Synthesis of dendrimers with phosphine end groups at each generation

Article abstract of DOI:10.1016/S0022-328X(01)01265-7

The synthesis of new phenoxydiphenylphosphino derivatives allows the formation of dendrimers having phosphine end groups at each generation. The dendrimers are grown up to the fourth generation (32 phosphine terminal groups) using Staudinger reactions with azides and deprotection of borane-phosphine complexes by amines.

Full text of DOI:10.1016/S0022-328X(01)01265-7

Journal of Organometallic Chemistry 643–644 (2002) 112–124
www.elsevier.com/locate/jorganchem
Synthesis of dendrimers with phosphine end groups at each
generation
Anna Balueva 1, Sonia Merino 2, Anne-Marie Caminade *, Jean-Pierre Majoral *
Laboratoire de Chimie de Coordination, CNRS, 205 route de Narbonne, 31077 Toulouse Cedex 4, France
Received 14 June 2001; accepted 18 September 2001
Dedicated to Professor Franc¸ois Mathey on the occasion of his 60th birthday
Abstract
The synthesis of new phenoxydiphenylphosphino derivatives allows the formation of dendrimers having phosphine end groups
at each generation. The dendrimers are grown up to the fourth generation (32 phosphine terminal groups) using Staudinger
reactions with azides and deprotection of borane–phosphine complexes by amines. © 2002 Elsevier Science B.V. All rights
reserved.
Keywords: Dendrimers; Phosphines; Borane; Staudinger reaction
interesting functions, due to their complexation ability,
leading in particular to new catalysts. The grafting of
1. Introduction
phosphine end groups can be accomplished at the end
Dendrimers are hyperbranched regular macromolec-
of the synthesis of the dendrimer, or can occur at each
ular trees characterized by the presence of a large
generation during the synthesis. Our previous investiga-
number of functional groups on the surface, which
tions concerning the latter case used the Staudinger
opens the way to a versatile reactivity [1]. Recent
reaction which creates PꢀNꢁPꢀS linkages within the
emphasis in this topic concerns the study of properties
of these intriguing macromolecules [2], but the search
dendritic structure. Furthermore, these linkages were
demonstrated to possess a very interesting reactivity [7],
for other methods of synthesis remains an active area.
but necessitated three steps at each generation to be
We have reported several ways of synthesis of phospho-
created and to multiply by two the number of phos-
rus-containing dendrimers possessing various functional
phine end groups. Thus, it appeared interesting to find
end groups at each step of the synthesis, mainly chlo-
straighter ways of synthesis, which could multiply more
rine and aldehyde, which allowed us to carry out
miscellaneous reactions [3] and to develop various ap-
plications [4]. We [5] and others [6] have also demon-
strated that phosphine end groups are particularly
rapidly the number of phosphine end groups and
PꢀNꢁPꢀS linkages with a smaller number of reactions.
We recently proposed two ways to fulfill these require-
ments by synthesizing new building blocks, i.e.
N3P(S)(OC6H4PPh2BH3)2, which allows to multiply by
two the number of phosphine end groups every two
steps [8], and H2NN(Me)P(S)(OC6H4PPh2)2, which al-
lows to multiply by four the number of phosphine end
groups every two steps [9].
We report here the synthesis of (phenoxy-
diphenyl)phosphines and their use as functional build-
ing blocks for the synthesis of new di- and
tetra-phosphine monomers, and of dendrimers up to
the fourth generation (32 RPPh2 end groups).
* Corresponding authors. Tel.: +33-561-333-123; fax: +33-561-
553-003.
E-mail addresses: caminade@lcc-toulouse.fr (A.-M. Caminade),
majoral@lcc-toulouse.fr (J.-P. Majoral).
1 Present address: A.E. Arbuzov Institute of Organic and Physical
Chemistry, Russian Academy of Sciences, Kazan Scientific Centre,
Arbuzov Street 8, Kazan 42088, Russia.
2 Present address: Area de Quimica Organica, Facultad de Quimi-
cas, Av. Camilo Jose Cela s/n, 13071 Ciudad Real, Spain.
0022-328X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)01265-7

