Carbonyl substitution chemistry of neutral and cationic triruthenium cluster complexes derived from 1, 1-dimethylhydrazine. Incorporation of two and three phosphane ligands

Article abstract of DOI:10.1016/S0022-328X(02)01777-1

The reactivity of the neutral triruthenium carbonyl cluster protonated derivative [Ru₃(μ-H)₂ (μ₃-HNNMe₂)(CO)₉][BF₄] (2), both containing a face-capping five-electron donor 1,1-dimethylhydrazido ligand, with an excess of triphenylphosphane and with bis(diphenylphosphanyl)methane (dppm) has been studied. With PPh₃, compound 1 gives initially two independent monosubstituted isomeric intermediates that react with more ligand to afford [Ru₃(μ-H)₂(μ₃ -HNNMe₂) (C₆H₄PPh₂) (PPh₃)(CO)₆] as the final product. This complex contains terminal and cyclometalated triphenylphosphane ligands attached to the same Ru atoms as the NMe₂ and the NH fragments, respectively. The reaction of complex 2 with PPh₃ affords, sequentially, the cationic mono-, di- and trisubstituted derivatives [Ru₃(μ-H)₂ (μ₃-HNNMe₂) (PPh₃)_n(CO) _9-n][BF₄](n=1-3). Unusually, the di- and trisubstituted complexes contain one PPh₃ ligand in an axial position. The reaction of complex 1 with dppm gives the disubstituted derivative [Ru₃(μ-H)(μ₃-HNNMe₂) (μ-dppm)(CO)₇], which contains the P atoms attached to the same Ru atoms as the NH fragment. Protonation of this complex with [HOEt₂][BF₄] gives the cationic derivative [Ru₃(μ-H)₂(μ₃ -HNNMe₂)(μ-dppm)(CO)₇][BF₄]. However, the reaction of complex 2 with dppm leads to an inseparable mixture of products. Many of these results contrast with those previously known for carbonyl substitution reactions on triruthenium clusters isostructural with compounds 1 and 2 but containing other face-capping five-electron donor ligands. The hardness of the donor atoms of the bridging ligand is presented as an important factor in relation to the observed regioselectivity.

Full text of DOI:10.1016/S0022-328X(02)01777-1

Journal of Organometallic Chemistry 663 (2002) 227Á234
/
www.elsevier.com/locate/jorganchem
Carbonyl substitution chemistry of neutral and cationic triruthenium
cluster complexes derived from 1,1-dimethylhydrazine.
Incorporation of two and three phosphane ligands
Javier A. Cabeza a,ꢀ, Ignacio del R´ıo a, Santiago Garc´ıa-Granda b,
Lorena Mart´ınez-Me´ndez a, V´ıctor Riera a
a
´ ´ ´ ´ ´
Departamento de Quımica Organica e Inorganica, Instituto de Quımica Organometalica ‘Enrique Moles’, Facultad de Quimica,
Universidad de Oviedo-CSIC, E-33071 Oviedo, Spain
´
b
´ ´
Departamento de Quımica-Fısica y Analıtica, Universidad de Oviedo, E-33071 Oviedo, Spain
Received 19 June 2002; accepted 26 July 2002
Dedicated to Professor Pascual Royo, an outstanding organometallic chemist, on the occasion of his 65th birthday
Abstract
The reactivity of the neutral triruthenium carbonyl cluster [Ru3(m-H)(m3-HNNMe2)(CO)9] (1) and its protonated derivative
[Ru3(m-H)2(m3-HNNMe2)(CO)9][BF4] (2), both containing a face-capping five-electron donor 1,1-dimethylhydrazido ligand, with an
excess of triphenylphosphane and with bis(diphenylphosphanyl)methane (dppm) has been studied. With PPh3, compound 1 gives
initially two independent monosubstituted isomeric intermediates that react with more ligand to afford [Ru3(m-H)2(m3-
HNNMe2)(C6H4PPh2)(PPh3)(CO)6] as the final product. This complex contains terminal and cyclometalated triphenylphosphane
ligands attached to the same Ru atoms as the NMe2 and the NH fragments, respectively. The reaction of complex 2 with PPh3
affords, sequentially, the cationic mono-, di- and trisubstituted derivatives [Ru3(m-H)2(m3-HNNMe2)(PPh3)n(CO)9ꢁn][BF4] (nꢂ
/
1Á
/
3). Unusually, the di- and trisubstituted complexes contain one PPh3 ligand in an axial position. The reaction of complex 1 with
dppm gives the disubstituted derivative [Ru3(m-H)(m3-HNNMe2)(m-dppm)(CO)7], which contains the P atoms attached to the same
Ru atoms as the NH fragment. Protonation of this complex with [HOEt2][BF4] gives the cationic derivative [Ru3(m-H)2(m3-
HNNMe2)(m-dppm)(CO)7][BF4]. However, the reaction of complex 2 with dppm leads to an inseparable mixture of products. Many
of these results contrast with those previously known for carbonyl substitution reactions on triruthenium clusters isostructural with
compounds 1 and 2 but containing other face-capping five-electron donor ligands. The hardness of the donor atoms of the bridging
ligand is presented as an important factor in relation to the observed regioselectivity.
