Decorating step-by-step and independently the surface and the core of dendrons

Article abstract of DOI:10.1016/j.jorganchem.2007.01.001

Dendrons possessing one activated vinyl group at the core and several chlorine atoms at the end of the branches are used as starting materials to study the possibility to react independently the surface functions and the core function. In particular, the most powerful sequence of reactions for decorating them by organometallic complexes as end groups and amine or alcohol at the core has been determined. In the first step, phenol phosphines are grafted as end groups of the dendrons, and they can be used for the complexation of metals. However, these phosphines must be kept free when amines are used to react with the vinyl core in the next step. Depending on the type of phosphine end groups and on the type of function of the core (amine or alcohol), the complexation of ruthenium ([RuCl₂(p-cymene)]₂) and rhodium ([RhCl(COD)]₂) derivatives by the phosphine end groups can occur without side reaction at the core.

Full text of DOI:10.1016/j.jorganchem.2007.01.001

Journal of Organometallic Chemistry 692 (2007) 1928–1939
www.elsevier.com/locate/jorganchem
Decorating step-by-step and independently the surface
and the core of dendrons
a,b
a
a
a
a
Inma Angurell , C e´ dric-Olivier Turrin , R e´ gis Laurent , Val e´ rie Maraval , Paul Servin ,
b,
b
a,
a,
*
Oriol Rossell , Miquel Seco , Anne-Marie Caminade *, Jean-Pierre Majoral
*
a
Laboratoire de Chimie de Coordination du CNRS, 205 Route de Narbonne, 31077 Toulouse Cedex 4, France
Departament de Qu ı´ mica Inorg a` nica, Universitat de Barcelona, Mart ı´ i Franqu e` s 1-11, 08028 Barcelona, Spain
b
Received 27 November 2006; received in revised form 4 January 2007; accepted 5 January 2007
Available online 13 January 2007
Abstract
Dendrons possessing one activated vinyl group at the core and several chlorine atoms at the end of the branches are used as starting
materials to study the possibility to react independently the surface functions and the core function. In particular, the most powerful
sequence of reactions for decorating them by organometallic complexes as end groups and amine or alcohol at the core has been deter-
mined. In the first step, phenol phosphines are grafted as end groups of the dendrons, and they can be used for the complexation of
metals. However, these phosphines must be kept free when amines are used to react with the vinyl core in the next step. Depending
on the type of phosphine end groups and on the type of function of the core (amine or alcohol), the complexation of ruthenium
(
[RuCl (p-cymene)] ) and rhodium ([RhCl(COD)] ) derivatives by the phosphine end groups can occur without side reaction at the core.
2 2 2
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Dendrons; Dendrimers; Phosphines; Complexes; Ruthenium; Rhodium
1
. Introduction
function located at the core for dendrons built by a diver-
gent process must be insensitive to the conditions used for
the growing [5]. Furthermore, this/these ‘‘non reactive’’
functional group(s) must be able to react after the synthesis
of the dendron.
Dendrons [1] also called dendritic wedges [2], are nano-
metric trees constituted of numerous branches linked to a
trunk (the core). Compared to dendrimers [3,4], this versa-
tile class of dendritic molecules possesses the advantage to
have functional groups (generally different) both at the
level of the core and at the end of the branches. Such fea-
ture is particularly interesting to elaborate special and com-
plex dendritic architectures [5–7]. However, this advantage
is often more theoretical than practical, due to the necessity
for one type of these functions to be non reactive during
the synthetic process; either the functions located at the
surface for dendrons built by a convergent process, or the
We have already described the synthesis of phosphorus-
containing dendrons possessing an activated vinyl group at
the core [8], and we have shown that this vinyl group can
easily react with primary and secondary amines, provide
the end groups are poorly reactive functions, such as a
nitrile or an aromatic tertiary amine [9]. The sole example
in this series in which the core and the surface react is when
the end groups are aldehydes; in this case, both functions
react with hydrazines, thus they are not useful because they
finally afford the same type of functions at both levels [8].
We report here the original strategy to react independently
the functions located on the surface and the function
located at the core of dendrons, and the possibility to graft
new functional and reactive groups by this way.
*
Corresponding authors. Tel.: +33 561 33 3125; fax: +33 561 55 3003
(A.-M. Caminade, J.-P. Majoral).
E-mail addresses: oriol.rossell@qi.ub.es (O. Rossell), caminade@
lcc-toulouse.fr (A.-M. Caminade), majoral@lcc-toulouse.fr (J.-P. Majoral).
0
022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.01.001

I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
1929
2
. Results and discussion
Amongst the various areas of researches about dendritic
molecules, one of the most active concerns organometallic
chemistry [10,11], often carried out with the aim of using
the resulting complexes as catalysts [10–16]. We reasoned
that dendrons possessing organometallic derivatives as
end groups and one reactive functional group at the core
would be valuable targets. One of the easiest way to obtain
metallic complexes consists in using phosphines, thus our
first aim was to graft phosphines as end groups of den-
drons. For this purpose, we synthesized first a series of phe-
nol phosphines 1a-d; the OH group was chosen to allow the
Scheme 2.
grafting on the P(S)Cl end groups of dendrons. The syn-
2
thesis of the monophosphine 1a was previously described
[
17]; monophosphine 1b and diphosphines 1c and 1d are
synthesized by Mannich-type reaction between
Ph PCH OH, generated in situ from Ph PH and parafor-
noted that in the three cases, the presence of phenol is com-
patible with the presence of Cl on the metal.
a
However, we did not succeed when trying to graft these
2
2
2
maldehyde, and NH or NH functions of phenols 2b, 2c
complexes in basic conditions on the P(S)Cl end groups of
2
2
and 2d (Scheme 1).
the first generation dendron G , which possesses four chlo-
1
The complexation ability of the monophosphines, con-
sidered as model compounds, was tested in order to deter-
mine the most convenient conditions of reactions and the
influence of the complexation on the NMR spectra. We
choose ruthenium and rhodium as metals to be complexed,
in view of their known ability to generate active catalytic
species [18]. In all cases, 1/2 equivalent of the metallic
dimer [RuCl (p-cymene)] or [RhCl(cod)] per phosphine
rine on the surface and one activated vinyl group at the
core [8]. This dendron will be our starting material for test-
ing the possibility to decorate independently and succes-
sively the surface and the core with other functional
groups. We have already shown that the vinyl group at
the core is able to undergo the addition of primary or sec-
ondary amines [8], but this reaction is not compatible with
the presence of the P(S)Cl end groups, which also react
2
2
2
2
3
1
is used (Scheme 2). Obviously, P NMR is the most infor-
mative tool to ascertain the complexation; an important
deshielding of the signal corresponding to the phosphine
easily with amines [19,20]. Thus, the first step to decorate
this dendron must concern the reactivity of the end groups.
The grafting of the free phosphines 1a-d as end groups
of dendron G1 was successfully attempted, using their
sodium salts generated by reaction with NaH. The reac-
tions proceed completely overnight for the monophos-
phines 1a and 1b, and after one day for the diphosphine
3
1
is observed upon complexation (Dd P = +24 ppm for
1
a ! 3a; +38 ppm for 1a ! 4a; +42 ppm for 1b ! 3b).
In the case of complex 4a, a doublet with a characteristic
1
JPRh coupling constant (149 Hz) is observed. It must be
1
c, to afford dendrons 5a-G , 5b-G , and 5c-G , respec-
1 1 1
3
1
tively (Scheme 3). Monitoring these reactions by
P
NMR shows first the disappearance of the signal corre-
3
1
sponding to the P(S)Cl end groups (d P = 63.5 ppm) on
2
behalf of the appearance of a new singlet corresponding
to the monosubstitution (P(S)ClOAr), for instance at
3
1
d P = 72.3 ppm for the reaction with 1c. This intermediate
signal totally disappears when the substitution is complete,
as shown by the appearance of a singlet at 66 ppm for the
P(S)(OAr) groups. Obviously the signal of the mono- or
2
3
1
di-phosphine end groups is also detected (d P = ꢀ3.1
ppm for 5a-G , ꢀ19.7 for 5b-G , ꢀ25.1 for 5c-G ), as well
1
1
1
as two doublets corresponding to the P@NAP@S linkage.
3
1
P NMR ascertains the purity of these dendrons with a
precision better than 1%, but it also showed that the reac-
tion between 1d and G did not afford a pure compound.
1
The signals corresponding to the expected 5d-G dendron
1
3
1
are observed (two doublets at d P = 15.1 and 56.3 ppm
with J = 32 Hz for the P@NAP@S linkage of the core,
2
PP
and two singlets at 65.4 and ꢀ22.7 ppm for the P(S) and
phosphine terminal groups, respectively). However, den-
Scheme 1.
dron 5d-G is accompanied by impurities impossible to
1

