Synthesis, reactivity and structures of ruthenium carbonyl clusters with telluride and hydride ligands

Article abstract of DOI:10.1016/S0022-328X(02)01663-7

The reaction of [Cp₂^*Nb(Te₂H)] (1) (Cp*-C₅Me₅) with [Ru₃(CO)₁₂] in boiling toluene gave known [Ru₄(CO)₁₁(μ₄-Te)₂] (5). Complexes 2-4 were analytically and spectroscopically characterized and X-ray diffraction analyses of 3 and 4 were carried out. The anion of 3 is built up of a triangular hexametallic core of C_3v symmetry, in which the central Ru₃ triangle, being bridged by a μ₃-H ligand, is composed of three corner-linked Ru₃Te tetrahedra. The main structural feature of the anion of 4 is a Ru₅Te octahedron. The cations in 3 and 4 are known niobocenedicarbonyl species. The reaction of 2 with bis(diphenylphosphino)methane (dppm) gave [Ru₃(μ₂-H)₂(CO)₇(dppm)(μ₃-Te)] (6). Low temperature ¹H-NMR spectroscopy and X-ray diffraction analysis show an unsymmetrical distribution of both hydride ligands over the triangular Ru₃ basis of the Ru₃Te tetrahedron. The reaction of 5 with dppm gave [Ru₃(CO)₇(dppm)(μ₃-Te)₂] (7) and known [Ru₄(CO)₉(dppm)(μ₄-Te)₂] (8). The crystal structure of 7 reveals a square pyramidal arrangement of the Ru₃Te₂ core. Electrochemical studies of 5 show this complex to be able to consume up to four electrons in reversible steps.

Full text of DOI:10.1016/S0022-328X(02)01663-7

Journal of Organometallic Chemistry 659 (2002) 22ꢂ28
/
www.elsevier.com/locate/jorganchem
Synthesis, reactivity and structures of ruthenium carbonyl clusters
with telluride and hydride ligands
Martin Brandl a, Henri Brunner a, Helene Cattey b, Yves Mugnier b,
Joachim Wachter a,*, Manfred Zabel a
a Institut fur Anorganische Chemie der Universitat Regensburg, D-93040 Regensburg, Germany
¨
¨
b Laboratoire de Synthe`se et d’Electrosynthe`se Organome´talliques (UMR 5632), Universite´ de Bourgogne, F-21100 Dijon, France
Received 4 April 2002; accepted 3 June 2002
Abstract
ꢀ
The reaction of [Cp2Nb(Te2H)] (1) (Cp*ꢁ
/
C5Me5) with [Ru3(CO)12] in boiling toluene gave [Ru3(m2-H)2(CO)9(m3-Te)] (2),
ꢀ
ꢀ
[Ru6(m3-H)(CO)15(m3-Te)3][Cp2Nb(CO)2] (3) and [Ru5(m2-H)(CO)14(m4-Te)][Cp2Nb(CO)2] (4) along with already known
[Ru4(CO)11(m4-Te)2] (5). Complexes 2ꢂ
/
4 were analytically and spectroscopically characterized and X-ray diffraction analyses of 3
and 4 were carried out. The anion of 3 is built up of a triangular hexametallic core of C3v symmetry, in which the central Ru3
triangle, being bridged by a m3-H ligand, is composed of three corner-linked Ru3Te tetrahedra. The main structural feature of the
anion of 4 is a Ru5Te octahedron. The cations in 3 and 4 are known niobocenedicarbonyl species. The reaction of 2 with
1
bis(diphenylphosphino)methane (dppm) gave [Ru3(m2-H)2(CO)7(dppm)(m3-Te)] (6). Low temperature H-NMR spectroscopy and
X-ray diffraction analysis show an unsymmetrical distribution of both hydride ligands over the triangular Ru3 basis of the Ru3Te
tetrahedron. The reaction of 5 with dppm gave [Ru3(CO)7(dppm)(m3-Te)2] (7) and known [Ru4(CO)9(dppm)(m4-Te)2] (8). The crystal
structure of 7 reveals a square pyramidal arrangement of the Ru3Te2 core. Electrochemical studies of 5 show this complex to be able
to consume up to four electrons in reversible steps. # 2002 Elsevier Science B.V. All rights reserved.
Keywords: Ruthenium; Tellurium; Carbonyl ligands; Cluster chemistry
1. Introduction
there are numerous synthetic routes towards metal
telluride clusters starting from other binary transition
metal carbonyls [5].