A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
113
singlets at l=58.4 (PꢀS) and 22.4 ppm (P“BH3)
(Scheme 1). This compound also was not perfectly
purified, but used to react with NaN3. The azide 7 thus
obtained is purified by column chromatography and
characterized in 31P-NMR by the presence of two sin-
glets (l=59.4 (PꢀS) and 22.4 ppm (P“BH3), and by
2. Results and discussion
In order to rapidly multiply the number of phosphine
end groups, we decided to synthesize the new function-
alized diphosphine 1,3-(PPh2)2-5-HO–(C6H3) (1)
(Scheme 1). For this purpose, we used a method
analogous to the one described for the synthesis of
1,2-(PPh2)2-4-HOCH2–(C6H3) [10]. The reaction of
Ph2PNa with 3,5-difluorophenol occurs very slowly at
130 °C in 1,4-dioxane and needs 12 days to go to
completion. After purification on silicagel, compound 1
is isolated, and characterized in 31P-NMR by a singlet
at l= −4.8 ppm. The phosphino groups are not very
sensitive to oxidation, however, we decided to protect
them by BH3 from this step. The reaction with
BH3·SMe2 affords cleanly the protected derivative 2,
characterized in 31P-NMR by a broad singlet at l=
21.4 ppm.
IR spectroscopy (w¯N =2189 cm−1).
3
We intended to use compounds 5 and 7 for the
synthesis of dendrimers. In this perspective, we reacted
first the azide 5 with Ph3P (Scheme 2). The reaction
affords compound 8, which is purified by column chro-
matography. The 31P-NMR spectrum of 8 consists of
three signals: two doublets at l=14.4 (PꢀN) and 52.6
3
ppm (PꢀS) with JPP=28.8 Hz, and one broad singlet
at l=21.7 ppm (P“BH3). IR spectroscopy indicates
the disappearance of the signal corresponding to N3.
The second step of the synthesis necessitates to depro-
tect both phosphino groups of 8. This is achieved by
using 1,4-diazabicyclo-[2,2,2]-octane (DABCO). Com-
pound 9-G1 is purified by chromatography, in spite of
the presence of two free phosphino groups. The 31P-
NMR spectrum confirms that the deprotection oc-
curred, characterized by the presence of a singlet at
l= −4.8 ppm, corresponding to the free PPh2 groups.
Compound 9-G1 can be considered as the first genera-
tion of the dendrimer, since it possesses two phosphino
groups whereas the core (PPh3) had only one.
The phenolate derivative 3 is readily obtained from 2,
by reaction with NaH. This compound is the precursor
of diphosphino and tetraphosphino derivatives usable
for the synthesis of dendrimers. For this purpose, the
sodium salt 3 is reacted with chlorothiophosphine
derivatives. Reaction of one equivalent of 3 with one
equivalent of PhOP(S)C12 at −95 °C gives derivative
4, possessing one chlorine and two protected phosphi-
nes. No attempt was made to perfectly purify this
compound, and it was directly used to react with NaN3
to yield the azide 5 (Scheme 1). Column chromatogra-
phy on silicagel affords pure 5, characterized by the
presence of two singlets in 31P-NMR (l=59.5 (PꢀS)
and 22.3 ppm (P“BH3)) and a strong band in IR
The next step to grow the dendrimer obviously con-
sists in reacting the azide 5 with the diphosphine 9-G1.
However, we had to face some problems in this case.
Indeed, the steric hindrance of both PPh2 groups in 1,3
position slackens the Staudinger reaction of the azide 5,
and side reactions are observed. In particular a migra-
tion of some BH3 groups from the phosphino group of
compound 5 to the phosphino group of compound
9-G1 occurs. In spite of this problem, compound 10-G1
spectroscopy (w¯N =2189 cm−1).
3
Two equivalents of the sodium salt 3 react with one
equivalent of P(S)C13 at −100 °C to afford compound
6, characterized in 31P-NMR by the presence of two
Scheme 1. Synthesis of various phenoxydiphenylphosphino derivatives usable for the synthesis of dendrimers.