1930
I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
Scheme 3.
eliminate, which might be due to the presence of a N–H
bond (absent in all the other compounds), thus no more
attempt to use diphosphine 1d was carried out. On the
other hand, in order to demonstrate that the grafting of
phosphines is not limited to the first generation dendron,
the sodium salt of 1a was also reacted with the second gen-
complexes 6a-G and 6b-G , respectively (Scheme 4). The
1 1
important deshielding effect observed upon complexation
3
1
(Dd P = +30 ppm for 5a ! 6a; + 49 ppm for 5b ! 6b)
is comparable to that observed for the model complexes
3a and 3b. It must be noted that no reaction occurs at
the level of the core, despite the presence of the vinyl group,
3
1
eration dendron G (Scheme 3). The expected dendron 5a-
as shown both by P NMR (no change for the proximate
2
1
G bearing 8 phosphine end groups is easily isolated and
2
P@NAP@S linkage) and by H NMR (no change for the
characterized as previously by multinucleus NMR, and
particularly by P NMR. The P NMR spectrum displays
vinyl group). We also attempted to react 4 equivalents
3
1
31
of [RuCl (p-cymene)] with one equivalent of dendron
2
2
3
1
exclusively the expected signals (two doublets at 14.0 and
5c-G , but the P NMR spectrum demonstrates that the
1
2
5
6.5 ppm with J = 31.9 Hz for the P@NAP@S linkage
complexation did not occur cleanly, presumably due to
the difficulty to accommodate two metallic fragments in
close proximity [21].
PP
of the core, and 3 singlets at ꢀ2.9 for the phosphine end
groups, 65.2 for the P(S) groups of the second layer, and
6
5.9 for the P(S) groups of the first layer).
Starting from the dendron complexes 6a-G and 6b-G ,
1
1
Having in hand this series of dendrons functionalized by
we attempted to react ethylenediamine to their vinyl core,
in order to have a primary amine, which is a highly versa-
tile function. We have already shown that primary and sec-
ondary amines react by Michael-type additions to activated
vinyl groups [8,9]; however, when the reaction is carried
out with a diamine, a large excess of diamine must be used
in order to avoid the connection of two dendrons together.
The use of such excess has no consequence when the end
an activated vinyl group at the core and decorated by 4 or 8
phosphines as end groups, we decided to study the reactiv-
ity of both sites. In a first attempt, we decided to use again
the reactivity of the surface, and in particular to complex
ruthenium derivatives. The reaction of two equivalents of
[
RuCl (p-cymene)] with one equivalent of dendrons 5a-
2 2
G and 5b-G occurs easily to afford the expected dendron
1
1
Scheme 4.

I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
1931
groups are non reactive, but in the case of 6a-G and 6b-G ,
properties of the dendrons shown in Scheme 5. For this
1
1
we observed a degradation of the dendrons, presumably
due both to a partial reaction of Ru–Cl with the diamines
and the leaching of the metal (the signal of free phosphine
is detected). Thus we decided to carry out the reactions at
the level of the core before the complexation by the phos-
phine end groups.
purpose, we tried to react [RuCl (p-cymene)] with den-
2
2
drons 7a-G and 7b-G . In the case of 7a-G , besides the
1
1
1
reactivity of the surface, we observed a parallel reaction
at the level of core. Both phenomena are easily detected
3
1
by P NMR. On one side, the spectrum displays the pres-
ence of free phosphine (d = ꢀ3 ppm) together with the
complex (d = 28 ppm), which induces the occurrence of
several singlets for the P(S) group of the first generation;
on the other side, an important broadening of both signals
of the P@NAP@S linkage indicates that ruthenium is also
presumably complexed at the core. In contrast, the reaction
A ten-fold excess of ethylenediamine was reacted with
dendrons 5a-G and 5b-G . The completion of the reaction
1
1
3
1
is first shown by P NMR, which displays an important
deshielding of the signal corresponding to the Ph P@N
2
group, from 14 ppm for 5a-G and 5b-G to 21 ppm for
1
1
1
7
a-G and 7b-G . It is also shown by H NMR, with the
with 7b-G occurs rapidly and cleanly, to afford dendron
1
1
1
3
1
disappearance of the signals corresponding to the vinyl
group. Furthermore, the presence of 4 different signals
9b-G1 (Scheme 6). P NMR ascertains both the com-
pletion of the complexation by the phosphine end groups
(d = 29.1 ppm) and the absence of reaction at the core.
We can presume that the higher reactivity of the diph-
enylphosphino groups of 7b-G1 compared to the trip-
1
3
for the CH groups in the C NMR spectrum indicates a
2
non symmetrical structure, corresponding to the reaction
of only one side of ethylene diamine. Indeed, the reaction
of both sides would give a symmetrical structure and only
henylphosphino groups of 7a-G explains the absence of
1
1
3
three signals for this fragment in the C NMR spectrum.
the side reaction at the core of 7b-G1.
Thus dendrons 7a-G and 7b-G possess both a primary
and a secondary amine at the core (Scheme 5). We have
also carried out addition reactions on the second genera-
In view of the problems encountered for the complexa-
tion, we decided to avoid the presence of the
NH CH CH NH linkage at the core, which might act as
1
1
2
2
2
tion dendron 5a-G with another functionalized primary
amine, aminopentanol. This reaction affords dendron 8a-
a chelate ligand towards the metal or substitute the chlo-
rides, and to use the rhodium derivative, which contains
only one Cl instead of two for the ruthenium derivative.
We tried to react [RhCl(cod)] with dendron 8a-G ; this
2
G possessing both an alcohol and a secondary amine at
2
the core (Scheme 5). The addition reaction induces the
expected deshielding of the signal corresponding to
2
2
reaction successfully afforded the expected complex 10a-
3
1
31
Ph P@N in P NMR. It must be noted that the alcohol
G after two hours at room temperature (Scheme 7).
2
P
2
part of aminopentanol does not react with the vinyl group.
After the reactivity of the end groups illustrated by the
grafting of phosphines, followed by the reactivity at the
core, with the addition of various functionalized primary
amines, we decided in the next step to move back to the
reactivity of the end groups, by studying the complexation
NMR ascertains the complete reaction of phosphines with
1
rhodium (d = 33.5 ppm, J
= 151 Hz), whereas the sig-
PRh
nals of the core remain unchanged.
3
1
The prominent role played by P NMR for the charac-
terization of these dendrons has been emphasized all along
this paper, and is demonstrated in Fig. 1. Indeed, all signals
Scheme 5.
Scheme 6.

1932
I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
Scheme 7.
corresponding to all types of phosphorus atoms are easily
distinguishable, as shown for the second generation den-
catalytically active metal complexes could lead to catalysts
possessing both the advantages of heterogeneous and
homogeneous catalysis. Furthermore, it must be empha-
sized that such methodology is not limited to the decora-
tion by metal complexes, and that numerous other fields
can benefit from this work, such as fluorescence, biology,
or nanomaterials [22] to name as a few.
drons a-G . Each reaction induces a clear shift of the signal
2
of the phosphorus atoms close to the place where the reac-
tion occurs. The dotted arrows show the deshielding of the
doublet corresponding to the core when the aminoalcohol
is added to the vinyl group of 5a-G (Figs. 1a and b),
2
and the deshielding of the singlet corresponding to the
phosphine end groups upon complexation of rhodium
4. Experimental
(
Fig. 1b and c).
4.1. General
3
. Conclusion
All manipulations were carried out with standard high
Starting from dendrons possessing one activated vinyl
vacuum and dry-argon techniques, due to the sensitivity
of phosphines towards oxidation. The solvents were freshly
dried and distilled (THF and ether over sodium/benzophe-
none, pentane and CH Cl over phosphorus pentoxide, tol-
uene over sodium). H, C, P NMR spectra were
recorded with Bruker AC 200, AC 250, DPX 300 or
AMX 400 spectrometers. References for NMR chemical
group at the core and 4 or 8 chlorine atoms on the surface,
we have determined the most powerful sequence of reac-
tions for decorating them by organometallic complexes.
The first step concerns the grafting of phenol phosphines
as end groups of the dendrons. These phosphines can be
used for the complexation of metals; however such com-
plexation precludes the use of amines to react with the core
in the next step. Thus, the phosphines must be kept free
when adding a primary diamine or an amino alcohol to
the vinyl core. Depending on the type of phosphine end
groups and on the type of function grafted to the core,
we were able to complex ruthenium and rhodium deriva-
tives by the end groups, without side reaction at the core.
Thus, we have shown ways to decorate step by step both
the extremities of the branches and the ‘‘root’’ (the core) of
these molecular ‘‘Christmas trees’’-like. For the particular
cases shown in this paper, the presence of amines or alco-
hols at the core could be useful for linking these functional
dendrons to materials, whereas the presence of potentially
2
1
2
13
31
3
1
1
shifts are 85% H PO for P NMR, SiMe for H and
3
4
4
1
3
13
C NMR. The attribution of C NMR signals has been
done using Jmod, two dimensional HMBC, and HMQC,
Broad Band or CW P decoupling experiments when nec-
essary. The numbering used for NMR assignments is
depicted in Fig. 2. The synthesis of compounds 1a [17],
G and G [8] was already described.
3
1
1
2
4.2. Synthesis of 2b
A mixture of 4-hydroxybenzaldehyde (4.0 g, 32 mmol),
and methylhydrazine (6.5 ml, 120 mmol) in absolute etha-
nol (50 ml) was refluxed for 5 h. After evaporation under