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Ruthenium; Ruthenium clusters; Carbonyl substitution reactions; 1,1-Dimethylhydrazine; Crystal structures
1. Introduction
In this field, we have previously reported the carbonyl
substitution chemistry of the cluster complexes [Ru3(m-
H)(m3-HNCONMe2)(CO)9] (A) [2], [Ru3(m-H)(m3-am-
The substitution of a phosphane ligand for a CO
ligand in carbonyl metal clusters is a common reaction
[1]. However, despite the great number of such reactions
reported to date, for a given cluster complex, the precise
coordination site that is prone to undergo a carbonyl
substitution cannot be predicted in many occasions.
py)(CO)9] (B; Hampyꢂ
7] and the protonated derivative [Ru3(m-H)2(m3-am-
py)(CO)9][BF4] (C) [3Á7]. These compounds contain
/
2-amino-6-methylpyridine) [3Á
/
/
face-capping five-electron donor ligands attached to the
three ruthenium atoms through two heteroatoms. With-
out exception, on complexes AÁC, the first substitution
/
process takes place at an equatorial site of a ruthenium
atom attached to both the hydride and the amido
fragment of the bridging ligand. This regioselectivity
ꢀ Corresponding author. Tel.:
103446
E-mail address: jac@sauron.quimica.uniovi.es (J.A. Cabeza).
ꢃ
/
34-985-103501; fax:
ꢃ34-985-
/
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 7 7 7 - 1

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J.A. Cabeza et al. / Journal of Organometallic Chemistry 663 (2002) 227Á234
/
has been associated with the cis-labilizing effect pro-
voked by the hardness of both the amido and hydride
ligands [3,4].
In 1990, Suss-Fink and coworkers published the
¨
synthesis of several triruthenium carbonyl derivatives
of the type [Ru3(m-H)(m3-HNNR1R2)(CO)9] by treat-
ment of [Ru3(CO)12] with hydrazines [8]. These com-
pounds are isostructural with complexes A and B, but
their face-capping five-electron donor ligands are hy-
drazido fragments, which are harder than ureato and 2-
amidopyridine fragments. This fact prompted us to
study the CO substitution chemistry of [Ru3(m-H)(m3-
HNNMe2)(CO)9] (1) and its protonated derivative
[Ru3(m-H)2)(m3-HNNMe2)(CO)9][BF4] (2) (Scheme 1),
in order to compare it with that known for the
derivatives AÁC and to draw some conclusions on the
/
influence of ligand electronic factors (hardness) in the
regioselectivity of CO substitution reactions by phos-
phane ligands on carbonyl cluster complexes.
We have already reported the reactions of complexes
1 and 2 with one equivalent of triphenylphosphane [9],
showing that the preferred site for CO substitution in
these compounds is an equatorial site on the Ru atom
attached to the NMe2 fragment and not to the amido
fragment, as occurred with compounds AÁC. We now
/
report the reactions of the hydrazido clusters 1 and 2
with an excess of triphenylphosphane and with bis(di-
phenylphosphanyl)methane (dppm), showing that the
hardness of the bridging ligand donor atoms along with
the position and the nature of the phosphane ligands
already present in the complexes are the main factors
governing the regioselectivity of successive CO substitu-
tion processes on these carbonyl clusters.
Scheme 2.
[Ru3(m-H)2(m3-HNNMe2)(PPh3)(CO)8] (3a and 3b) in
the initial stages of the reaction, but both were converted
into complex 4 as the reaction progressed. A mixture of
3a and 3b was isolated from the reaction of complex 1
with one equivalent of PPh3 [9].
2. Results
2.1. Reactions with triphenylphosphane
The structure proposed for complex 4 in Scheme 2 is
mainly based on NMR data and on the fact that both 3a
and 3b gave 4 when treated with PPh3. Its composition
was indicated by its microanalysis and FAB MS data.