The actual interest in the chemistry of ruthenium
chalcogenido clusters is mainly focussed on the combi-
nation of sulfido [1] and selenido [2] ligands with
2
ꢀ
Recently, we described the synthesis of [Cp2 Nb(h -
Te2H)] [6] (1) (Cp*ꢁh-C5Me5) and its application in
/
Ru(CO)n (nꢁ2, 3, 4) fragments and the investigation
/
the synthesis of transition-metal telluride clusters [7]. Its
reactions with binary metal carbonyls are characterized
by the deliberation of ‘active’ Te ligands from the
unique h2-Te2H ligand and the ability of the niobocene
fragment to serve as redox-active CO ligand acceptor,
leading to a series of novel structures. Here, we report
on the reaction of 1 with [Ru3(CO)12] as a new synthetic
route for the formation of neutral or salt-like ruthenium
clusters with three, four, five and six metal atoms, held
together by m3- or m4-Te bridges, and in some cases m2-
or m3-hydrido ligands.
of the reactivity potential of the resulting products. By
contrast only a few examples of ruthenium clusters with
bridging tellurium ligands have been structurally char-
acterized thus far [3,4]. This may be explained by the
apparent lack of suitable Te transfer reagents, although
* Corresponding author. Tel.: ꢃ
943-44139
E-mail address: joachim.wachter@chemie.uni-regensburg.de (J.
Wachter).
/
49-941-943-4419; fax: ꢃ49-941-
/
0022-328X/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 3 2 8 X ( 0 2 ) 0 1 6 6 3 - 7

M. Brandl et al. / Journal of Organometallic Chemistry 659 (2002) 22ꢂ
/
28
23
˚
forming the central triangle are by ca. 0.2 A longer
2. Results
than those forming the peripheral RuꢂRu bonds. Planar
/
triangular hexametallic metal clusters with C3v symme-
try are rare, and as far as we know the only known
example is the sulfur analogue of 3 [12]. A comparison
ꢀ
2.1. The reaction of [Ru3(CO)12] with [Cp2Nb(Te2H)]
(1)
of both cluster cores reveals an elongation of all ‘inner’
˚
0.1 A in 3 due to the
ꢀ
larger size of Te. The structure of the [Cp2 Nb(CO)2]
cation is identical with those observed in
The reaction of 1 with two equivalents of [Ru3(CO)12]
in boiling toluene gave after chromatographic work-up
and ‘outer’ Ruꢂ
/
Ru bonds by 0.04ꢂ
/
ꢃ
yellow 2 (11% yield), orange 3 (4%), redꢂ
/
brown 4 (31%)
and orangeꢂbrown 5 (27%) (Scheme 1). All compounds
/
ꢀ
[Co11(CO)10Te7][Cp2Nb(CO)2] [7] or [Fe3H(CO)9Te]-
ꢀ
[Cp2Nb(CO)2] [13] cluster salts.
The IR spectrum of 4 reveals three strong absorptions
in the range of terminal CO ligands and one absorption
in the CO bridging region. The 1H-NMR spectrum
1
were investigated by means of IR, H-NMR and mass
spectra as well as elemental analyses. X-ray diffraction
studies were carried out on complexes 3ꢂ5. The result of
/
the structure determination of 5 was completely iden-
tical with that of octahedral [Ru4(CO)11(m4-Te)2], which
had been obtained from [Ru3(CO)12] and [Fe3(CO)9Te2]
in poor yield [3].
shows resonances at dꢁ
/
ꢄ12.2 and 1.94 in a ratio 1:30,
/
they are assigned to m2-H and C5Me5 hydrogens. ESI
mass spectra of 4 exhibit peaks attribuable to a
ꢃ
[Cp2Nb(CO)2] cation and a [Ru5H(CO)14Te]ꢄ anion,
Complex
2
has been identified as [Ru3(m2-
ꢀ
H)2(CO)9(m3-Te)], spectroscopic data of which are
identical with those of a product obtained in low yields
from [Ru3(CO)12] and TeO3 [8] or from [Ru3(CO)12] and
elemental tellurium (35 bar of CO/H2) [9]. However,
complete characterization was not achieved in these
reports. Since then the related 48 valence electron
respectively. The negative mass spectrum shows four
peaks characteristic of successive loss of CO groups.
An X-ray crystallographic study of 4 reveals a slightly
distorted square-pyramidal Ru5 geometry spanned by a
m4-Te ligand (Fig. 2). Three edges of the nearly square
basis are bridged in a slightly unsymmetric manner by
CO ligands. The fourth edge may be spanned by a
clusters [M3H2(CO)9Te] (Mꢁ
/
Fe [10]; MꢁOs [11])
/
were prepared while a crystal structure determination
was carried out on [Os3H2(CO)9Te] [11]. As 2 did not
crystallize well we investigated its reaction with bis(di-
phenylphosphino)methane (dppm), which gave the or-
ange complex 6 (see below).