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A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
Scheme 2. Synthesis of the first generation of the dendrimer 10-G1.
is isolated by column chromatography, but in low yield
(22%). The 31P-NMR spectrum of 10-G1 consists of five
signals: two sets of two doublets in a 2:1 ratio at
H3(PPh2)2) is 631, these values indicate that only four
to six monomeric units are linked. On the other hand,
both 31P-NMR and IR spectroscopies indicate the total
disappearance of the N3 groups. The only way to
explain both phenomena is to consider that macrocy-
cles are formed in most cases, instead of hyperbranched
polymers. Indeed, the meta position should favour the
formation of such macrocycles instead of the growing
of the chain.
This problem, in addition to the steric constraints
induced by the presence of both phosphino groups in
meta position should prevent the use of these 1,3
diphosphino compounds to build dendrimers, and we
did not tried to use the tetraphosphine 7 in such a way.
However, compound 7 could be grafted on the surface
of dendrimers. Thus, we decided to built the dendrimer
using the same sequence of reactions, but with a less
hindered building block, N3P(S)(OC6H4PPh2BH3)2 (12)
[8]. The reaction with PPh3 affords compound 13 which
is deprotected with DABCO, leading to compound
14-G1 (Scheme 4). The presence of the phosphino group
in para position in 14-G1 compared to the bis(meta)
position in 10-G1 induces a higher reactivity, and we do
not observe transfer reactions of BH3 when 14-G1 is
reacted with the azide 12. Compound 15-G1 is isolated
2
l=13.5 (Ph2PꢀN) and 52.7 ppm (PꢀS) with JPP=29.4
2
Hz, l=14.6 (Ph3PꢀN) and 52.6 ppm (PꢀS) with JPP
=
28.2 Hz, and a broad singlet at l=21.7 ppm (P“
BH3). The presence of two sets of two doublets
confirms that the Staudinger reaction occurred, but we
decided to stop the synthetic process at this step, be-
cause the phenomenon of exchange of BH3 observed
during the synthesis of 10-G1 should occur at each step
and hamper the synthesis and purification of further
generations.
However, we thought that this exchange phe-
nomenon would not be a constraint for the synthesis of
hyperbranched polymers issued from compound 5. For
this purpose, we treated compound 5 with an amine,
either NEt3 or DABCO (Scheme 3). Such treatment
should result in a polymerization, the deprotected phos-
phines reacting with the azide. The end of the reaction
is characterized by the disappearance of both the signal
corresponding to the P“BH3 groups in 31P-NMR and
the signal of the N3 groups in IR. The 31P-NMR
spectrum of compound 11 displays large signals at
l=13 (Ph2PꢀN) and 52 ppm (PꢀS) and two relatively
thin singlets at l= −4.7 and −4.8 ppm corresponding
to free PPh2. The presence of two signals is presumably
due to ‘terminal’ and ‘linear’ groups, corresponding,
respectively, to two phosphino groups linked to one
aromatic group, and one phosphino group linked to
one aromatic group bearing also a phosphazene group.
Size exclusion chromatography (SEC) and laser light
scattering (LLS) give an average value for the molecu-
lar weight of the hyperbranched polymer 11: 3000 for
the sample obtained with NEt3, and 3800 for the sam-
ple obtained with DABCO. Considering that the molec-
ular weight of the monomeric unit NP(S)(OC6H5)(OC6-
Scheme 3. One-step synthesis of the hyperbranched polymers 11 and
11%.