I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
1933
31
Fig. 1. P NMR spectra (81 MHz, CDCl
3
) of dendrons 5a-G
2
(a), 8a-G
2
2
(b), and 10a-G (c).
3
3
vacuum, the residue was crystallized in hot ethyl actetate.
(d, J = 8.7 Hz, 2H, H–C ), 7.50 (s, 1H, CH@N), 8.45
HH
1
3
1
Compound 2b was isolated as a white powder in 81% yield.
(br s, 1H, OH) ppm. C { H} NMR (CD COCD ): d
37.5 (s, CH ), 118.5 (s, C ), 130.2 (s, C ), 132.4 (s, C ),
137.5 (s, CH@N), 160.5 (s, C ) ppm. Anal. Calcd for
3 3
1
2
3
4
2
b. H NMR (CD COCD ): d 2.87 (s, 3H, CH ), 6.28
3
3
3
2
3
3
1
(
br s, 1H, HN), 6.81 (d, JHH = 8.7 Hz, 2H, H–C ), 7.42

1934
I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
Fig. 2. Numbering used for NMR assignments.
1
3
C H N O (150.2): C, 63.98; H, 6.71; N, 18.65. Found: C,
{ H} NMR (CDCl ): d 32.4 (s, NCH CH ), 58.7 (t, J
=
8
10
2
3
2
2
CP
3
1
6
4.07; H, 6.75; N, 18.58%.
9.1 Hz, CH ), 59.2 (dd,
J
= 6.0 Hz,
J
CP
m
= 9.1 Hz,
2
CP
3
2
CH P), 115.8 (s, C ), 128.9 (d, J = 6.8 Hz, C ), 129.0 (s,
2
CP
p
3
4
2
4
.3. Synthesis of phosphine 1b
C ), 130.3 (s, C ), 132.1 (s, C ), 133.7 (d, J = 18.3 Hz,
CP
C ), 138.6 (d, J = 12.7 Hz, C ), 154.7 (s, C ) ppm.
CP
o
1
i
1
A mixture of Ph PH (3.5 ml, 20 mmol) and paraformal-
2
dehyde (0.59 g, 19 mmol), was heated neat in a closed
Schlenck tube at 120 °C for 4 h. After cooling to room tem-
perature, THF was added, and the resulting solution was
added via canula to compound 2b (2.64 g, 18 mmol). The
solution was evaporated to dryness and the resulting vis-
cous syrup was heated overnight at 85 °C, then it was
heated at 60 °C under vacuum to eliminate water. The res-
idue was dissolved in a minimum amount of a mixture
4.5. Synthesis of 2d
Hydrazine hydrate (10 ml) was added to a solution of 4-
hydroxybenzaldehyde (2.0 g, 13.1 mmol) in THF (10 ml).
The solution was stirred for 12 h at room temperature, then
allowed to decant. The superior liquid phase was elimi-
nated and the inferior viscous phase was washed with
diethylether to obtain compound 2d as a white powder in
78% yield.
CHCl /pentane (1:1); then a powder deposited with time.
3
1
3
This powder was washed with the same mixture of solvents,
2d. H NMR (DMSO d ): d 6.77 (d, J = 8.1 Hz, 2H,
6 HH
3
13
1
to afford 1b as a white powder in 38% yield.
C H ), 7.68 (d, JHH = 8.1 Hz, 2H, C H ) ppm. C { H}
6 4 6 4
3
1
1
1
2
4
1
b. P { H} NMR (CDCl ): d ꢀ19.8 (s, PPh ) ppm. H
NMR (DMSO d ): d 115.7 (s, C ), 124.8 (s, C ), 129.7 (s,
6
3
2
2
3
1
NMR (CDCl ): d 2.95 (s, 3H, CH ), 4.17 (d, J = 2.7 Hz,
H, CH ), 5.05 (br s, 1H, OH), 6.72 (d, J = 8.7 Hz, 2H,
H–C ), 7.20 (s, 1H, CH@N), 7.27 (d, J = 8.7 Hz, 2H,
H–C ), 7.3 (m, 6H, Ph), 7.5 (m, 4H, Ph) ppm. C { H}
C ), 160.9 (s, C ), 166.8 (s, C@O) ppm. Anal. Calcd for
3
3
HP
3
2
C H N O (152.15): C, 55.26; H, 5.30; N, 18.41. Found:
2
HH
7
8
2
2
2
3
C, 55.29; H, 5.31; N, 18.40%.
HH
3
13
1
3
NMR (CDCl ): d 39.2 (d, J = 7.7 Hz, CH ), 61.3 (d,
4.6. Synthesis of phosphine 1d
3
CP
3
1
2
3
JCP = 10.3 Hz, CH ), 115.3 (s, C ), 127.2 (s, C ), 128.4
2
m
3
p
4
(
d, J = 6.4 Hz, C ), 128.6 (s, C ), 129.7 (s, C ), 133.0
A mixture of Ph PH (29 mmol) and paraformaldehyde
CP
2
2
o
(
s, CH@N), 133.2 (d, JCP = 18.3 Hz, C ), 137.9 (d,
(0.89 g, 28 mmol), was heated neat in a closed Schlenck
tube at 120 °C for 4 h. After cooling to room temperature,
THF was added, and the resulting solution was added via
canula to compound 2d (2.0 g, 13 mmol). The mixture was
evaporated to dryness and heated at 85 °C for 12 h, then
heated at 60 °C under vacuum to eliminate water. The res-
idue was washed with diethylether to afford 1d as a white
powder in 75% yield.
1
i
1
JCP = 13.5 Hz, C ), 155.1 (s, C ) ppm.
4
.4. Synthesis of phosphine 1c
A mixture of Ph PH (1.4 ml, 8 mmol) and paraformal-
2
dehyde (230 mg, 7.4 mmol) was heated neat in a closed
Schlenck tube at 120 °C for 4 h. After cooling to room tem-
perature, the reaction mixture was diluted with THF (2 ml)
and added via canula to tyramine (500 mg, 3.64 mmol).
The reaction mixture was degassed (freeze–thaw–pump)
and heated at 85 °C overnight. The crude mixture was
heated at 60 °C under vacuum to remove the volatiles.
The residue was dissolved in the minimum amount of
3
1
1
1
1d P { H} NMR (CDCl ): d ꢀ22.9 (s, PPh ) ppm. H
3
2
NMR (CDCl ): d 4.15 (s, 4H, CH P), 6.78 (br s, 2H,
3
2
C H ), 7.25–7.75 (m, 22H, C H , C H ), 8.39 (br s, 1H,
6
4
6
4
6
5
1
3
1
OH) ppm.
C { H} NMR (CDCl ): d 60.4 (dd,
3
3
1
2
JCP = 6.0 Hz, J = 9.0 Hz, CH P), 115.6 (s, C ), 124.1
(s, C ), 128.5 (d, J = 6.8 Hz, C ), 128.8 (s, C ), 128.9
(s, C ), 133.0 (d, JCP = 19.0 Hz, C ), 137.0 (d,
JCP = 11.8 Hz, C ), 160.3 (s, C ), 167.3 (s, C@O) ppm.
CP
3
2
m
4
p
CP
3
2
o
CHCl and precipitated with a mixture of pentane and
3
1
i
1
ether (1:1). The resulting powder was subjected twice to
the same treatment to afford 1c as a white powder.
3
1
1
1
c. 45% yield. P { H} NMR (CDCl ): d ꢀ24.9 (s, PPh )
4.7. Synthesis of complex 3a
3
3
2
1
ppm. H NMR (CDCl ): d 2.72 (t, J = 8.1 Hz, 2H,
NCH CH ), 3.22 (t, J = 8.1 Hz, 2H, NCH CH ), 3.78
br d, J = 1.8 Hz, 4H, CH P), 6.5 (br s, 1H, OH), 6.80
d, JHH = 8.1 Hz, 2H, H–C ), 6.94 (d, JHH = 8.1 Hz,
3
HH
3
[RuCl (p-cymene)] (67 mg, 0.11 mmol) was added to a
2
2
HH
2
2
2
2
2
(
(
2
solution of 1a (61 mg, 0.22 mmol) in THF (8 ml). The
resulting mixture was stirred for 1 h at room temperature,
then evaporated to dryness. The residue was washed with
HP
2
2
3
3
3
13
H, H–C ), 7.4 (m, 6H, Ph), 7.5 (m, 4H, Ph) ppm.
C