hydrogen bridge, for this bond [d{Ru(1)ꢂ
/
Ru(4)}ꢁ
/
˚
(3.025(1) A] is significantly longer than the other ones
[dmean
˚
ꢁ2.830(1) A] of the Ru4 square (Table 1). The
/
presence of a hydride ligand is in agreement with the 1H-
NMR spectrum and it is also supported by the fact that
The IR spectrum of 3 contains four strong absorp-
tions typical of terminal CO bands. The 1H-NMR
hydrogen bridges tend to lengthen the concerned metalꢂ
/
metal bond [14]. All RuꢂRu and RuꢂTe distances are
/
/
spectrum exhibits two singlets at dꢁ
/
ꢄ
/
36.45 and dꢁ
/
comparable to those in [Ru4(CO)11(m4-Te)2] (5) [3]. The
cluster anion of 4 has 74 valence electrons. According to
1.94 in a ratio 1:30, which may be assigned to m3-H and
C5Me5 hydrogens, respectively. This finding is consis-
the WadeꢂMingos rules it is a closo-octahedron with
/
tent with the presence of a [Cp2Nb(CO)2]ꢃ cation and a
ꢀ
seven sceletal electron pairs. Thus, it may be derived
from the class of neutral clusters of the type
[Ru6H(CO)15Te3]ꢄ anion. Positive and negative ESI
mass spectra exhibit each ion respectively. The negative
mass spectrum indicates in addition successive loss of
eight CO groups.
[Ru5(CO)15X] (XꢁS, Se, Te), for which as the only
/
actual representative [Ru5(CO)15S] has been synthesized
thus far [15]. As in the structure for 3 there are no
ꢃ
The composition of 3 is confirmed by an X-ray
crystallographic investigation. The molecular structure
of the anion consists of a Ru3 triangle composed of three
corner-linked Ru3Te tetrahedra (Fig. 1). Their Te
vertices are co-oriented at one side whereas the wingtips
of their Ru3 bases form a shallow bowl. In the centre of
this bowl and bridging the central Ru3 triangle a m3-H
ligand has been found in the difference Fourier map.
Due to the EAN rule 3 has 92 valence electrons. There
ꢀ
peculiarities for the [Cp2Nb(CO)2] cation [7,13].
2.2. The reaction of 2 and 5 with dppm
The reaction of 2 with one equivalent of dppm gave
the orange complex [Ru3(m2-H)2(CO)7(dppm)(m3-Te)]
(6). Its composition was confirmed by means of field
desorption (FD) mass spectrum and elemental analyses.
The IR spectrum exhibits five strong bands typical of
1
are two kinds of RuꢂRu bonds (Table 1). Those
/
terminal CO groups. The H-NMR spectrum at room
temperature consists of three groups of signals: A singlet
at dꢁ
and a multiplet at dꢁ
Monitoring the RuH resonance at low temperatures
reveals a dynamic process (kꢁ 11.459
687 sꢄ1, DG%249
0.5 kcal molꢄ1) which is frozen at ꢄ
90 8C. The low
/
ꢄ
/
17.95 for RuH, a multiplet at dꢁ
/
3.67 for CH2
/
7.27ꢄ7.48 for the C6H5 rings.
/
/
ꢁ
/
/
Scheme 1.
/

24
M. Brandl et al. / Journal of Organometallic Chemistry 659 (2002) 22ꢂ28
/
Fig. 1. Molecular structure of the [Ru6H(CO)15Te3]ꢄ anion of 3 in top (left) and side (right) views.
phosphorus resonances in the 31P spectrum at dꢁ
and 26.8.
/
21.3
Table 1
Selected
˚
(A)
bond
lengths
and
angles
(8)
for
[Ru6H(CO)15Te3][Cp*2Nb(CO)2] (3), [Ru5H(CO)14Te][Cp*2Nb(CO)2]
(4), [Ru3(CO)7H2(dppm)Te] (6) and [Ru3(CO)7(dppm)Te2] (7)
The solid state structure of the molecule (Fig. 3)
shows a Ru3Te tetrahedron as the central feature with
attached terminal CO ligands and the dppm ligand
coordinated at Ru(1) and Ru(3). The difference Fourier
synthesis reveals the presence of two hydride bridges,
which are distributed throughout the Ru3 triangle in an
unsymmetrical manner. This finding is consistent with
3
4
6
7
Bond lengths
Ru(1)ꢂ
Ru(1)ꢂ
Ru(1)ꢂ
Ru(1)ꢂ
Ru(1)ꢂ
Ru(2)ꢂ
Ru(2)ꢂ
Ru(3)ꢂ
Ru(3)ꢂ
Ru(4)ꢂ
Ru(5)ꢂ
Ru(1)ꢂ
Ru(2)ꢂ
Ru(3)ꢂ
Ru(4)ꢂ
Ru(1)ꢂ
Ru(3)ꢂ
Ru(1)ꢂ
Ru(3)ꢂ
Ru(5)ꢂ
Nb(1)ꢂ
Nb(1)ꢂ
/
Ru(2)
Ru(3)
Ru(4)
Ru(5)
Ru(6)
Ru(3)
Ru(5)
Ru(4)
Ru(5)
Ru(5)
Ru(6)
Te(1)
Te(1)
Te(1)
Te(1)
P(1)
2.820(1) 2.826(1) 2.970(1)
3.099(1) 2.913(1)
3.025(1)
2.871(1)
/
/
/
3.086(1) 2.931(1)
2.819(1)
the low temperature NMR spectra. The bridged Ruꢂ
/Ru
/
˚
bonds [average 2.942(1) A] are significantly longer than
/
2.821(1) 2.847(1) 2.790(1)
2.843(1)
2.945(1)
˚
Ru(3) bond [2.7898(5) A] (Table
/
the unbridged Ru(2)ꢂ
/
/
2.830(1) 2.818(1)
3.146(1) 2.861(1)
2.827(1) 2.923(1)
2.818(1)
1).