The compound [Ru3(m-H)(m3-HNNMe2)(CO)9] (1)
reacted with at least two equivalents of PPh3 in THF
at reflux temperature to give [Ru3(m-H)2(m3-
HNNMe2)(C6H4PPh2)(PPh3)(CO)6] (4) as the final pro-
duct (Scheme 2). IR monitoring of the reaction showed
the presence of the isomeric monosubstituted derivatives
Its 1H-NMR spectrum (Table 1) shows four CÃ
/H
resonances clearly separated from those of the normal
phenyl rings, indicating orthometalation. The observa-
tion of two hydride resonances also supported the
orthometalation; the fact that they are doublets with
small coupling constants (12.3 and 11.3 Hz) indicated
that each P atom is cis to a hydride [3,4,9] and that the
PRuÃ
such a case, that hydride would be trans to at least one P
atom and a larger J(HÃP) coupling constant would be
expected [4Á
6]. Its 31P{1H}-NMR spectrum consists of
two doublets with a large J(PÃP) coupling constant
(51.3 Hz), in agreement with a colinear arrangement of
the two P atoms with a RuÃRu bond [4]. As suggested
/
RuP edge is not spanned by a hydride because, in
/
/
/
Scheme 1.
/

J.A. Cabeza et al. / Journal of Organometallic Chemistry 663 (2002) 227Á
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229
Table 1
1H- and 31P{1H}-NMR data for the new complexes
a
Compounds 1H-NMR
31P{1H}-NMR
NH
Me2
m-H
Phosphane
7.90 (t, 6.8, 1 H), 7.45 (m, 25 H), 6.93 (t, 6.8, 1 H), 27.7 (d, 51.3), 0.3 (d,
4
6
7
8
9
4.30 (d, 2.65 (s),
6.8) 2.12 (s)
ꢁ10.90 (d, 12.3), ꢁ13.37 (d,
11.3)
6.82 (t, 6.8, 1 H), 6.66 (t, 6.8, 1 H)
51.3)
b
4.76 (d, 3.04 (s),
7.9) 2.41 (s)
ꢁ12.33 (ddd, 3.5, 2.6, 1.2),
ꢁ14.71 (ddd, 4.6, 2.6, 1.2)
7.40 (m, 30 H)
39.1 (s), 29.8 (s)
4.37 (d, 2.41 (s),
7.6) 2.30 (s)
ꢁ12.02 (m), ꢁ12.95 (m)
7.40 (m, 45 H)
38.5 (s), 27.1 (d, 62.3),
22.3 (d, 62.3)
7.06 (t, 2.86 (s)
6.9)
ꢁ12.36 (t, 8.6)
7.30 (m, 20 H), 4.88 (m, 1 H), 4.27 (m, 1 H)
7.40 (m, 20 H), 4.17 (m, 1 H), 3.57 (m, 1 H)
11.5 (s)
6.88 (t, 3.13 (s)
5.5)
ꢁ12.41 (s, br), ꢁ13.72 (d, br,
38.1)
7.0 (d, 37.1), 2.3 (d,
37.1)
a
Spectra run in CDCl3 at room temperature; multiplicities and coupling constants (Hz) are given in parentheses.
Data extracted from the spectra of a mixture of complexes 5, 6 and 7.
b
in Scheme 2, it is the phosphane ligand attached to the
same Ru atom as the NH fragment that underwent
orthometalation. We feel inclined to this proposal
because the hydride that spans the same RuÃ
/Ru edge
as the NH fragment is well out of the plane of the metal
atoms, thus allowing the approach of a phenyl ring to
the neighbouring metal atom, whereas the other hydride
ligand is ca. coplanar with the metal triangle [3,4,9] (see
Figs. 2 and 3 for related dihydrido complexes). Related
cyclometalations of PPh3 in trinuclear clusters have been
observed before [10].
These results contrast with those previously known
for the reactions of compounds A and B with two
equivalents of PPh3, which give disubstitution on the
two Ru atoms spanned by the NH fragment, without
cyclometalation [2,4].
The reaction of complex 2 with two equivalents of
PPh3 in THF at reflux temperature gave a ca. 1.5:1:1.5
mixture of the cationic mono-, di- and trisubstituted
derivatives [Ru3(m-H)2(m3-HNNMe2)(PPh3)n(CO)9ꢁn]-
Scheme 3.
view of the cationic complex. A selection of bond
lengths is given in Table 2. The structure is reminiscent
of that of cluster 5, with the difference that 7 has two
more PPh3 ligands and two less CO ligands than 5.
