CH), 137.72 (d, JPC = 52 Hz,
3
2
C
ipso of PPh2), 213.30 (d, 2JPC = 19 Hz, C„O); the CP sig-
4.93 (dd, JHH = 10.7, JHH = 1.6 Hz, 1H, @CH2), 5.18
3 2
nal of fc was not found, probably due to overlaps with the
solvent signal. 31P{1H} NMR (CDCl3): d +66.7 (s). IR
(Nujol): m/cmꢀ1 m(C„O) 2049 (vs), 1979 (vs), 1944 (br
vs), 1906 (br vs). EI MS: m/z (relative abundance) 564
(10, M+ꢀ), 508 (9, [Mꢀ2CO]+ꢀ), 478 (8), 452 (96,
(dd, JHH = 17.5, JHH = 1.5 Hz, 1H, @CH2), 6.12 (dd,
3JHH = 17.5, 10.7 Hz, 1 H, @CH), 7.31–7.56 (m, 10H,
PPh2). 13C{1H} NMR (CDCl3): d 67.73, 70.99, 73.23
(virtual t, J0 = 7 Hz), 74.89 (virtual t, J0 = 6 Hz) (4 · CH
of fc); 82.49 (virtual t (1:1:1), J0 = 22 Hz, CP of fc), 84.23

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P. Steˇpnicˇka / Journal of Organometallic Chemistry 693 (2008) 297–306
305
Table 4
(CCH@CH2 of fc), 111.84 (@CH2), 127.53 (virtual t,
J0 = 5 Hz), 128.94, 132.61 (virtual t, J0 = 6 Hz) (3 · CH
Crystallographic data, data collection and structure refinement parameters
for 4 and 6
of PPh2); 133.77 (@CH), 140.48 (virtual
t (1:1:1),
2
J0 = 22 Hz, Cipso of PPh2), 204.05 (t, JPC = 6 Hz, C„O).
31P{1H} NMR (CDCl3): d +16.3 (s with 183W satellites,
1JWP = 282 Hz). IR (Nujol): m/cmꢀ1 m(C„O) 1886 (vs),
1878 (vs), 1861 (sh). FAB MS: m/z 1088 (M+). The com-
pound shows very poorly abundant ions due to M+ in its
mass spectrum, not allowing for HR MS analysis.
Compound
Formula
M (g molꢀ1
4
6
C
564.12
28H21Fe2O4P
C52H42Fe2O4P2W
1088.35
Monoclinic
C2/c (no. 15)
150(2)
25.3510(5)
9.4562(2)
17.8789(4)
95.499(1)
4266.3(2)
4
1.694
3.484
0.668–0.842
30981
4888/3610
3.03
)
Crystal system
Space group
T (K)
Monoclinic
P21/c (no. 14)
150(2)
13.3091(8)
11.6271(7)
15.6662(9)
92.208(5)
2422.5(2)
4
1.547
1.297
0.631–0.907
27557
5071/2199
4.09
˚
a (A)
˚
b (A)
˚
c (A)
4.7. Preparation of trans-tetracarbonylbis[1-(diphenyl-
phosphanyl-jP)-10-(dimethylvinylsilyl)ferrocene]-
tungsten(0) (7)
b (ꢁ)
3
˚
V (A )
Z
Dcalc (g mLꢀ1
)
l(Mo Ka) (mmꢀ1
Ta
)
[W(cod)(CO)4] (41 mg, 0.10 mmol) and
2 (92 mg,
0.20 mmol) were dissolved in toluene (8 mL) and the solu-
tion was heated at reflux for 3 h. The reaction mixture was
cooled to room temperature, evaporated and the residue
purified by column chromatography on silica gel using hex-
ane–diethyl ether (5:1) as the eluent. The first and only
orange band was collected and evaporated under vacuum
to give 7 as an orange brown glassy solid. Yield: 98 mg
(96%). The product is typically contaminated with
[W(CO)5(2)] (8) (5–15%).
Diffractions total
Unique/observedc diffractions
R (observed data)b,c (%)
R, wR (ꢀa3ll data) (%)c
12.97, 5.86
0.71, ꢀ0.47
660757
5.29, 6.76
0.57, ꢀ0.80
660758
˚
Dq (e A
)
CCDC entry
a
The range of transmission coefficients.
b
c
Diffractions with Io > 2r(Io).
R = RiFoj ꢀ jFci/RjFoj, wR = [Rw(F2o ꢀ Fc2)2}/Rw(Fo2)2]1/2
.
1H NMR (CDCl3): d 0.18 (s, 6 H, SiMe2), 3.74 and 4.11
(2 · apparent t, 2H, fc); 4.31 (m, 2H, fc), 4.42 (apparent t,
2H, fc), 5.63 (dd, 3JHH = 20.3, 2JHH = 3.8 Hz, 1H, @CH2),
Full-set diffraction data for 4 ( h
k
l, 2h 6 53ꢁ) were
collected with an Oxford Diffraction XCalibur 2 diffrac-
tometer with CCD detector Sapphire 2 equipped with an
Oxford Instruments Cryojet HT Cooler and the data for
3
2
5.93 (dd, JHH = 14.6, JHH = 3.8 Hz, 1H, @CH2), 6.16
3
(dd, JHH = 20.3, 14.6 Hz, 1H, @CH), 7.12–7.57 (m, 10H,
PPh2). 13C{1H} NMR (CDCl3): d ꢀ2.15 (SiMe2), 70.84
(CSi of fc), 71.31 (virtual t, J0 = 4 Hz), 73.50, 73.89
(2 · CH of fc); 74.19 (virtual t, J0 = 5 Hz, CH of fc),
82.22 (dd, JPC = 23 and 21 Hz, CP of fc), 127.52 (virtual
t, J0 = 5 Hz), 128.95 (2 · CH of PPh2); 131.70 (@CH2),
132.61 (virtual t, J0 = 6 Hz, CH of PPh2), 138.64 (@CH),
140.5 (virtual t, J0 = 21 Hz, Cipso of PPh2), 204.08 (t,
2JPC = 6 Hz, C„O). 31P{1H} NMR (CDCl3): d +16.5 (s
6 ( h
k
l, 2h 6 55ꢁ) were collected on a Nonius Kap-
paCCD diffractometer equipped with a Cryostream Cooler
(Oxford Cryosystems). The measurements were performed
at 150(2) K with graphite monochromatised Mo Ka radia-
˚
tion (k = 0.71073 A). In both cases, the data were corrected
for absorption using routines included in the diffractometer
software. The ranges of transmission factors and all other
relevant crystallographic data are given in Table 4.