/
Due to the difficulties in recognizing the true nature
of 2 we employed in the beginning of our studies
unconsciously mixtures of 2 and 5 for the reaction
with dppm. From these reactions we got along with the
above described tetrahedral cluster 6 another cluster
which analyzed as [Ru3(CO)7(dppm)Te2] (7). In order to
verify the source of this compound, we repeated the
reaction of pure 5 with dppm, which has already been
carried out by Mathur et al. [3]. Under similar reaction
conditions (stoichiometry 1:1, CH2Cl2, 8 h, 20 8C),
orange 7 and brown 8 were formed (Scheme 2). The
latter turned out by means of analytical and spectro-
scopic data to be identical with the already published
octahedral cluster [Ru4(CO)9(dppm)(m4-Te)2] [3],
whereas 7 was not observed in the previous reaction.
The composition of 7 was confirmed by means of FD
mass spectrum and elemental analyses. The IR spectrum
exhibits three strong absorptions typical of terminal CO
groups, while the 1H-NMR spectrum contain signals
which may be assigned to the dppm ligand. The crystal
structure determination of 7 reveals a Ru3Te2 square
pyramid as the central feature (Fig. 4). The CO ligands
are all terminally coordinated and the dppm ligand
/
/
/
2.659(1) 2.688(1) 2.683(1)
2.586(1) 2.732(1) 2.688(1)
2.655(1) 2.710(1) 2.656(1)
2.696(1)
2.652(1)
2.683(1)
2.636(1)
/
/
/
b
/
2.333(1)
2.325(1)
2.320(2)
2.336(2)
/P(2)
a
/H
1.85(5)
1.74(4)
/H
1.95(5)
/H
1.95(5)
/
C(15)
2.057(5) 2.076(3)
2.073(5) 2.073(3)
/
C(16)
Bond angles
Ru(2)ꢂRu(1)ꢂ
Ru(2)ꢂRu(1)ꢂ
Ru(1)ꢂRu(2)ꢂ
Ru(1)ꢂRu(3)ꢂ
Ru(1)ꢂRu(5)ꢂ
Ru(1)ꢂTe(1)ꢂ
C(15)ꢂNb(1)ꢂ
/
/
Ru(4)
Ru(6)
Ru(3)
Ru(5)
Ru(3)
88.2(1)
151.6(1)
66.7(1)
/
/
/
/
60.7(19
66.1(1)
/
/
59.2(1)
/
/
89.3(1)
/
/Ru(3)
97.9(1)
97.9(1)
/
/C(16)
86.3(2) 87.5(1)
a
Mean.
b
Ru(2)ꢂP(1).
/
temperature limit spectrum exhibits two RuH reso-
nances at dꢁ 18.35 and 17.57, what indicates
hydride bridges in different environment. Con-
/
ꢄ
/
ꢂ
/
bridges the edge Ru(2)ꢂ
/
Ru(3). The latter bond is longer
by 0.075 A than the unbridged Ru(1)ꢂRu(2) one. All
RuꢂRu and RuꢂTe distances are within the same range
˚
/
comittantly, at the same temperature there are two
/
/

M. Brandl et al. / Journal of Organometallic Chemistry 659 (2002) 22ꢂ
/
28
25
ꢀ
Fig. 2. Molecular structure of [Ru5H(CO)14Te][Cp2Nb(CO)2] (4), anion left and cation right.
Fig. 4. Molecular structure of [Ru3(CO)7(dppm)Te2] (7).
Fig. 3. Molecular structure of [Ru3H2(CO)7(dppm)Te] (6).