I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
1935
3
1
1
diethyl ether. Complex 3a was isolated as an orange pow-
4a
P
{ H} NMR (DMSO d6):
d
32.5 (d,
1
1
der in 89% yield.
JPRh = 149.0 Hz, Ph PRh). H NMR (DMSO d ): d 1.9
(br s, 4H, CH ), 2.3 (br s, 4H, CH ), 3.0 (br s, 2H,
2 2
CH@CH), 5.3 (br s, 2H, CH@CH), 6.85 (d, J = 7.2 Hz,
2H, C H ), 7.30–7.70 (m, 12H, C H , C H ). C { H}
6 4 6 5 6 4
2
6
3
1
1
1
3
a
P { H} NMR (DMSO d ): d 18.7 (s, Ph PRu). H
6
2
3
3
NMR (DMSO d ): d 0.92 (d, JHH = 6.9 Hz, 6H,
6
HH
3
13 1
CH(CH ) ), 1.73 (s, 3H, CH ), 2.51 (sept., J = 6.9 Hz,
3
2
3
HH
3
1
H, CH(CH ) ), 5.18 (d, J = 5.9 Hz, 2H, CHArCymene),
NMR (DMSO d ): d 28.3 and 32.4 (2 br s, CH ), 70.1
6 2
3
2
HH
3
3
5
.27 (d, JHH = 5.9 Hz, 2H, CHArCymene), 6.76 (d,
and 103.8 (2 br s, CH@CH), 115.2 (d, J = 10.8 Hz,
CP
3
2 1 4 3
JHH = 7.3 Hz, 2H, C H ), 7.35 (m, 6H, C H ), 7.55 (m,
C ), 119.0 (d, J = 47.8 Hz, C ), 127.9 (d, J = 9.8 Hz,
CP CP
6
4
6
5
m
p
1
i
2
H, C H ), 7.69 (m, 4H, C H ), 9.96 (s, 1H, OH) ppm.
C ), 130.0 (s, C ), 131.9 (d, J = 42.1 Hz, C ), 133.9 (d,
CP
JCP = 11.1 Hz, C ), 136.7 (d, J = 13.1 Hz, C ), 159.4
CP
(s, C ) ppm. Anal. Calcd for C H OPClRh (524.8): C,
6
1
4
6
5
1
3
2
o
2
3
C { H} NMR (DMSO d ): d 19.5 (s, CH ), 23.7 (s,
6
3
1
CH(CH ) ), 32.1 (s, CH(CH ) ), 89.0 (d, J = 5.6 Hz,
3
2
3 2
CP
26 27
CHArCymene), 91.7 (d, JCP = 3.5 Hz, CHArCymene), 97.4 (s,
CH C ), 110.7 (s, (CH ) CHC ), 117.2 (d,
59.50; H, 5.19. Found: C, 59.51; H, 5.21%.
3
ArCymene
3 2
1
ArCymene
3
2
4
JCP = 10.8 Hz, C ), 124.6 (d, JCP = 50 Hz, C ), 130.0
4.10. Synthesis of dendron 5a-G1
3
m
p
(
d,
J
= 9.6 Hz, C ), 132.2 (s, C ), 136.2 (d,
CP
2
o
1
i
JCP = 9.2 Hz, C ), 137.2 (d, J = 83 Hz, C ), 138.3 (d,
JCP = 10.9 Hz, C ), 161.6 (s, C ) ppm. Anal. Calcd for
A solution of compound 1a (390 mg, 1.40 mmol) in
THF (20 ml) was added to sodium hydride (33 mg,
1.40 mmol). The resulting suspension was stirred at room
temperature until it became a solution then 240 mg
CP
1
2
3
C H OPCl Ru (584.5): C, 57.54; H, 5.00. Found: C,
2
8
29
2
5
7.58; H, 4.98%.
(
0.28 mmol) of G were added. The resulting mixture was
1
4
.8. Synthesis of complex 3b
stirred overnight at room temperature, then centrifuged
and evaporated to dryness. The resulting powder was
[
RuCl (p-cymene)] (74 mg, 0.12 mmol) was added to a
washed thrice with THF/pentane (1/5) to afford 5a-G as
2
2
1
solution of 1b (84 mg, 0.24 mmol) in CH Cl (10 ml). The
a white powder in 92% yield.
2
2
3
1
1
0
1
resulting mixture was stirred for 1 h at room temperature,
then evaporated to dryness. The residue was washed with
diethyl ether. Complex 3b was isolated as an orange pow-
der in 91% yield.
5a-G1: P { H} NMR (CDCl ): d ꢀ3.1 (s, P ), 14.9 (d,
3
2
0
2
JPP = 30.0 Hz, P ), 56.2 (d, J = 30.0 Hz, P ), 65.2 (s,
0
PP
0
1
3
P ) ppm. H NMR (CDCl ): d 3.37 (d, J = 11.0 Hz,
1
3
HP
3
3
6H, N–CH ), 6.12 (ddd, J = 24.1 Hz, J
= 18.3 Hz,
3
HP
HHa
3
3
1
1
2
3
2
3
b
P { H} NMR (DMSO d ): d 22.4 (s, Ph PRu), ppm.
JHH = 1.1 Hz, 1H, H ), 6.41 (ddd, JHP = 46.0 Hz,
6
2
c
1
3
2
H NMR (DMSO d ): d 0.73 (d, JHH = 6.8 Hz, 6H,
JHHa = 12.5 Hz, JHH = 1.1 Hz, 1H, H ), 6.8 (dddd,
6
b
3
3
4
CH(CH ) ), 1.77 (s, 3H, CH ), 2.06 (s, 3H, CH NCH ),
JHP = 25.3 Hz, J
= 18.3 Hz, J
= 12.5 Hz, J
=
3
2
3
3
2
HHc
HHb
HP
3
2
2
5
.26 (sept., JHH = 6.8 Hz, 1H, CH(CH ) ), 4.61 (br s,
1.1 Hz, 1H, H ), 7.2–7.9 (m, 76H, H , CH@N) ppm.
3 2
a
13 1 2
Ar
3
H, CH P), 5.23 (d, JHH = 5.8 Hz, 2H, CHArCymene),
C { H} NMR (CDCl ): d 32.8 (d, J = 13.0 Hz, N–
3 CP
2
3
3
2
3
.45 (d, JHH = 5.8 Hz, 2H, CHArCymene), 6.57 (d,
CH ), 121.4 (d, J = 5 Hz, C ), 121.9 (d, J = 5 Hz,
1
3 CP CP
3
2
1
3
i
JHH = 8.0 Hz, 2H, C H ), 6.65 (s, 1H, CH@N), 6.97 (d,
C ), 127.7 (dd, J = 91.0 Hz, J = 4.5 Hz, C ), 127.9
0 0
CP CP
6
4
3
3
3
m
1
JHH = 8.0 Hz, 2H, C H ), 7.45 (m, 6H, C H ), 7.88 (m,
(s, C ), 128.4 (d, JCP = 7.0 Hz, C ), 128.6 (d,
JCP = 13.0 Hz, C ), 128.8 (s, C ), 130.3 (s, C ), 132.0 (d,
1
0 0
JCP = 11.0 Hz, C ), 132.6 (d, J = 2.3 Hz, C ), 133.0
0
CP
0
(d, JCP = 10.1 Hz, C ), 133.5 (d, JCP = 19.5 Hz, C ),
1 1
6
4
6
5
0
1
3
1
3
m
p
4
4
H, C H ), 9.34 (s, 1H, OH) ppm. C { H} NMR (DMSO
6
5
2
o
4
p
d ): d 19.4 (s, CH ), 23.6 (s, CH(CH ) ), 31.9 (s,
6
3
3 2
1
1
4
2
o
CH(CH ) ), 39.6 (s, CH NCH ), 56.7 (d, J = 23.0 Hz,
CH P), 88.5 (br s, CH
3
2
3
2
CP
2
2
3
1
), 91.6 (d, J = 5.0 Hz,
135.0 (d, J = 20.5 Hz, C ), 136.6 (d, J = 10.5 Hz,
1
CP CP
2
ArCymene
CP
i
1
3
CHArCymene), 96.8 (s, CH CArCymene), 110.6 (s,
C ), 136.7 (s, CH @), 140.1 (d,
J
CP
= 13.7 Hz, CH@
3
2
3
2
2
1
2
(
(
CH ) CHC
), 117.2 (d, J = 10 Hz, C ), 128.0
NNP ), 150.8 (d, JCP = 8.0 Hz, C ), 153.1 (d, JCP
10.5 Hz, C ) ppm. Anal. Calcd for C H N O P S
0
102 85 5 6 8 3
=
3
3
2
ArCy mene
3
CP
1
1
m
p
1
s, C ), 130.0 (d, J = 9 Hz, C ), 132.0 (s, C ), 132.1 (s,
CP
4
1
o
C ), 136.0 (d, J = 9.0 Hz, C ), 136.2 (s, CH@N), 136.7
d, JCP = 83.0 Hz, C ), 149.1 (d, JCP = 7.3 Hz, C ),
1
61.1 (s, C ) ppm. Anal. Calcd for C H N OPCl Ru
31 35 2 2
(1821): C, 67.29; H, 4.71; N, 3.85. Found: C, 67.12; H,
4.63; N, 3.80%.
CP
1
i
2
1
(
1
1
(
654.6): C, 56.88; H, 5.39; N, 4.28. Found: C, 56.93; H,
4.11. Synthesis of dendron 5a-G2
3
.43; N, 4.25%.
A solution of compound 1a (420 mg, 1.51 mmol) in
4
.9. Synthesis of complex 4a
THF (20 ml) was added to sodium hydride (37 mg,
1.51 mmol). The resulting suspension was stirred for
[
RhCl(cod)] (45 mg, 0.090 mmol) was added to a solu-
30 min at room temperature to afford a solution, which
2
tion of 1a (50 mg, 0.180 mmol) in CH Cl (10 ml). A yellow
was added to 300 mg (0.167 mmol) of G . The resulting
2
2
2
precipitate appeared after a few minutes, but the mixture
was stirred for 1 h at room temperature. After filtration
the precipitate was recovered and washed with CH Cl .
mixture was stirred overnight at room temperature, then
centrifuged and evaporated to dryness. The resulting pow-
der was washed 3 times with THF/pentane (1/5) to afford
2
2
Complex 4a was isolated as a yellow powder in 93% yield.
5a-G as a white powder in 90% yield.
2