A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
115
Scheme 4. Step-by-step synthesis of dendrimers 14-Gn, 15-Gn, 16-G3, and 17-G4.
in good yield, then deprotected with DABCO, to give
the second generation of the dendrimer 14-G2. This
compound is characterized in 31P-NMR by the pres-
ence of two sets of doublets at l=14.8 and 49.9 ppm
four sets of two doublets (l=14.9 and 50.0,
Ph3PꢀNꢁPꢀS; 14.5 and 49.8, Ph2PꢀNꢁPꢀS of the first
generation; 14.3 and 49.6, Ph2PꢀNꢁPꢀS group of the
second generation; 13.5 and 52.7, Ph2PꢀNꢁPꢀS groups
of the third generation). Fig. 1 displays all the 31P-
NMR spectra of dendrimers from 15-G1 to 17-G4. It is
important to note that all the signals corresponding to
each type of phosphorus are detected, even for 17-G4
(17 peaks corresponding to eight types of phosphorus).
Beside 31P-NMR, all these compounds are analyzed
by 1H-, and 13C-NMR, IR, and elemental analyses,
but in all cases, 31P-NMR appears as the best tool to
characterize each step of the synthesis. During the
construction of the skeleton of the dendrimer, the
Staudinger reaction induces a deshielding of the signal
of the PPh2 group from l: −6 for 14-Gn to :14
ppm for 15-Gn, and the shielding of the signal of the
PꢀS group from 57.8 for 12 to :51 ppm for 15-Gn.
The deprotection reaction induces a shielding of the
signal of the PPh2 group from :20 for 15-Gn to
: −6 ppm for 14-Gn+1. Analogous phenomena are
observed in the last step, with the grafting of the azide
7 (Fig. 1).
2
(Ph3PꢀNꢁPꢀS) with JPP=28.9 Hz, and l=13.2 and
2
50.8 ppm (Ph2PꢀNꢁPꢀS) with JPP=29.4 Hz, and one
singlet at l= −6.4 ppm (free Ph2P). Dendrimer 14-G2
reacts with the azide 12 to give compound 15-G2,
which is deprotected with DABCO, leading to the
third generation 14-G3, whose 31P-NMR spectrum is
depicted Fig. 1.
Starting from the third generation 14-G3, we could
use again the azide 12, but we preferred to multiply
more rapidly the number of terminal phosphino
groups. Thus, the azide 7 was used instead of 12. The
reaction occurs easily, leading to dendrimer 16-G3,
whose protected phosphino groups are deprotected
with DABCO (Scheme 4). The fourth generation den-
drimer 17-G4 possesses 32 PPh2 groups, that is to say
four times the number of phosphino groups of the
preceding generation (Fig. 2). The 31P-NMR spectrum
confirms the obtaining of dendrimer 17-G4, with the
presence of one singlet (l= −4.9 ppm, free PPh2) and

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A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
Fig. 1. 31P-NMR spectra of all dendrimers from 15-G1 to 17-G4.

A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
117
sized possesses 32 PPh2 end groups and 15 PꢀNꢁPꢀS
groups. Since, we have previously demonstrated with
other dendrimers that both types of functions display a
versatile reactivity, work is in progress to study the
reactivity and the complexation properties of this new
series of dendrimers.
3. Conclusions
The functionalized 1,3-diphosphines that we have
obtained are difficult to use as building blocks for the
synthesis of dendrimers, but it is interesting to graft
them on the surface of dendrimers, in order to multiply
rapidly the number of phosphino end groups in the last
step. We have shown in particular that the grafting of
N3P(S)[OC6H3(PPh2BH3)2]2 allows to multiply by four
the number of end groups when going from the third to
the fourth generation. The largest compound synthe-
4. Experimental
General. All reactions were carried out in the absence
of air using standard Schlenk techniques and vacuum-
Fig. 2. Chemical structure of dendrimer 17-G4.