[M3(CO)9Te2] (MꢁFe [16], Os [17]) belonging to the
/
nido-octahedral structure type.
observed for the other clusters reported in this paper
and [Ru4(CO)11(m4-Te)2] (5). The structure of 7 may be
derived from that of 5 by removal of one Ru(CO)2
vertex and subsequent substitution of two CO groups.
Thus, 7 is like [Ru3(CO)6(PPh3)3Te2] [3] a further
derivative of the class of 50 valence electron clusters
2.3. Electrochemistry of 2 and 5
The electrochemical behavior of 2 has been studied by
cyclic voltammetry and rotating disk electrode (RDE)
Scheme 2.

26
M. Brandl et al. / Journal of Organometallic Chemistry 659 (2002) 22ꢂ28
/
voltammetry. In the cathodic area, two irreversible
systems have been obtained with Ecꢁ 1.26 V and
2.18 V/SCE (saturated calomel electrode).
THF solutions of 5 exhibit in rotating disk electrode
voltammetry three reduction steps at E1/2 0.38,
0.74 and ꢄ1.97 V/SCE. The height of these waves
are in the ratio: 1:0.92:1.54. The second wave is smaller
than the first one because the diffusing species may be
[Ru4(CO)11(m4-Te)2]ꢄ, which has a smaller diffusion
coefficient than 5.
indicate a rearrangement of the initial Ru4Te2 frame-
work of 5.
/
ꢄ
/
This behavior may indicate an interesting ability of 5
for reversible and multiple electron uptake. In this
regard 5 resembles homoleptic transition-metal carbonyl
clusters with electron-sink features [19]. No other
ruthenium chalcogenide cluster has been investigated
before with respect to its redox properties. It may be
noted that [Ru3(CO)12] behaves completely different.
ꢄ
/
ꢁ
/
ꢄ
/
ꢄ
/
/
The only reduction wave at ꢄ
/
1.05 V is followed by
In cyclic voltammetry three reversible systems are
observed at sweep rates between 0.02 and 0.2 V sꢄ1. The
two first waves are monoelectronic and the third one is
bielectronic (Fig. 5). The ratio ip/v1/2 was verified to be
constant and the ratio ipa/ipc was close to 1, in accord
with diffusion control. The halfwave potentials are
independent of potential scan rate and the peak shapes
rapid chemical reactions [20].
In conclusion, a new synthetic route for the formation
of several neutral and salt-like ruthenium carbonyl
clusters with telluride and hydride ligands has been
found. It is striking that the compounds obtained are
relatively poor in tellurium content giving rise to a
preferential metal carbonyl character of the clusters and
it has been impossible to increase the tellurium content
by varying the stoichiometry of the title reaction.
Further studies are necessary to explore the reactivity
are characterized by jEpcꢄ
/
Epaj:
/
60 mV for the first two
systems. The mechanism, at the time scale of cyclic
voltammetry, is schematically given in Eq. (1).
eꢄ
eꢄ
2eꢄ
[Ru4(CO)11Te2] X [Ru4(CO)11Te2]ꢄ X [Ru4(CO)11Te2]2ꢄ X [Ru4(CO)11Te2]4ꢄ
(1)
A1=A2
A2=A2?
A3=A3?
52ꢄ
54ꢄ
5
5ꢄ
Some DFT/B3LYP/Lanl2DZ calculations [18] have
been performed on 5 and on its reduced species 5ꢄ and
of the new compounds and to reveal whether the
hydrogens in 3 and 4 arise from the Te2H ligand in 1
or from the solvent.
52ꢄ, respectively, showing that mainly the Ru(3)ꢂ
Ru(4)
distances are affected by reduction process. For the
/
optimized structures these distances vary from 3.097
(neutral) through 3.222 (5ꢄ) to 3.359 (52ꢄ) A. Conse-
˚
3. Experimental
quently, the dianion may exhibit a nido (pentagonal
bipyramid) structure. Further reduction (e.g. 53ꢄ) does
not lead to convergence of metric parameters, what may
3.1. General and methods
All procedures were carried out under nitrogen using
Schlenk techniques and dry solvents. Elemental analyses
were performed by the Mikroanalytisches Laborator-
ium, Universitat Regensburg. IR spectra were obtained
¨
with a Mattson Genesis Series FTIR instrument, ESI
mass spectra and FD mass spectra were obtained on
Finnigan TSQ 7000 and MAT 95 instruments, respec-
1
tively. The H-NMR and 31P-NMR spectra were taken
on a Bruker ARX 400 instrument at 400.1 and 161.9
ꢀ
MHz, respectively. [Cp2Nb(Te2H)] (1) was prepared
ꢀ
from [Cp2 NbBH4] and elemental tellurium [6]. Electro-
chemistry: cyclic voltammetry was carried out in a
standard three-electrode cell with a Tacussel UAP4
unit cell. The reference electrode was a saturated
calomel electrode (SCE) separated from the solution
by a sintered glass disk. The auxiliary electrode was a
platinum wire. For all voltammetric measurements, the
working electrode was a vitreous carbon electrode. The
Fig. 5. Cyclic voltammogram of 5 in THF (0.2 mol lꢄ1 of NBu4PF6)
on a carbon electrode. Sweep rate: 0.1 V sꢄ1. Starting potential: 0 V.