1
2
936
I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
3
1
1
0
5
a-G2: P { H} NMR (CDCl ): d ꢀ2.9 (s, P ), 14.0 (d,
temperature, then evaporated to dryness. The residue was
dissolved in THF, filtered through celite, and evaporated
again. Washings with diethyl ether and pentane afforded
3
2
0
2
JPP = 31.9 Hz, P ), 56.5 (d, J = 31.9 Hz, P ), 65.2 (s,
0
PP
0
1
P ), 65.9 (s, P ) ppm. H NMR (CDCl ): d 3.34 (d,
2
1
3
3
3
JHP = 10.5 Hz, 12H, P –N–CH ), 3.37 (d, J = 10.3 Hz,
5c-G as a white powder in 91% yield.
2
3
HP
1
3
1
1
0
1
6
H, P –N–CH ), 6.12 (m, 1H, H ), 6.42 (m, 1H, H ), 6.8
5c-G : P { H} NMR (CDCl ): d ꢀ25.1 (s, P ), 14.9
1
3
c
b
1
3
2 2
1
3
0
(
m, 1H, H ), 7.1–7.8 (m, 152H, H , CH@N) ppm.
C
(d, J = 28.5 Hz, P ), 56.3 (d, J = 28.5 Hz, P ), 66.8
PP 0 PP 0
a
Ar
1
2
1
3
{
H} NMR (CDCl ): d 32.8 (d, J = 13.0 Hz, P –N–
(s, P ) ppm. H NMR (CDCl ): d 2.61 (t,
JHH
=
3
CP
1
1
3
2
2
2
3
CH , P –N–CH ), 121.2 (br s, C ), 121.8 (br s, C , C ),
1
8.0 Hz, 8H, NCH CH ), 3.09 (t, JHH = 8.0 Hz, 2H,
3
2
3
2
0
1
2
2
3
3
0
3
1
3
m
27.9 (s, C ), 128.1 (s, C ), 128.4 (d, J = 7.0 Hz, C ,
NCH CH ), 3.28 (d, JHP = 10.4 Hz, 6H, P –N–CH ),
2 2 1 3
CP
0
m
2
p
2
4
4
3
3
C ), 128.8 (s, C ), 130.1 (s, C ), 130.7 (s, C ), 132.0 (d,
3.62 (br s, 16H, CH P), 6.10 (dd, J = 24 Hz, J
=
HHa
0
1
2
HP
2
o
p
2
3
3
J
= 10.1 Hz, C ), 132.5 (s, C ), 133.5 (d, J = 19.8 Hz,
17 Hz, 1H, H ), 6.33 (dd, J = 47 Hz, J
= 12 Hz,
HHa
CP
o
2
0
0
CP
c
HP
1
4
2
3
2
C ), 133.8 (d, JCP = 10.0 Hz, C ), 134.8 (d, JCP
=
1H, H ), 6.68 (d, JHH = 8.2 Hz, 4H, H–C ), 6.87 (d,
b 0
2
3
2
1
i
3
3
3
2
0.4 Hz, C ), 136.7 (d, JCP = 10.6 Hz, C ), 138.7 (d,
JHH = 8.0 Hz, 4H, H–C )), 6.91 (d, J = 8.0 Hz, 8H,
0
HH
2
3
3
2
3
3
JCP = 13.7 Hz, CH@NNP ), 139.2 (d,
J
= 13.7 Hz,
H–C ), 7.04 (d, JHH = 8.0 Hz, 8H, H–C ), 7.2-7.8
1 1
2
CP
1
2
13
1
CH@NNP ), 150.9 (d, JCP = 7.5 Hz, C ), 151.1 (d,
(m, 116H, H , CH@N) ppm. C { H} NMR (CDCl ):
1
2
Ar
3
2
1
1
2
1
2
JCP = 8.0 Hz, C ), 152.9 (d, JCP = 10.2 Hz, C ) ppm.
d 32.0 (s, NCH CH ), 33.1 (d, JCP = 13.0 Hz, P –N–
0
2
2
3
1
Anal. Calcd for C206H173N O P S (3775): C, 65.55;
H, 4.62; N, 4.82. Found: C, 65.39; H, 4.58; N, 4.77%.
CH ), 57.7 (t,
JCP = 5.9 Hz, JCP = 7.9 Hz, CH P), 115.3 (s, C ),
2
1
JCP = 8.9 Hz, CH2), 58.6 (dd,
13
14 16
7
3
3
1
2
3
2
2
1
21.2 (d, JCP = 3.0 Hz, C ), 122.0 (br s, C ),128.4 (d,
1 0
3
m
p
3
4
.12. Synthesis of dendron 5b-G1
JCP = 7.0 Hz, C ), 128.5 (s, C ), 128.0 (s, C ), 128.9
0
3
m
3
4
(
d, JCP = 10.0 Hz, C ), 129.8 (s, C ), 131.2 (s, C ),
0 1 0
2
o
2
A solution of the sodium salt of 1b (388 mg, 1.11 mmol)
132.2 (d, J = 11.0 Hz, C ), 133.1 (d, J = 18.4 Hz,
0
CP CP
o
4
1
(
obtained by reaction of NaH with 1b) in THF (20 ml) was
C ), 136.8 (s, CH @), 137.2 (s, C ), 138.1 (d, JCP =
1 1
i 1 i
2
added to a solution of G (216 mg, 0.25 mmol) in THF
12.7 Hz, C ), 138.2 (d, JCP = 12.7 Hz, C ), 138.9 (d,
1
1
0
3
2
(
10 ml). The resulting mixture was stirred for 12 h at room
J
= 12.6 Hz, CH@NNP ), 148.7 (d, JCP = 6.8 Hz,
CP
1
2 1
1
temperature then centrifuged and evaporated to dryness.
The residue was dissolved in THF and precipitated with
C ), 153.0 (d, J = 8.6 Hz, C ) ppm.
1 0
CP
pentane (repeated 3 times). Compound 5b-G was isolated
4.14. Synthesis of complex 6a-G1
1