Interestingly, one PPh3 ligand occupies an axial position
trans to the NH fragment, while the other two are in
[BF4] (nꢂ1 (5), 2 (6), 3 (7)) (Scheme 3) which could
/
not be separated. The use of at least three equivalents of
PPh3 led to the trisubstituted derivative 7 as the final
product. When the reaction of 2 with five equivalents of
PPh3 was monitored by 31P{1H}-NMR spectroscopy
(Fig. 1), it was observed that the monosubstituted
derivative 5 was rapidly formed (singlet at 27.2 ppm)
and that the trisubstituted derivative 7 (singlet at 38.7
and two doublets at 25.0 and 22.5 ppm) started to
appear at the same time as the disubstituted complex 6
(two singlets at 39.8 and 25.9 ppm). These data explain
why complex 6 could not be isolated.
equatorial positions forming a nearly linear P(1)Ã
Ru(1)ÃRu(3)ÃP(3) arrangement. The hydride ligands
H(1) and H(2) span the Ru(1)ÃRu(2) and Ru(2)ÃRu(3)
/
/
/
/
/
edges, respectively, both being trans to CO ligands.
This structure clearly explains the 31P{1H}-NMR
spectrum of this compound (Fig. 1, Table 1), which
shows a singlet and two doublets with a large J(PÃ
/
P)
coupling constant (62.3 Hz), assignable to the axial and
the two equatorial PPh3 ligands, respectively.
Once the structures of 5 and 7 were known, that of the
disubstituted derivative 6 (Scheme 3) was easily assigned
from its NMR spectra (Fig. 1, Table 1) and from the
The monosubstituted compound 5 was isolated from
the reaction of complex 2 with one equivalent of PPh3
[9]. Its structure was confirmed by X-ray diffraction [9].
The structure of the trisubstituted derivative 7 has
been determined by X-ray diffraction. Fig. 2 shows a

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/
Table 2
Selected interatomic distances (A) in 7 and 9
˚
7
9
Ru(1)ÃRu(2)
Ru(1)ÃRu(3)
Ru(2)ÃRu(3)
Ru(1)ÃN(1)
Ru(2)ÃN(1)
Ru(3)ÃN(2)
Ru(1)ÃP(1)
Ru(2)ÃP(2)
Ru(3)ÃP(3)
Ru(1)ÃC(12)
Ru(1)ÃC(13)
Ru(2)ÃC(21)
Ru(2)ÃC(22)
Ru(2)ÃC(23)
Ru(3)ÃC(31)
Ru(3)ÃC(32)
Ru(3)ÃC(33)
Ru(1)ÃH(1)
Ru(2)ÃH(1)
Ru(2)ÃH(2)
Ru(3)ÃH(2)
N(1)ÃN(2)
2.8379(5)
2.7583(5)
2.9897(5)
2.135(4)
2.131(4)
2.207(4)
2.411(1)
2.376(1)
2.413(1)
1.867(5)
1.904(8)
1.903(6)
1.902(5)
2.7996(4)
2.7444(4)
2.9555(4)
2.118(4)
2.122(3)
2.170(3)
2.373(1)
2.343(1)
1.896(5)
1.876(5)
1.900(5)
1.903(5)
1.915(5)
1.962(5)
1.881(5)
1.72(5)
1.873(8)
1.858(5)
1.95(6)
1.70(7)
1.68(6)
1.80(5)
1.473(5)
1.80(5)
1.79(5)
1.80(5)
1.477(5)
fact that it is an intermediate in the formation of
complex 7 from complex 5. The multiplicity (singlets)
and the chemical shifts of its two 31P{1H} resonances
indicate that one PPh3 ligand is in an equatorial position
(as in 5) and the other one is in an axial position (as in
7).
Fig. 1. 31P{1H}-NMR spectra (THF, room temperature, D2O external
lock) of aliquots taken at different reaction times from the reaction of
complex 2 with triphenylphosphane (1:5 mol ratio) in THF at reflux
temperature.
Fig. 2. Structure of the cationic part of compound 7. Ellipsoids are drawn at the 30% probability level.

J.A. Cabeza et al. / Journal of Organometallic Chemistry 663 (2002) 227Á
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234
231
These results contrast with those previously reported
for the reaction of the cationic complex [Ru3(m-H)2(m3-
ampy)(CO)9][BF4] (C), structurally related to 2, with an
excess of triphenylphosphane [4]. Although C also gives
a trisubstituted complex as the final product, the
stereochemistries of its mono-, di- and trisubstituted
derivatives are quite different from those of the com-
plexes derived from 2: (a) the first substitution occurs on
a Ru atom attached to the NH fragment, (b) the second
one occurs on the Ru atom attached to the pyridyl
tion process to give a different isomer [6]. It seems
probable that the different substitution regiochemistry
of compound 2 as compared to that of C, in addition to
the possibility of thermal isomerization processes, are
responsible for the formation of a mixture of com-
pounds in the reaction of 2 with dppm.