M. Brandl et al. / Journal of Organometallic Chemistry 659 (2002) 22ꢂ
/
28
27
Table 2
Crystallographic data for complexes 3, 4, 6 and 7
3
4
6×CH2Cl2
7×C7H8
Formula
C37H31NbO17Ru6Te3
1829.75
C36H31NbO16Ru5Te
1444.46
C33H26Cl2O7P2Ru3Te
1098.19
C39H30O7P2Ru3Te2
1230.98
Moleculat weight
Crystal size (mm)
Crystal system
0.28ꢅ0.20ꢅ0.18
Monoclinic
15.680(1)
0.30ꢅ0.16ꢅ0.04
Triclinic
11.418(1)
0.60ꢅ0.42ꢅ0.24
Triclinic
12.036(2)
0.24ꢅ0.12ꢅ0.06
Triclinic
9.949(1)
˚
a (A)
˚
b (A)
11.270(1)
28.005(1)
13.872(2)
15.119(1)
12.142(1)
13.063(2)
20.224(2)
22.378(2)
˚
c (A)
a (8)
b (8)
g (8)
V (A )
Space group
Z
75.39(1)
68.72(1)
93.92(2)
93.23(2)
104.42(1)
101.71(1)
91.81(1)
88.49(1)
2153.6(4)
¯
P1
101.27(2)
1863.0(3)
¯
P1
100.11(1)
4146.8(6)
¯
P1
3
˚
4946.3(5)
P21/n
4
2.457
2
2.227
2
1.958
4
1.972
rcalc (g cmꢄ3
Instrument
)
Stoe IPDS
173
3.80
Stoe IPDS
173
2.70
Stoe IPDS
173
2.241
Stoe IPDS
173
2.581
Temperature (K)
m (mmꢄ1
)
Absorption correction
Transmission
Scan range
numerical
0.619/0.501
1.95BU B25.85.0
35081
numerical
0.814/0.596
1.92BU B25.82
30370
numerical
0.442/0327
2.69BU B26.69
23893
numerical
0.895/0.705
1.95BU B25.84
34867
Total reflections
Observed reflections (I ꢀ2.0s(I))
No. of LS parameters
9372
580
7744
532
7293
439
11420
955
ꢄ3
˚
Residual density (e A
R1
)
0.704/ꢄ0.392
0.022
0.048
0.889/ꢄ0.366
0.018
0.046
1.063/ꢄ1.077
0.026
0.073
0.815/ꢄ0.511
0.027
0.059
wR2
controlled potential electrolysis was performed with an
Amel 552 potentiostat coupled to an Amel 721 electro-
nic integrator. Electrolyses were performed in a cell with
three compartments separated with fritted glasses of
medium porosity. A carbon gauze was used as the
cathode, a platinum plate as the anode and a saturated
calomel electrode as the reference electrode.
3: Anal. Found: C, 24.32; H, 1.72. Calc. for
C37H31NbO17Ru6Te3 (1829.8): C, 24.28; H, 1.71%. NI-
128
15
ESIMS (from CH2Cl2) 1410.4 ([101Ru6H(CO) Te3]ꢄ).
1H-NMR (CD2Cl2): d ꢄ
36.45 (s, 1H, RuH), 1.94 (s,
/
30H, Me). IR (KBr, cmꢄ1): nCO 2066s, 2035s, 1993s,
1957s.
4: Anal. Found: C, 29.89; H, 2.29; Te, 8.01. Calc. for
C36H31NbO16Ru5Te (1445.5): C, 29.91; H, 2.16; Te,
8.86%.
NI-ESIMS
128
14
(from
CH2Cl2)
1026.6
12.20
3.2. Reaction of 1 with [Ru3(CO)12]
1
([101Ru5H(CO) Te]ꢄ). H-NMR (CD2Cl2), d ꢄ
/
(s, 1H, RuH), 1.94 (s, 30H, Me). IR (CH2Cl2, cmꢄ1):
nCO 2062s, 2010s, 1959s, 1814s.