as a white powder in 95% yield.
3
1
1
0
1
5
b-G1: P { H} NMR (CDCl ): d ꢀ19.7 (s, P ), 14.8 (d,
[RuCl (p-cymene)] (125 mg, 0.20 mmol) was added to a
3
2
2
2
0
2
JPP = 30.4 Hz, P ), 56.1 (d, J = 30.4 Hz, P ), 66.3 (s,
P ) ppm. H NMR (CDCl ): d 2.94 (s, 12H, CH NCH ),
.31 (d, JHP = 10.7 Hz, 6H, P –N–CH ), 4.17 (d,
1 3
JHP = 3.1 Hz, 8H, CH ), 6.10 (ddd, JHP = 24.1 Hz,
JHHa = 18.3 Hz, J = 1.2 Hz, 1H, Hc), 6.34 (ddd,
JHP = 45.9 Hz, JHHa = 12.4 Hz, JHH = 1.2 Hz, 1H,
solution of 5a-G (187 mg, 0.10 mmol) in THF (10 ml). The
0
PP
0
1
1
resulting mixture was stirred for 2 h at room temperature,
then evaporated to dryness. The residue was washed with
1
3
3
2
3
3
2
3
pentane. Complex 6a-G was isolated as an orange powder
2
1
3
3
2
in 83% yield.
HH
3
2
31
1
2
6a-G1: P { H} NMR (CDCl ): d 14.7 (d, JPP =
3
2
3
0
29.4 Hz, P ), 27.2 (s, Ph PRu), 55.6 (d, J = 29.4 Hz,
0 2 PP
2
H ), 6.80 (dddd,
JHP = 25.2 Hz,
JHHc = 18.3 Hz,
b
3
4
1
JHHb = 12.4 Hz, JHP = 1.2 Hz, 1H, H ), 7.0–7.9 (m,
0H, H , CH@N) ppm. C { H} NMR (CDCl ): d 33.1
d, JCP = 13.0 Hz, P –N–CH ), 38.9 (d, JCP = 6.7 Hz,
P ), 64.2 (s, P ) ppm. H NMR (CDCl ): d 1.06 (d,
a
0
1
3
1
3
1
3
8
(
JHH = 7.0 Hz, 24H, CH(CH ) ), 1.81 (s, 12H, CH ), 2.79
Ar
3
3 2 3
2
3
3
(sept.,
JHH = 7.0 Hz, 4H, CH(CH ) ), 3.33 (d,
3 2
1
3
1
3
3
CH NCH ), 61.1 (d, JCP = 10.6 Hz, CH ), 121.5 (d,
JHP = 10.8 Hz, 6H, P –N–CH ), 4.95 (d, J = 6.0 Hz,
1 3 HH
3
2
2
3
2
3
2
0
3
J
3
1
= 4.7 Hz, C ), 122.0 (d, J = 4.9 Hz, C ), 126.6 (s,
8H, CHArCymene), 5.16 (d, J = 6.0 Hz, 8H, CHArCymene),
CP
1
CP
3
HH
1
i
C ), 127.6 (dd, J = 91.0 Hz, J = 4.0 Hz, C ), 128.0
6.3 (m, 1H, H ), 6.8 (m, 2H, H C@), 7.1–7.8 (m, 76H,
CP
3
CP
m
0
c
2
3
0
p
13
1
(
(
(
1
s, C ), 128.5 (d, J = 6.7 Hz, C ), 128.7 (s, C ), 128.8
H , CH@N) ppm. C { H} NMR (CDCl ): d 17.8
CP
m
0
1
1
Ar
3
3
4
4
d, J = 13.0 Hz, C ), 131.0 (s, C ), 131.1 (s, C ), 132.2
(s, CH ), 21.9 (s, CH(CH ) ), 30.3 (s, CH(CH ) ), 32.8
CP
1
0
3 3 2 3 2
2
o
4
p
0
2
d, JCP = 10.9 Hz, C ), 132.7 (d,
33.1 (d, J = 18.6 Hz, C ), 134.2 (s, C -CH@N), 136.8
s, CH @), 137.6 (d, JCP = 13.3 Hz, C ), 139.0 (d,
CP
J
= 2.0 Hz, C ),
(d, JCP = 13.0 Hz, P –N–CH ), 87.2 (d, J = 5.2 Hz,
1 3 CP
0
CP
4
1
o
1
CHArCymene), 89.1 (s, CHArCymene), 96.0 (s, CH CArCymene),
3
CP
1
1
i
2
(
111.2 (s, (CH ) CHC
), 120.7 (m, C ), 122.0 (br s,
ArCymene
1
2
1
3 2
3
3
2
2
m
3
J
1
= 13.7 Hz, CH@NNP ), 149.7 (d, JCP = 7.3 Hz,
C ), 128.1 (d, J = 9.6 Hz, C ), 128.7 (s, C ), 128.8 (d,
1
0
CP
m
1
0
2
1
3
1
4
C ), 153.1 (d, J = 9.5 Hz, C ) ppm.
CP
JCP = 12.4 Hz, C ), 130.3 (br d, JCP = 46.0 Hz, C ),
0 1
1
0
p
1
2
o
1
30.4 (s, C ), 132.1 (d, J = 10.1 Hz, C ), 132.8 (br s,
CP
0
p
1
i
2
4
.13. Synthesis of dendron 5c-G1
C ), 133.5 (d, J = 50.0 Hz, C ), 134.2 (d, J = 9.4 Hz,
0
1
CP CP
o
1
2
3
1
C ), 135.9 (d, J = 10.1 Hz, C ), 136.9 (s, CH @), 139.8
CP
2
3
1
A solution of G (179 mg, 0.2 mmol) in THF (5 ml) was
(d, J = 13.0 Hz, CH@NNP ), 152.0 (br s, C ), 153.1
1
1
1
CP
1
added to a solution in THF (5 ml) of the sodium salt of 1c
466 mg, 0.83 mmol) (obtained by reaction of NaH with
c). The resulting mixture was stirred for 1 day at room
(br s, C ) ppm. Anal. Calcd for C142H141N O P S Cl Ru
0
5 6 8 3 8 4
(
1
(3046): C, 56.00; H, 4.67; N, 2.30. Found: C, 56.07; H,
4.71; N, 2.28%.