Treatment of complex 8 with tetrafluoroboric acid in
dichloromethane allowed the isolation of the cationic
dihydride
derivative
[Ru3(m-H)2(m3-HNNMe2)(m-
dppm)(CO)7][BF4] (9) (Scheme 4). Curiously, complex
9 is not present in the mixture obtained by treating 2
with dppm, as mentioned above. Its 31P{1H}-NMR
fragment, in such a way that there is a linear PÃ
/
RuÃ
/
RuÃP arrangement, and (c) the third one takes place on
/
1
the remaining Ru atom in an equatorial site [4]. The
reasons for these differences are commented below.
spectrum shows inequivalent P atoms and its H-NMR
spectrum indicates that one of the two hydride ligands is
trans to a P atom (J(HÃ
/
P)ꢂ38.1 Hz). This protonation
/
reaction reminds that of the dppm derivative of complex
C [6].
2.2. Reactions with bis(diphenylphosphanyl)methane
The structure depicted for this compound in Scheme 4
is supported by an X-ray diffraction study (Fig. 3, Table
2), which determined that the dppm ligand spans the
Treatment of compound 1 with dppm in THF at
reflux temperature led to the disubstituted compound
[Ru3(m-H)(m3-HNNMe2)(m-dppm)(CO)7] (8). The struc-
ture depicted for this compound in Scheme 4 was easily
deduced from its NMR spectra, which indicate Cs
symmetry. Its 31P{1H}-NMR spectrum is just a singlet
and its 1H-NMR spectrum shows a singlet for both
methyl groups and triplets for the hydride and NH
resonances (Table 1). This regiochemistry is analogous
to that previously observed for the reaction of the
amidopyridine complex B with dppm [6].
same RuÃ
fragment of the hydrazido ligand. The other hydride
bridges one of the remaining RuÃRu edges, being trans
/
Ru edge as one of the hydrides and the NH
/
to a P atom. This structure also indicates that the atom
connectivity in compound 8 is maintained after its
protonation.
Disappointingly, the reaction of the cationic com-
pound 2 with dppm in THF at reflux temperature led to
a mixture of compounds which could not be separated.
Interestingly, the analogous reaction of the cationic
amidopyridine complex C with dppm gives a disubsti-
tuted compound, which undergoes a thermal isomeriza-
3. Discussion
The reactivity study reported herein, coupled with the
previous one on monosubstitution reactions [9], and the
comparison of these results with those known for
analogous carbonyl substitution reactions on structu-
rally related triruthenium clusters containing other face-
capping ligands allow the conclusion that the regios-
electivity of substitution reactions on these systems is
more influenced by electronic factors associated with the
ligands present in the starting complexes than by
structural factors, since structurally related compounds
display different reactivity.
As far as the influence of the face-capping ligand is
concerned, the entering phosphane ligand ends up cis to
a hydride ligand in an equatorial site attached to the
most electrophilic metal atom, which is generally
bonded to the hardest fragment of the bridging ligand.
This statement is particularly applicable for the first
substitution process with monophosphanes, since the
observed results are in accordance with the facts that: (a)
hard N-donor ligands are cis-labilizers [3Á7]; and (b) the
/
NMe2 group is at least as hard as the NH group of the
dimethylhydrazido ligand of 1 and 2 [9] and harder than
the oxygen atom of the ureato ligand of A and the
pyridyl N atom of the 2-aminopyridine ligand of B and
C (both are involved in p-bonding).
Scheme 4.

232
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/
Fig. 3. Structure of the cationic part of compound 9. Ellipsoids are drawn at the 30% probability level.
The regioselectivity observed in the di- and trisub-
Therefore, although some aspects of the regiochem-
istry of these reactions have been satisfactorily ex-
plained, more work is needed, supported by theoretical
studies, to completely rationalise the obtained results.
stitution reactions by monophosphanes is more difficult
to rationalise since the electrophilic effect caused by the
bridging ligand is compensated to a great extent by the
presence of a phosphane ligand in the complexes. It
seems that these substitutions also occur on the most
electrophilic metal atoms, i.e. those free of phosphane
ligands, in positions cis to hydrides, but we have found
no reasons to account for the differences observed in the
derivatives of 2, which contain an axial phosphane
ligand (trans to a N atom), as compared with those of
complex C, which only contain equatorial phosphanes.
We are not aware of a previous example of an axial CO
substitution reaction in a ligand-bridged triruthenium
cluster complex.