The mixture of 260 mg (0.42 mmol) of
ꢀ
[Cp2Nb(Te2H)] (1), 540 mg (0.84 mmol) of
[Ru3(CO)12] and 140 ml of toluene was refluxed for 18
h. After cooling the solvent was evaporated and the
3.3. Synthesis of [Ru3(m2-H)2(CO)7(dppm)(m3-Te)]
(6)
redbrown residue dissolved in 20 ml of CH2Cl2ꢂ
3:1. Chromatography on SiO2 (column 28ꢅ3 cm) gave
upon elution with CH2Cl2ꢂtoluene 3:1 an orangeꢂ
brown band and then two bands containing orange 3
(30 mg, 4% yield) and redꢂbrown 4 (190 mg, 31%).
/
toluene
/
/
/
The mixture of 120 mg (0.18 mmol) of 2, 90 mg (0.23
mmol) of dppm and 100 ml of CH2Cl2 was stirred at
room temperature (r.t.) for 10 h. After evaporation of
/
Repeated chromatography of the first band gave after
elution with pentane a yellow band containing 2 (65 mg,
11% yield) and an orange band. The latter has been
identified by comparison of spectroscopic and analytical
data as the known complex 5 (100 mg, 27%).
the solvent the residue was dissolved in CH2Cl2ꢂ
pentane 1:1 and chromatographed on SiO2 (column
15ꢅ3 cm). Elution with CH2Cl2ꢂpentane 1:1 gave a
yellowꢂorange band containing 100 mg (56%) of 6. The
complex was recrystallized from CH2Cl2.
6: Anal. Found: C, 36.85; H, 2.52. Calc. for
/
/
/
/
2: Anal. Found: C, 15.95; H, 0.41. Calc. for
C9H2O9Ru3Te (684.9): C, 15.78; H, 0.29%. FD MS
C32H24O7P2Ru3Te×
2.39%. FDMS 1014.8 ([101Ru3H2(CO)7(dppm)128Te]ꢃ).
{31P}1H-NMR (CD2Cl2, 183 K): d ꢂ
18.35 [d, 1H, RuH;
/CH2Cl2 (1098.2): C, 36.09; H,
1
685. H-NMR (CD2Cl2): d ꢄ
/
19.03 (s, 2H, RuH). IR
(KBr, cmꢄ1): nCO 2112s, 2076s, 2041s, 2006s, 1978s.
/

28
M. Brandl et al. / Journal of Organometallic Chemistry 659 (2002) 22ꢂ28
/
2
2J(Hꢂ
Hz], 3.69 [d, 1H, CH2; 2J(Hꢂ
/
H)ꢁ
/
2.7 Hz], ꢄ
/
17.57 [d, 1, RuH; J(Hꢂ
H)ꢁ13.1 Hz], 3.87 [d, 1H,
13.1 Hz], 7.10ꢂ7.54 (m, 20H, C6H5).
{1H}31P-NMR (CD2Cl2, 183 K): d 21.3 (2J(Pꢂ
P)ꢁ53
Hz), 26.8 (2J(Pꢂ 53 Hz). IR (KBr, cmꢄ1): nCO
P)ꢁ
2057s, 2039s, 1999s, 1974s, 1944s.
/
H)ꢁ
/
2.7
Acknowledgements
/
/
2
CH2; J(Hꢂ
/
H)ꢁ
/
/
We are grateful to the Deutsche Forschungsge-
meinschaft for financial support. Parts of this work
were supported by the Deutscher Akademischer Aus-
landsdienst and the Ministe`re des Affaires Etrange`res
(program PROCOPE).
/
/
/
/
3.4. Reaction of [Ru4(CO)11Te2] (5) with dppm
References
The mixture of 100 mg (0.10 mmol) of 5, 50 mg (0.13
mmol) of dppm and 70 ml of CH2Cl2 was stirred at r.t.
for 8 h. After evaporation of the solvent the residue was
[1] A.J. Deeming, in: E.W. Abel, F.G.A. Stone, G. Wilkinson (Eds.),
Comprehensive Organometallic Chemistry, vol. 7, Pergamon,
Oxford, 1995, p. 726.
purified by chromatography on SiO2 (column 15ꢅ
/
3
[2] D. Cauzzi, C. Graiff, G. Predieri, A. Tiripicchio, in: P. Braun-
stein, L.A. Oro, P.R. Raithby (Eds.), Metal Clusters in Chemistry,
vol. 1, Wiley-VCH, New York, 1999, p. 193.
cm). Elution with CH2Cl2ꢂpentane 2:1 gave an orange
/
band containing 42 mg (36.8%) of 7. A subsequent
brown band contained 42 mg (32.4%) of 8, which has
been identified by comparison of IR and 1H-NMR
spectra with already known data [3].
[3] P. Mathur, B.H.S. Thimmappa, A.L. Rheingold, Inorg. Chem. 23
(1990) 4658.
[4] S.-P. Huang, M.G. Kanatzidis, J. Am. Chem. Soc. 114 (1992)
5477.