I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
1937
2
3
1
1
i
1
4
.15. Synthesis of complex 6b-G1
RuCl (p-cymene)] (62 mg, 0.10 mmol) was added to a
(d, JCP = 20.5 Hz, C ), 136.7 (d, JCP = 10.6 Hz, C ),
1
3
36.8 (s, CH @), 139.2 (d, J = 13.9 Hz, CH@NNP ),
151.0 (d, J = 7.3 Hz, C ), 152.8 (d, J = 9.3 Hz, C )
CP CP
1 0
2 CP
2 2
1
1
1
[
2
2
solution of 5b-G (105 mg, 0.05 mmol) in THF (10 ml).
ppm. Anal. Calcd for C104H N O P S (1879): C,
91 7 6 8 3
1
The resulting mixture was stirred for 4 h at room tempera-
ture, then evaporated to dryness. The residue was washed
66.48; H, 4.88; N, 5.22. Found: C, 66.34; H, 4.81; N,
5.17%.
with pentane. Complex 6b-G was isolated as an orange
1
powder in 94% yield.
4.17. Synthesis of dendron 7b-G1
3
1
1
6
b-G1:
P
{ H} NMR (CDCl3):
d
15.0 (d,
2
2
0
JPP = 30.0 Hz, P ), 29.2 (s, Ph PRu), 56.1 (d,
JPP = 30.0 Hz, P ), 62.3 (s, P ) ppm. H NMR (CDCl ):
d 0.84 (d, JHH = 7.0 Hz, 12H, CH(CH ) ), 0.87 (d,
JHH = 7.0 Hz, 12H, CH(CH ) ), 1.85 (s, 12H, CH ), 2.15
Ethylenediamine (0.50 ml, 7.5 mmol) was rapidly added
to a solution of dendron 5b-G (174 mg, 0.08 mmol) in
THF (15 ml) under vigorous stirring. After 2h30 at room
temperature, the solution was evaporated to dryness. The
residue was washed 3 times with a mixture THF/pentane
0
2
1
0
1
3
1
3
3 2
3
3 2
3
3
(
s, 12H, CH NCH ), 2.47 (sept., JHH = 7.0 Hz, 4H,
3 2
3
CH(CH ) ), 3.31 (d, JHP = 10.4 Hz, 6H, P –N–CH ),
(1:5) to afford the dendron 7b-G as a white powder in
3
2
1
3
1
4
.83 (br s, 8H, CH P), 5.10 (m, 8H, CHArCymene), 5.25
84% yield.
2
3
1
1
0
1
(
m, 8H, CHArCymene), 6.00–6.75 (m, 3H, CH @CH),
7b-G1: P { H} NMR (CDCl ): d ꢀ19.6 (s, P ), 21.1 (d,
2
3
1
3
1
2 2
0
6
.95–8.10 (m, 76H, H , CH@N) ppm. C { H} NMR
JPP = 33.8 Hz, P ), 55.7 (d, J = 33.8 Hz, P ), 66.4 (s,
0 PP 0
Ar
1
(
CDCl ): d 17.4 (s, CH ), 21.4 (s, CH(CH ) ), 29.9 (s,
P1) ppm. H NMR (CDCl ): d 2.40–2.65 (m, 4H,
3
3
3 2
3
2
CH(CH ) ), 33.1 (d, J = 12.7 Hz, P –N–CH ), 38.6 (s,
CH NCH ), 54.9 (d, JCP = 22.9 Hz, CH P), 85.6 (s,
CHArCymene), 89.9 (d, J = 5.5 Hz, CHArCymene), 94.1 (s,
NCH CH N), 2.80–3.05 (m, 4H, CH CH P), 2.93 (s,
3
2
CP
1
1
3
2
2
2
2
3
12H, CH NCH ), 3.30 (d, JHP = 10.6 Hz, 6H, P –N–
3 2 1
CH ), 4.17 (d, J = 3.1 Hz, 8H, CH P), 7.00-7.70 (m,
3 HP 2
3
2
2
2
2
CP
1
3
1
CH C
), 108.0 (s, (CH ) CHC
), 121.2 (d,
80H, H , CH@N) ppm. C { H} NMR (CDCl ): d 27.8
3
ArCymene
3 2
ArCymene
Ar
3
3
2
3
2
1
0
(d, J = 64.9 Hz, CH P ), 33.4 (d, J = 12.8 Hz, P1–
CP 2 0 CP
2
J
= 4.0 Hz, C ), 122.0 (d, J = 4.0 Hz, C ), 126.0 (s,
CP
1
CP
0
3
1
3
0
3
m
3
C ), 127.5 (s, C ), 128.0 (d, J = 8.5 Hz, C ), 128.8 (d,
N–CH ), 39.3 (d, JCP = 6.8 Hz, CH NCH ), 41.7 and
3 3 2
42.7 (2s, H NCH CH NHCH ), 52.1 (s, H NCH -
2 2 2 2 2 20
CP
1
1
3
m
i
1
JCP = 12.8 Hz, C ), 130.4 (d, J = 97.1 Hz, C ), 130.7
0
CP
p
1
4
4
2
1
(
s, C ), 131.1 (s, C ), 131.3 (s, C ), 132.1 (d, J = 10.8 Hz,
CH NH), 61.4 (d, J = 7.5 Hz, NCH P), 121.8 (br s,
2 CP 2
1
0
CP
o
p
4
2
2
3
3
C ), 132.7 (s, C ), 134.2 (s, C CH@N), 134.4 (d,
C ), 122.4 (br s, C ), 127.0 (s, C ), 128.4 (s, C ), 128.9 (d,
1 0 1 0
0
0
1
1
o
1
3
3
m
p
3
JCP = 7.5 Hz, C ), 136.9 (s, CH @), 139.0 (d, JCP
J
= 7.0 Hz, C ), 129.1 (s, C ), 129.3 (d, J = 15.0 Hz,
1
1
CP CP
2
2
1
1
m
4
4
2
o
=
1
12.6 Hz, CH@NNP ), 149.1 (d, JCP = 7.3 Hz, C ),
53.1 (d, JCP = 9.5 Hz, C ) ppm. Anal. Calcd for
C ), 131.3 (s, C , C ), 131.7 (d, J = 8.0 Hz, C ), 133.0 (s,
0 0 1 0
CP
1
2
1
0
p
1
o
4
C ), 133.5 (d, J = 15.1 Hz, C ), 134.6 (s, C –CH@N),
0
1 1
1 i 3
CP
C154H165N O P S Cl Ru (3326): C, 55.61; H, 5.00; N,
138.1 (d, J = 15.1 Hz, C ), 139.4 (d, J = 15.1 Hz,
1
CP CP
13
6
8
3
8
4
2
1
5
.48. Found: C, 55.68; H, 5.03; N, 5.45%.
CH@NNP ), 150.0 (d, JCP = 7.5 Hz, C ), 152.7 (br s,
1
1
1
C ) ppm.
0
4
.16. Synthesis of dendron 7a-G1
4.18. Synthesis of dendron 8a-G2
Ethylenediamine (0.44 ml, 6.6 mmol) was rapidly added
to a solution of dendron 5a-G (120 mg, 0.066 mmol) in
Aminopentanol (308 mg, 20 equivalents) was rapidly
added to solution of dendron 5a-G2 (560 mg,
0.148 mmol) in THF (15 ml). The resulting solution was
heated in a sealed Schlenck at 70 °C overnight then evapo-
rated to dryness. The residue was washed 4 times with a
mixture THF/pentane (1:5) then ether/pentane (1:2) to
1
THF (15 ml) under vigorous stirring. After 3h at room
temperature, the solution was evaporated to dryness. The
residue was washed 3 times with a mixture THF/pentane
a
(
1:5) to afford the dendron 7a-G as a white powder in
1
9
2% yield.
3
1
1
0
1
7
a-G : P { H} NMR (CDCl ): d ꢀ2.9 (s, P ), 21.4
afford the dendron 8a-G as a white powder in 90% yield.
1
3
2
2
0
2
31
1
0
(
d, JPP = 34.0 Hz, P ), 56.0 (d,
J
= 34.0 Hz, P ),
8a-G2. P{ H} NMR (CDCl ) d: ꢀ3.1 (s, P ), 21.3 (d,
0
PP
0
3
2
1
2 2
0
6
5.5 (s, P ) ppm. H NMR (CDCl ): d 2.40–2.65 (m,
JPP = 32.6 Hz, P ), 55.8 (d, J = 32.6 Hz, P ), 65.0 (s,
0 PP 0
1
3
1
4
H, NCH CH N), 2.70–2.95 (m, 4H, CH CH P), 3.35
P ), 66.1 (s, P ) ppm. H NMR (CDCl ) d: 1.30–1.70 (m,
2 1 3
2
2
2
2
3
(
d, J = 10.6 Hz, 6H, P –N–CH ), 7.10–7.70 (m, 76H,
6H, HO–CH –CH –CH –CH –CH –NH), 2.47 (t,
2 2 2 2 2
HP
1
1
3
1
3
3
H , CH@N) ppm. C { H} NMR (CDCl ): d 27.3 (d,
JHH = 6.3 Hz, 2H, –CH –CH –CH –NH), 2.7–3.0 (m,
2 2 2
Ar
3
1
0
2
0
4H, CH –CH –P ), 3.34 (d, JHP = 10.5 Hz, 18H, N–
2 2 0
CH ), 3.52 (t, JHH = 6.4 Hz, 2H, HO–CH –), 7.1–7.8
3 2
(m, 152H, H , CH@N) ppm. C{ H} NMR (CDCl ) d:
23.1 (s, C H ), 27.2 (d, J = 58 Hz, CH –P ), 29.3 (s,
c 2 CP 2
C H ), 32.2 (d, J = 12.8 Hz, N–CH ), 34.0 (s, C H ),
d 2 CP 3 b 2
42.3 (s, CH –CH –P ), 49.1 (s, C H ), 62.3 (s, C H ),
2 2 e 2 a 2
3
JCP = 64.7 Hz, CH P ), 32.8 (d, J = 13.5 Hz, P –N–
2
0
CP
1
3
CH ), 41.1 and 42.1 (2s, H NCH CH NHCH ), 51.6 (s,
3
2
2
2
2
2
1
3
13
1
H NCH CH NH), 121.3 (m, C ), 121.8 (d, J = 4.5 Hz,
C ), 127.8 (s, C ), 128.3 (s, C ), 128.5 (d, J = 10.2 Hz,
C ), 128.7 (d, J = 12.9 Hz, C ), 130.7 (s, C ), 131.1 (d,
JCP = 10.3 Hz, C ), 131.9 (dd, J = 101.0 Hz, J
.0 Hz, C ), 132.4 (d, JCP = 3.0 Hz, C ), 133.5 (d,
JCP = 19.3 Hz, C ), 133.8 (d, J = 11.0 Hz, C ), 134.8
CP
2
2
2
CP
Ar
3
2
3
0
p
1
3
1
0
0
0
CP
4
0
m
3
m
0
2
1
CP
2
o
0
1
3
0
=
CP
CP
0
i
0
4
p
0
3
3
2
6
121.3 (‘‘t’’,
J
0
= J
= 5.8 Hz, C ), 121.8 (d,
CP2
2
CP 3
2
o
1
1
4
1
3
2
2
3
3
JCP = 5.1 Hz, C , C ), 127.9 (s, C ), 128.1 (s, C ), 128.4
0 1 0 1