4. Experimental
4.1. General data
Solvents were dried over sodium diphenylketyl (THF,
Et2O and hydrocarbons) or CaH2 (CH2Cl2, 1,2-dichlor-
oethane) and distilled under nitrogen prior to use. The
reactions were carried out under nitrogen, using
Schlenk-vacuum line techniques, and were routinely
monitored by solution IR spectroscopy and by spot
TLC. Compounds 1 [11] and 2 [9] were prepared as
described previously; all the remaining reagents were
purchased from commercial suppliers. IR spectra were
In the case of the reactions with dppm, it seems that the
bite angle of this ligand makes it particularly appropriate
to span the same RuÃ
/
Ru edge as the NH fragment (at
least in the neutral complexes) and that this factor is
important in the regiochemistry of the reactions.
The positive charge of the cationic complexes en-
hances the electrophility of their metal atoms, allowing
the preparation of trisubstituted products, while only
disubstitutions can be obtained with neutral precursors.
For these reactions, it is important to emphasise that
the stereochemistry of the final observed product should
not necessarily correspond the initial substitution pro-
cess (kinetic product), since rearrangements of ligand-
substituted cluster carbonyls are well established, in-
cluding migration of phosphane and CO ligands from
recorded in solution on a PerkinÁElmer Paragon 1000
/
FT spectrophotometer. NMR spectra (Table 1) were run
on a Bruker DPX-300 instrument, using the residual
solvent peak (for 1H) or external 85% H3PO4 (for 31P) as
references. Microanalyses were obtained from the Uni-
versity of Oviedo Analytical Service. FAB MS were
obtained from the University of Santiago de Compos-
tela Mass Spectrometric Service; data given refer to the
most abundant molecular ion isotopomer.
one metal atom to another [3Á6].
/

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233
4.2. Synthesis of [Ru3(m-H)2(m3-
HNNMe2)(C6H4PPh2)(PPh3)(CO)6] (4)
solid, subsequently identified by NMR (1H and 31P) as a
ca. 1.5:1:1.5 mixture of complexes 5, 6 and 7.
A solution of compound 1 (50 mg, 0.081 mmol) and
PPh3 (50 mg, 0.186 mmol) in THF (20 ml) was stirred at
reflux temperature for 3 h. The colour changed from
yellow to orange. The solvent was removed under
reduced pressure and the residue was washed with cold
4.4. Synthesis of [Ru3(m-H)2(m3-
HNNMe2)(PPh3)3(CO)6][BF4] (7)
PPh3 (59 mg, 0.227 mmol) was added to a solution of
compound 2 (50 mg, 0.071 mmol) in THF (30 ml). The
solution was stirred at reflux temperature for 1 h. The
solvent was removed under reduced pressure and the
(ꢁ
/
10 8C) C6H14 (2ꢄ5 ml) and dried in vacuo to give
/
complex 4 as an orange solid (64 mg, 73%). Anal.
Found: C, 49.64; H, 3.60; N, 2.41. Calc. for
C44H37N2O7P2Ru3: C, 49.43; H, 3.48; N, 2.62%. FAB
MS (m/z): 1072 [Mꢃ]. IR, n(CO) (CH2Cl2): 2027 (m),
oily residue was washed with cold (ꢁ
/
10 8C) Et2O (2ꢄ6
/
ml) and dried in vacuo to give complex 7 as a yellow
solid (66 mg, 66%). Anal. Found: C, 52.66; H, 3.95; N,
1.91. Calc. for C62H54BF4N2O6P3Ru3: C, 52.96; H, 3.87;
2008 (vs), 1976 (m), 1952 (s) cmꢁ1
.
N, 1.99%. FAB MS (m/z): 1320 [Mꢃꢁ
BF4]. IR, n(CO)
/
(CH2Cl2): 2051 (w), 2029 (vs), 1995 (m), 1968 (s) cmꢁ1
.