The structures were solved by direct methods (SIR97 [31])
and refined by weighted full-matrix least squares on F2
(SHELXL97 [32]). All non-hydrogen atoms were refined with
anisotropic displacement parameters while the hydrogens
were included in the calculated positions and refined using
the ‘‘riding’’ model. Final geometric calculations were car-
ried out with a recent version of PLATON program [33]. The
calculated numerical values are rounded with respect to
their estimated standard uncertainties given with one
decimal.
1
with 183W satellites, JWP = 282 Hz). HR MS calc. for
C56H5456Fe2O4P2Si2184W, 1204.1244; found, 1204.1259.
NMR data for pentacarbonyl[1-(diphenylphosphanyl-
jP)-10-(dimethylvinylsilyl)ferrocene]tungsten(0) (8). 1H
NMR (CDCl3): d 0.17 (s, 6H, SiMe2), 3.82 and 4.16
(2 · apparent t, 2H, fc); 4.24 (apparent q, 2H, fc), 4.48 (f
3
2
of apparent t, 2H, fc), 5.64 (dd, JHH = 20.1, JHH
=
3
2
3.8 Hz, 1H, @CH2), 5.95 (dd, JHH = 14.5, JHH = 3.8 Hz,
3
1H, @CH2), 6.14 (dd, JHH = 20.1, 14.5 Hz, 1H, @CH),
7.12–7.57 (m, 10H, PPh2). 13C{1H} NMR (CDCl3): d
2
2
197.33 (d, JPC = 7 Hz, four cis-C„O), 207.77 (d, JPC
=
20 Hz, four trans-C„O). 31P{1H} NMR (CDCl3): d
Acknowledgements
+11.6 (s with 183W satellites, JWP = 236 Hz).
1
This study was financially supported by the Czech
Science Foundation (Grant No. GA CR 203/05/0276)
and is a part of the long-term research project supported
by the Ministry of Education, Youth and Sports of the
Czech Republic (Project No. MSM0021620857). The
4.8. X-ray crystallography
Single crystals suitable for X-ray diffraction analysis
were obtained by crystallisation from hot heptane (4:
orange needle, 0.07 · 0.09 · 0.60 mm3) or from a toluene–
heptane mixture (6: orange plate, 0.03 · 0.10 · 0.15 mm3).
´
ˇ
´
author is indebted to Dr. Ivana Cısarova for recording
the X-ray diffraction data.

ˇ
P. Steˇpnicˇka / Journal of Organometallic Chemistry 693 (2008) 297–306
306
[7] Compound 1 has been reported previously as a by-product arising
from acid-catalysed dehydration of 1-(diphenylphosphanyl)-10-(1-
hydroxyethyl)ferrocene and its reaction with [(Cy3P)2Cl2Ru@CHPh]
(Cy = cyclohexyl) was studied: (a) I.R. Butler, W.R. Cullen, Can. J.
Chem. 61 (1983) 147;
Appendix A. Supplementary material
CCDC 660757 and 660758 contain the supplementary
crystallographic data for 4 and 6. These data can be
obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.jorganchem.2007.10.056.
(b) I.R. Butler, S.J. Coles, M.B. Hursthouse, D.J. Roberts, N.
Fujimoto, Inorg. Chem. Commun. 6 (2003) 760.
ˇ
[8] P. Steˇpnicˇka, I. C´ısarˇova´, Collect. Czech. Chem. Commun. 71 (2006)
215.
ˇ
´
ˇ
´
[9] (a) P. Steˇpnicˇka, I. Cısarova, Inorg. Chem. 45 (2006) 8485;
ˇ
´
ˇ
´
(b) P. Steˇpnicˇka, M. Lamacˇ, I. Cısarova, J. Organomet. Chem., in
press, doi:10.1016/j.jorganchem.2007.11.016.
[10] For a phosphane modified with the dimethylvinylsilyl group, see:
E.C. Alyea, P.R. Meehan, G. Ferguson, S. Kannan, Polyhedron 16
(1997) 3479.
[11] (a) L.-L. Lai, T.-Y. Dong, Chem. Commun. (1994) 2347;
(b) T.-Y. Dong, L.-L. Lai, J. Organomet. Chem. 509 (1996)
131;
References
[1] (a) L.H. Pignolet (Ed.), Homogeneous Catalysis with Metal Phos-
phine Complexes, Plenum Press, New York, 1983;
(b) C. Masters, Homogeneous Transition-metal Catalysis, A Gentle
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(c) I.R. Butler, R.L. Davies, Synthesis (1996) 1350.
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Phosphorus Ligands in Comprehensive Coordination Chemistry, vol.
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phosphine complexes can be found in the whole compendium in the
chapters dealing with the coordination chemistry of particular metals.
[2] For introductory information about phosphines modified with polar
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