1938
I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
3
m
0
m
2
p
2
(
d, JCP = 7.1 Hz, C , C ), 128.7 (s, C ), 128.8 (dd,
CH – CH –CH -NH), 1.96 (m, 32H, CH cod), 2.36 (br s,
2 2 2 2
3
CP
1
i
4
J
= 7.1 Hz, JCP = 95.1 Hz, C ), 130.7 (s, C ), 131.2
d, J = 10.1 Hz, C ), 131.9 (s, C ), 132.4 (s, C ), 133.5
34H, CH cod, –CH –CH –CH –NH), 2.7–3.0 (m, 4H,
2 2 2 2
0
0
2
o
0
4
1
p
0
(
(
1
CH –CH –P ), 3.09 (br s, 16H, CHcod), 3.34 (d,
2 2
CP
0
0
2
o
1
4
3
d, JCP = 19.5 Hz, C ), 133.9 (s, JCP = 9.8 Hz, C ),
JHP = 10.5 Hz, 18H, N–CH ), 3.52 (br s, 2H, HO–CH ),
3 2
2
2
2
3
2
1
34.9 (d, J = 20.4 Hz, C ), 136.7 (d, J = 10.4 Hz,
5.53 (br s, 16H, CHcod), 7.1–7.9 (m, 152H, H , CH@N)
CP
CP
Ar
i
2
3
13 1
C ), 138.7 (d, JCP = 13.6 Hz, CH@NNP ), 139.4 (d,
ppm. C{ H} NMR (CDCl ) d: 23.3 (s, C H ), 27.3 (d,
3 c 2
JCP = 56.0 Hz, CH -P ), 29.1 (s, CH cod), 29.4 (s,
2 2
C H ), 32.3 (d, J = 13.0 Hz, N–CH ), 33.4 (s, CH cod),
d 2 CP 3 2
34.1 (s, C H ), 42.4 (s, CH –CH –P ), 49.3 (s, C H ), 62.4
b 2 2 2 e 2
2
3
2
1
0
J
1
2
= 14.7 Hz, CH@NNP ), 151.0 (d, JCP = 7.6 Hz,
CP
1
0
2
1
1
2
2
C ), 151.1 (d, J = 7.7 Hz, C ), 152.9 (d, J = 8.8 Hz,
CP
CP
1
0
0
C ). Anal. Calcd for C211H186N O P S (3878): C,
14 15 16
7
0
6
5.35; H, 4.83; N, 5.06. Found: C, 65.28; H, 4.79; N, 4.98%.
(s, C H ), 71.2 (br s, CHcod), 105.0 (br s, CHcod), 121.3
a 2
2
2
2
3
3
(
m, C ), 121.8 (br s, C , C ), 128.1 (s, C , C ), 128.5 (d,
2 0 1 0 1
3
m
m
p
4
4
.19. Synthesis of complex 9b-G1
JCP = 7.0 Hz, C ), 128.7 (br s, C ) 130.7 (s, C , C ),
2 0 0
2
2
o
1
1
31.2 (d, J = 10.1 Hz, C ), 131.7 (d, J = 42.1 Hz,
CP CP
0
i
4
p
2
A solution of [RuCl (p-cymene)] (76 mg, 0.124 mmol)
C ), 131.9 (s, C ), 132.4 (s, C ), 134.5 (d, J = 11.5 Hz,
2 1
0
CP
2
2
o
2
3
in CH Cl (5 ml) was added to a solution of 7b-G1
C ), 137.1 (d, J = 13.4 Hz, C ), 139.9 (m, CH@NNP),
2 2
1 2 1
2
2
CP
(
134 mg, 0.062 mmol) in CH Cl (15 ml). After stirring
151.7 (br s, C ), 152.6 (d, J = 7.0 Hz, C ), 153.1 (br s,
1 2
CP
2
2
1
for 1h at room temperature, the solution was evaporated
to dryness. The residue was washed several times with
diethylether, to afford 9b-G as an orange powder in 80%
C ). Anal. Calcd for C275H282Cl N O P Rh S
0
8 14 15 16 8 7
(5850.2): C, 56.46; H, 4.86; N, 3.35. Found: C, 56.53; H,
4.89; N, 3.28.
1
yield.
3
1
1
2
9
b-G1:
P { H} NMR (CDCl ): d 20.8 (d, JPP =
3
Acknowledgements
0
2
3
3.7 Hz, P ), 29.1 (s, Ph PRu), 55.0 (d, J = 33.7 Hz,
0
2
PP
1
P ), 66.3 (s, P ) ppm. H NMR (CDCl ): d 0.84 (d,
0
1
3
Thanks are due to the European Community through
the contract MRTN-CT-2003-503864 (AQUACHEM) for
a grant to P. Servin, and through the Marie Curie training
site HPMTGH010039808 for a grant to I. Angurell. This
work was also supported by the CNRS.
3
JHH = 6.3 Hz, 12H, CH(CH ) ), 1.84 (s, 12H, CH ), 2.14
3 2
3
(
(
s, 12H, CH NCH ), 2.46 (m, 4H, CH(CH ) ), 2.40–2.65
3 2 3 2
m, 4H, CH N), 2.80–3.05 (m, 4H, CH N), 2.92 (s, 12H,
2
2
3
CH NCH ), 3.30 (d, JHP = 10.4 Hz, 6H, P –N–CH ),
4
(
C CH@N), 6.90–8.00 (m, 80H, H , CH@N) ppm.
{
2
(
(
(
(
1
1
3
2
1
3
.82 (br s, 8H, NCH P), 5.10 (m, 8H, CHArCymene), 5.27
2
2
d, JHP = 6.0 Hz 8H, CHArCymene), 6.53 (s, 4H,
References
4
1
13
C
Ar
1
H} NMR (CDCl ): d 17.4 (s, CH ), 21.4 (s, CH(CH ) ),
3 3 3 2
[1] C.J. Hawker, J.M.J. Fr e´ chet, J. Am. Chem. Soc. 112 (1990) 7638.
[2] J.S. Moore, Z. Xu, Macromolecules 24 (1991) 5893.
1
0
0
7.0 (d, J = 65 Hz, CH P ), 29.9 (s, CH(CH ) ), 33.1
d, J = 12.4 Hz, P –N–CH ), 38.6 (s, CH NCH ), 54.9
CP 1 3 3 2
d, J = 23.1 Hz, NCH P), 85.5 (s, CHArCymene), 89.9
CP 2
CP
2
3 2
2
[
3] G.R. Newkome, F. V o¨ gtle, C.N. Moorefield, Dendrimers and
Dendrons, John Wiley and Sons, Weinheim Germany, 2001.
4] J.M.J. Fr e´ chet, D.A. Tomalia, Dendrimers and Other Dendritic
Polymers, John Wiley and Sons, Chichester, UK, 2001.
1
[
br s, CHArCymene), 94.1 (s, CH C
), 109.0 (s,
ArCymene
3
2
2
CH ) CHC
), 121.2 (br s, C ), 122.0 (br s, C ),
ArCymene
1 0
3
2
[5] A.M. Caminade, A. Maraval, J.P. Majoral, Eur. J. Inorg. Chem.
(2006) 887.
3
3
3
m
26.0 (s, C ), 126.6 (s, C ), 128.0 (d, J = 8.4 Hz, C ),
1 0 1
CP
3
m
1
[6] Y. Ishida, M. Jikei, M.A. Kakimoto, Macromolecules 33 (2000)
3202.
28.9 (d, J = 12.0 Hz, C ), 130.1 (d, J = 98.0 Hz,
CP
0
CP
4
i
p
4
C ), 130.7 (s, C ), 131.3 (s, C ), 131.6 (s, C ), 132.4 (d,
1
1
1
0
2
o
0
p
o
4
1
[7] K. Sivanandan, B.S. Sandanaraj, S. Thayumanavan, J. Org. Chem.
JCP = 10.0 Hz, C ), 132.4 (s, C ), 134.3 (m, C , C CH@N),
39.0 (br s, CH@NNP ), 149.1 (br s, C ), 152.9 (d,
1
1
JCP = 9.5 Hz, C ) ppm. Anal. Calcd for C156H173N -
0
1
6
9 (2004) 2937.
1
1
1
[8] V. Maraval, R. Laurent, B. Donnadieu, M. Mauzac, A.M. Caminade,
J.P. Majoral, J. Am. Chem. Soc. 122 (2000) 2499.
2
0
15
[
9] V. Maraval, R. Laurent, S. Merino, A.M. Caminade, J.P. Majoral,
Eur. J. Org. Chem. (2000) 3555.
O P S Cl Ru (3386): C, 55.34; H, 5.15; N, 6.21. Found:
C, 55.48; H, 5.21; N, 6.16%.
6
8
3
8
4
[
10] A.M. Caminade, V. Maraval, R. Laurent, J.P. Majoral, Curr. Org.
Chem. 6 (2002) 739.
[11] P.A. Chase, R.J.M. Klein Gebbink, G. van Koten, J. Organomet.
Chem. 689 (2004) 4016.
4
.20. Synthesis of complex 10a-G2
[
[
12] B. Helms, J.M.J. Fr e´ chet, Adv. Synth. Catal. 348 (2006) 1125.
13] A. Dahan, M. Portnoy, J. Polym. Sci. A. Polym. Chem. 43 (2005)
A solution of [RhCl(cod)]2 (246 mg, 0.500 mmol) in
CH Cl (5 ml) was added to a solution of 8a-G (484 mg,
2
2
2
2
35.
0
.125 mmol) in CH Cl (15 ml). After stirring for 2h at
2 2
[14] R. van de Coevering, R.J.M. Klein Gebbink, G. van Koten, Prog.
room temperature, the solution was evaporated to dryness.
The residue was washed several times with CH Cl /pen-
Polym. Sci. 30 (2005) 474.
[15] R. van Heerbeek, P.C.J. Kamer, P.W.N.M. van Leeuwen, J.N.H.
Reek, Chem. Rev. 102 (2002) 3717.
[16] B. Romagnoli, W. Hayes, J. Mater. Chem. 12 (2002) 767.
17] O. Herd, A. Hessler, M. Hingst, M. Tepper, O. Stelzer, J. Organomet.
Chem. 522 (1996) 69.
[18] I. Angurell, G. Muller, M. Rocamora, O. Rossell, M. Seco, Dalton
Trans. (2003) 1194.
2
2
tane, to afford 10a-G as a yellow powder in 80% yield.
2
3
1
1
1
0a–G2:
P{ H} NMR (CDCl3) d: 20.5 (d,
[
2
0
1
0
JPP = 32.9 Hz, P ), 33.5 (d, J
5.3 (d, J = 32.9 Hz, P ), 64.1 (s, P ), 66.1 (s, P ) ppm.
PP 0 2 1
H NMR (CDCl ) d: 1.30–1.70 (m, 6H, HO–CH –CH -
= 151.0 Hz, P 2 Rh),
0
PRh
2
5
1
3
2
2

I. Angurell et al. / Journal of Organometallic Chemistry 692 (2007) 1928–1939
1939
[
[
19] M.L. Lartigue, M. Slany, A.M. Caminade, J.P. Majoral, Chem. Eur.
J. 2 (1996) 1417.
20] M. Slany, A.M. Caminade, J.P. Majoral, Tetrahedron Lett. 37 (1996)
[21] I. Angurell, G. Muller, M. Rocamora, O. Rossell, M. Seco, Dalton
Trans. (2004) 2450.
[22] D.C. Tully, J.M.J. Fr e´ chet, Chem. Commun. (2001) 1229.
9053.