4.3. Reaction of compound 2 with two equivalents of
triphenylphosphane
4.5. Synthesis of [Ru3(m-H)(m3-HNNMe2)(m-
dppm)(CO)7] (8)
PPh3 (39 mg, 0.149 mmol) was added to a solution of
compound 2 (50 mg, 0.071 mmol) in THF (30 ml). The
solution was stirred at reflux temperature for 45 min. The
solvent was removed under reduced pressure and the oily
A solution of compound 1 (50 mg, 0.081 mmol) and
dppm (34 mg, 0.089 mmol) in THF (20 ml) was stirred
at reflux temperature for 30 min. The colour changed
residue was washed with C6H14 (2ꢄ5 ml) to give a yellow
/
Table 3
Crystal data and structure refinement details for compounds 7×C2H4Cl2 and 9
7×C2H4Cl2
9
Empirical formula
Formula weight
Temperature (K)
C62H54BF4N2O6P3Ru3×C2H4Cl2
1504.95
120(2)
C34H31BF4N2O7P2Ru3
1031.57
120(2)
˚
Radiation (l, A)
Crystal system
CuÁ
/
Ka (1.54180)
Orthorhombic
CuÁKa (1.54180)
Monoclinic
P21/n
/
Space group
˚
Pbna
a (A)
˚
13.7325(1)
23.4938(2)
17.3035(4)
12.7792(3)
17.5747(4)
90
b (A)
˚
c (A)
38.0230(3)
90
a (o)
b (o)
g (o)
90
90
91.491(1)
90
3
˚
V (A )
12267.3(1)
8
1.630
3884.9(1)
4
1.764
Z
Dcalc (g cmꢁ3
)
m (mmꢁ1
F(000)
Crystal size (mm)
)
7.996
6048
10.692
2032
0.28ꢄ0.15ꢄ0.13
0.15ꢄ0.10ꢄ0.08
u Limits (8)
Min/max
2.32Á
/
69.65
3.54Á68.47
05h 520, 05k 515, ꢁ215l 521
38 687
/
05h 516, 05k 528, 05l 546
89 372
Reflections collected
Unique reflections
11524 (Rintꢂ0.042)
9905
7132 (Rintꢂ0.053)
6120
Reflections with I ꢀ2s(I)
Absorption correction
Max/min transmission
Parameters, restraints
Final R1 (on F, I ꢀ2s(I))
Final wR2 (on F2, all data)
Goodness-of-fit on F2
RefDelF (XABS2
0.355/0.204
891, 12
)
RefDelF (XABS2
0.395/0.234
490, 0
)
0.0484
0.1874
0.0356
0.1143
1.067
ꢁ1.201/2.569
1.051
ꢁ0.736/1.767
ꢁ3
˚
Min/max residuals (e A
)

234
J.A. Cabeza et al. / Journal of Organometallic Chemistry 663 (2002) 227Á234
/
from yellow to orange. The solvent was removed under
reduced pressure and the residue was washed with
package was used throughout the structure determina-
tions [17]. A selection of crystal data and structure
refinement details are given in Table 3.
C6H14 (2ꢄ5 ml) and dried in vacuo to give complex 8
/
as an orange solid (57 mg, 75%). Anal. Found: C, 43.39;
H, 3.01; N, 2.94. Calc. for C34H28N2O7P2Ru3: C, 43.36;
H, 2.99; N, 2.97%. FAB MS (m/z): 943 [Mꢃ]. IR, n(CO)
(CH2Cl2): 2049 (s), 2032 (s), 1982 (vs), 1968 (s), 1945 (s),
5. Supplementary material
1917 (m), 1891 (w) cmꢁ1
.
Complete crystallographic data for the structural
analyses have been deposited with the Cambridge
Crystallographic Data Centre, CCDC nos. 187603 and
187604 for compounds 7 and 9, respectively. Copies of
this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge CB2
4.6. Synthesis of [Ru3(m-H)2(m3-HNNMe2)(m-
dppm)(CO)7][BF4] (9)
A drop of a solution of tetrafluoroboric acid (54% w/
w in Et2O) was added with a Pasteur pipette to a
solution of complex 8 (50 mg, 0.052 mmol) in CH2Cl2
(10 ml). The solvent was removed and the oily residue
was dissolved in Et2O (ca. 2 ml). Addition of C6H14 (5
ml) led to the precipitation of an orange solid, which
1EZ, UK (Fax: ꢃ44-1223-336033; e-mail: deposit@
/
ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
Acknowledgements
was filtered, washed with C6H14 (2ꢄ5 ml) and dried in
/
vacuo to give complex 9 as an orange solid (49 mg,
92%). Anal. Found: C, 39.69; H, 2.89; N, 2.71. Calc. for
C34H28BF4N2O7P2Ru3: C, 39.66; H, 2.84; N, 2.72%.
Financial support from the Spanish DGESIC (grants
PB98-1555 to J.A.C., and BQU2000-0219 to S.G.-G.) is
gratefully acknowledged.
FAB MS (m/z): 944 [Mꢃꢁ
/
BF4]. IR, n(CO) (CH2Cl2):
2080 (s), 2059 (m), 2020 (s), 1012 (s), 1962 (w) cmꢁ1
.