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A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
Fig. 3. Numbering used for NMR.
line manipulations. All solvents were dried, distilled
and degassed before use. Instrumentation: Bruker
AC80, AC200, or AM250 (1H-, 13C-, 31P-NMR),
Perkin–Elmer 1725X (FT-IR). The numbering used for
NMR assignment is depicted in Fig. 3. Elemental
analyses were performed by the Service d’Analyse du
Laboratoire de Chimie de Coordination, Toulouse
(France). Compound 12 was prepared according to a
published procedure [8]. The actual molar masses were
calculated from the response of a multi-angle Laser-
Light-Scattering detector (Wyatt Technology) ASTRA
software version 4.20, which was connected to the size
exclusion chromatography (MALLS/SEC) line.
was obtained as a white powder (yield 2.4 g, 65%).
Compound 1: 31P{1H}-NMR (CDCI3): l −4.8 (s).
1H-NMR (CDCl3): l 5.76 (br D, 1H, OH), 6.66 (ddd,
3JHP=7.64 Hz, 4JHH=1.27 Hz, 5JHP=2.5 Hz, 2H,
3
4
C2ꢁH), 6.88 (tt, JHP=7.65 Hz, JHH=1.27 Hz, 1H,
C4ꢁH), 7.19–7.35 (m, 20H, C6H5). 13C{1H}-NMR
2
(CDCl3): l 120.36 (d, JCP=18.8 Hz, C2), 128.33 (d,
2
3JCP=7.2 Hz, Cm), 128.66 (s, Cp), 130.89 (t, JCP=21.1
Hz, C4), 133.56 (d, 2JCP=19.1 Hz, Co), 136.38 (d,
1
3
1JCP=10.2 Hz, Ci), 139.12 (dd, JCP=13.0 Hz, JCP
=
7.2 Hz, C3), 155.72 (t, 3JCP=7.3 Hz, C1). Calc. for
C30H24OP2 (462.46): C, 77.91; H, 5.23. Anal. Found: C,
78.14; H, 5.28%.
4.2. Synthesis of 3,5
4.1. Synthesis of 3,5-bis(diphenylphosphino)phenol (1)
bis(borane-diphenylphosphino)phenol (2)
Ph2PCl (9 ml, 50 mmol) was added dropwise under
reflux to a stirred mixture of Na chips (2.6 g, 113
mmol) and dry 1,4-dioxane (6.5 ml). The mixture was
refluxed for a further 4 h and stirred overnight at room
temperature (r.t.). The suspension of Ph2PNa was
added to 3,5-difluorophenol (1.05 g, 8 mmol). The
mixture was stirred at 130–135 °C in a sealed Schlenk
flask for 12 days, then cooled. EtOH (15–20 ml) was
added to remove the residual Na metal and the mixture
was stirred for 0.5 h. The solution was evaporated to
dryness and the residue was extracted by CH2Cl2 (60
ml) for 1 h. The resulting suspension was centrifugated
and the precipitate was removed by a careful decanta-
tion. The solvent was removed in vacuo, and the most
part of the side-product Ph2PH was distilled off under
vacuum (0.5 mm, 130–150 °C). Compound 1 was iso-
lated by column chromatography of the residue on
silica gel (THF–pentane 15:85 as eluent). Compound 1
BH3·SMe2 (2 M solution in toluene, 2.7 ml, 5.4
mmol) was added to a solution of 1 (0.95 g, 2.05 mmol)
in degassed THF (7 ml) at 0 °C. The reaction mixture
was stirred overnight at r.t., then evaporated to dry-
ness. Compound 2 was isolated by chromatography on
silica gel (ether–pentane (2:1) as eluent). Compound 2
was obtained as colorless crystals (yield 0.9 g, 89%).
M.p.: 77 °C (dec.).
Compound 2: 31P{1H}-NMR (CDCl3): l 21.4 (br s).
1H-NMR (CDCl3): l 1.1 (br s, 6H, BH3), 6.96 (tt,
3JHP=10.04 Hz, 4JHH=1.25 Hz, 1H, C4ꢁH), 7.27 (ddd,
3JHP=11.74 Hz, 4JHH=1.25 Hz, 5JHP=2.4 Hz, 2H,
C2ꢁH), 7.31–7.54 (m, 20H, C6H5). 13C{1H}-NMR
(CDCl3): l 122.60 (d,2JCP=12.2 Hz, C2), 128.13 (d,
3
1JCP=58 Hz, Ci), 128.67 (d, JCP=9.5 Hz, Cm), 131.29
1
3
(s, Cp), 131.75 (dd, JCP=54.5 Hz, JCP=10.7 Hz, C3),
132.84 (d, JCP=10.2 Hz, Co), 133.30 (t, JCP=12 Hz,
2
2
C4), 156.75 (t, 3JCP=13.6 Hz, C1). Calc. for