7: Anal. Found: C, 37.64; H, 2.48. Calc. for
C7H8 (1231.0): C, 38.05; H, 2.46%.
[5] (a) J.W. Kolis, Coord. Chem. Rev. 105 (1990) 195;
(b) L.C. Roof, J.W. Kolis, Chem. Rev. 93 (1993) 1037.
[6] O. Blacque, H. Brunner, M.M. Kubicki, B. Nuber, B. Stubenho-
fer, J. Wachter, B. Wrackmeyer, Angew. Chem. Int. Ed. Engl. 36
(1997) 351.
C32H22O7P2Ru3Te2×
/
FDMS 1140 ([101Ru3(CO)7(dppm)128Te2]ꢃ). H-NMR
1
(CD2Cl2): 4.19 [m, 2H, CH2], 7.43ꢂ7.70 [m, 20H, C6H5].
/
IR (KBr, cmꢄ1): nCO 2057s, 1996vs, 1944s.
[7] (a) H. Brunner, D. Lucas, T. Monzon, Y. Mugnier, B. Nuber, B.
Stubenhofer, A.C. Stuckl, J. Wachter, R. Wanninger, M. Zabel,
¨
Chem. Eur. J. 6 (2000) 493;
(b) H. Brunner, A.C. Stuckl, J. Wachter, R. Wanninger, M.
¨
3.5. X-ray structure solution
Zabel, Angew. Chem. Int. Ed. Engl. 40 (2001) 2529.
[8] E. Sappa, O. Gambino, G. Cetini, J. Organomet. Chem. 35 (1972)
375.
The structures of 3, 4, 6 and 7 were solved by direct
methods and refined by full-matrix least-squares tech-
niques with the program SHELXL-97. Subsequent differ-
ence Fourier syntheses revealed the position of the non-
hydrogen atoms and all these atoms were refined with
anisotropic thermal parameters. All H atoms attached
to C were calculated geometrically and a riding model
was used during refinement process. The hydrogen
bridges in the structures of 3 [H(1)] and 6 [H(34, 35)]
were found in the difference Fourier map. Details for the
structure refinements are listed in Table 2.
[9] B.F.G. Johnson, J. Lewis, P.G. Lodge, P.R. Raithby, J. Chem.
Soc. Chem. Commun. (1979) 719.
[10] L.C. Roof, D.M. Smith, G.W. Drake, W.T. Pennington, J.W.
Kolis, Inorg. Chem. 34 (1995) 337.
[11] H.T. Schacht, A.K. Powell, H. Vahrenkamp, M. Koite, H.J.
Kneuper, J.R. Shapley, J. Organomet. Chem. 368 (1989) 269.
[12] U. Bodensieck, H. Stoeckli-Evans, G. Suss-Fink, Angew. Chem.
¨
Int. Ed. Engl. 30 (1991) 1126.
[13] H. Brunner, J. Wachter, R. Wanninger, M. Zabel, J. Organomet.
Chem. 603 (2000) 135.
[14] C.J. Gilmore, P. Woodward, J. Chem. Soc. A (1971) 3453.
[15] R.D. Adams, J.E. Babin, M. Tasi, Organometallics 7 (1988) 503.
[16] (a) W. Hieber, J. Gruber, Z. Anorg. Allg. Chem. 296 (1958) 91;
(b) D.A. Lesch, T.B. Rauchfuss, Inorg. Chem. 20 (1981) 3583;
(c) D.A. Lesch, T.B. Rauchfuss, Organometallics 1 (1982) 499;
4. Supplementary material
(d) H. Schumann, M. Magerstadt, J. Pickardt, J. Organomet.
¨
Chem. 240 (1982) 407.
Crystallographic data for the structural analysis have
been deposited with the Cambridge Crystallographic
Data Centre, CCDC nos. 171078 (3), 171079 (4), 182718
(6) and 182719 (7), respectively. Copies of this informa-
tion may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
[17] J. Zhang, W.K. Leong, J. Chem. Soc. Dalton Trans. (2000) 1249.
[18] E. Vigier, M.M. Kubicki, Private communication.
[19] G. Longoni, C. Femoni, M.C. Iapalucci, P. Zanello, in: P.
Braunstein, L.A. Oro, P.R. Raithby (Eds.), Metal Clusters in
Chemistry, vol. 2, Wiley-VCH, New York, 1999, p. 1137.
[20] (a) A.J. Downard, B.H. Simpson, A.M. Bond, J. Organomet.
Chem. 320 (1987) 363;
(Fax: ꢃ
/
44-1223-336033; e-mail: deposit@ccdc.cam.a-
(b) M.I. Bruce, J.G. Matisons, B.K. Nicholson, J. Organomet.
Chem. 247 (1983) 321.
c.uk or www: http://www.ccdc.cam.ac.uk).