References
4.7. X-ray structure determinations of 7×
/
C2H4Cl2 and 9
[1] For reviews on general reactivity of triruthenium carbonyl
clusters, see: (a) M.I. Bruce, in: G. Wilkinson, F.G.A. Stone,
E.W. Abel (Eds.), Comprehensive Organometallic Chemistry, vol.
4, Pergamon, London, UK, 1982, p. 843;
Suitable crystals were obtained by slow diffusion of
hexanes into 1,2-dichloroethane (7) or CH2Cl2 (9)
solutions of the appropriate complexes. Diffraction
data were collected on a Nonius Kappa-CCD diffract-
ometer equipped with a 95 mm CCD camera on a k-
(b) M.I. Bruce, Coord. Chem. Rev. 76 (1987) 1;
(c) A.J. Deeming, in: E.W. Abel, F.G.A. Stone, G. Wilkinson,
D.F. Shriver, M.I. Bruce (Eds.), Comprehensive Organometallic
Chemistry II, vol. 7, Pergamon, London, UK, 1995, p. 683.
[2] J.A. Cabeza, I. del R´ıo, V. Riera, S. Garc´ıa-Granda, S.B. Sanni,
Organometallics 16 (1997) 3914.
goniostat, using graphite-monochromated CuÁKa ra-
/
diation. Data were reduced to Fo2 values. The structures
were solved by Patterson methods with DIRDIF-96 [12]
and refined with SHELX-97 [13] against F2 of all
reflections. Empirical absorption corrections were ap-
plied using XABS2 [14], with maximum and minimum
transmission factors of 0.355 and 0.204, respectively, for
[3] P.L. Andreu, J.A. Cabeza, V. Riera, C. Bois, Y. Jeannin, J. Chem.
Soc. Dalton Trans. (1990) 3347.
[4] P.L. Andreu, J.A. Cabeza, M.A. Pellinghelli, V. Riera, A.
Tiripicchio, Inorg. Chem. 30 (1991) 4611.
[5] P.L. Andreu, J.A. Cabeza, V. Riera, Inorg. Chim. Acta 186 (1991)
225.
7×
/
C2H4Cl2, and 0.395 and 0.234, respectively, for 9. All
[6] P.L. Andreu, J.A. Cabeza, J.L. Cuya´s, V. Riera, J. Organomet.
Chem. 427 (1992) 363.
non-H atoms were refined anisotropically. The hydride
H atoms of both complexes and the hydrogen atoms
[7] S. Alvarez, P. Briard, J.A. Cabeza, I. del R´ıo, J.M. Ferna´ndez-
Colinas, F. Mulla, L. Ouahab, V. Riera, Organometallics 13
(1994) 4360.
H(3a), H(3b), H(10), H(303) and H(603) of 7×
/C2H4Cl2
were located in the corresponding Fourier maps, and
were refined with free coordinates and thermal para-
meters. The hydrogen atom H(10) of complex 9 was
located and refined with a fixed thermal parameter. All
the remaining hydrogen atoms were geometrically
calculated and refined riding on their parent atoms.
[8] T. Jemke, H. Stoeckli-Evans, G. Suss-Fink, J. Organomet. Chem.
¨
391 (1990) 395.
[9] J.A. Cabeza, I. del R´ıo, S. Garc´ıa-Granda, L. Mart´ınez-Me´ndez,
V. Riera, Inorg. Chim. Acta, in press.
[10] (a) C.W. Bradford, R.S. Nyholm, G.J. Gainsford, J.M. Guss,
P.R. Ireland, R. Mason, Chem. Commun. (1972) 87;
(b) Y. Chi, H.F. Hsu, L.K. Liu, S.M. Peng, G.H. Lee,
Organometallics 11 (1992) 1763.
Two of the nine phenyl rings of 7×
/
C2H4Cl2 were found
disordered over two positions, with a 50% occupancy
[11] B. Hansert, H. Vahrenkamp, Chem. Ber. 126 (1993) 2017.
[12] P.T. Beurskens, G. Beurskens, W.P. Bosman, R. de Gelder, S.
Garc´ıa-Granda, R.O. Gould, R. Israel, J.M.M. Smits, The
¨
each. For 7×
/
C2H4Cl2, both the solvent molecule and the
[BF4]ꢁ anion were disordered and were treated with a
mixture of constraints and restraints as described else-
where [15]. Drawings and structure calculations were
performed with PLATON [16]. The WINGX program
DIRDIF-96 Program System, Crystallography Laboratory, Uni-
versity of Nijmegen, The Netherlands, 1996.
[13] G.M. Sheldrick, SHELXL-97, version 97-2, University of Gottin-
¨
gen, Germany, 1997.