A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
119
C30H30B2OP2 (490.13): C, 73.51; H, 6.16. Anal. Found:
C, 73.40; H, 6.25%.
Calc. for C36H34B2N3O2P3S (687.29): C, 62.91; H, 4.98;
N, 6.11. Anal. Found: C, 62.79; H, 4.85; N, 6.03%.
4.3. Synthesis of the sodium salt of
3,5-bis(borane-diphenylphosphino)phenol (3)
4.5. Synthesis of azido bis(3,5-bis(borane-diphenyl-
phosphino)phenoxy)thiophosphate (7)
A solution of 2 (0.9 g, 1.84 mmol) in THF (6 ml) was
added dropwise to a stirred suspension of NaH (0.05 g,
2.08 mmol) in THF (3 ml). The reaction mixture was
stirred at r.t. for 2.5 h, the residual NaH was removed
by filtration under Ar and the filtrate was evaporated to
dryness overnight to give [3·2 THF] as a yellow powder
(yield 0.88 g, 73%).
A solution of [3·2 THF] (2.24 g, 3.4 mmol) in THF
(60 ml) was added dropwise very slowly to a stirred
solution of P(S)C13 (0.164 ml, 1.62 mmol) in THF (15
ml) between −95 and −100 °C. Then, the reaction
mixture was allowed to reach the r.t. very slowly and
was stirred overnight. The reaction mixture was par-
tially concentrated in vacuo, centrifugated and filtered
to remove NaCl. Evaporation of the filtrate in vacuo
gave chloro bis(3,5-bis(borane-diphenylphosphino)-
phenoxy)thiophosphate (6) (yield 1.7 g, 97.5%) as a
very viscous yellow oil, which was not further purified.
Compound 6: 31P{1H}-NMR (CDCl3): l 22.4 (br s,
P1), 58.4 (s, P0).
Compound 3: 31P{1H}-NMR (CDCl3): l 19.8 (br s).
1H-NMR (CDCl3): l 1.1 (br s, 6H, BH3), 1.66 (m, 8H,
3
CH2), 3.55 (m, 8H, ꢁCH2ꢁOꢁ), 6.25 (t, JHP=10.1 Hz,
3
1H, C4ꢁH), 6.79 (d, JHP=13.26 Hz, 2H, C2ꢁH), 7.16–
7.44 (m, 20H, C6H5).
4.4. Synthesis of azido (3,5-bis(borane-diphenyl-
phosphino)phenoxy)(phenoxy)thiophosphate (5)
Previously dried in vacuo NaN3 (0.12 g, 1.85 mmol)
was added to a stirred solution of unpurified 6 (1.70 g,
1.58 mmol) in acetone (10 ml) and the reaction mixture
was stirred overnight at r.t., then centrifugated and
filtered to remove NaCl. The filtrate was evaporated to
dryness. Compound 7 was isolated by chromatography
of the residue on silicagel (eluent: CHCl3) as a white
powder (yield 0.62 g, 33%). M.p.: 78–81 °C.
A solution of [3·2 THF] (2.49 g, 3.96 mmol) in THF
(60 ml) was added dropwise very slowly to a solution of
dichloro(phenoxy)thiophosphate (0.9 g, 3.96 mmol) in
THF (15 ml) between −90 and −100 °C under stir-
ring. The reaction mixture was allowed to reach slowly
the r.t. and was stirred overnight. The reaction mixture
was partially concentrated in vacuo, the precipitate was
removed by centrifugation and filtration under Ar.
Evaporation of the filtrate gave chloro(3,5-bis(borane-
diphenylphosphino)phenoxy)(phenoxy) thiophosphate
4 (yield 2.63 g, 98%) as a yellow oil which was not
further purified.
Compound 7: 31P{1H}-NMR (CDCl3): l 22.4 (br s,
1
P1), 59.4 (s, P0). H-NMR (CDCl3): l 7.17–7.78 (m,
C6H3, C6H5). 13C{1H}-NMR (CDCl3): l 127.49 (d,
1JCP1=58.1 Hz, Ci), 128.16 (dd, 2JCP1=11.4 Hz,
3JCP0=3.6 Hz, C2), 129.09 (d, 3JCP1=10.0 Hz, Cm),
2
131.84 (s, Cp), 133.06 (d, JCP1=9.8 Hz, Co), 133.82
(dd, 1JCP1=54.2 Hz, 3JCP1=9.8 Hz, C3), 134.86 (t,
Compound 4: 31P{1H}-NMR: l 58.7 (s, P0), 22.4 (br s,
P1).
2JCP1=7.9 Hz, C4), 149.82 (dt, JCP0=8.5 Hz, JCP1
=
2
3
12.8 Hz, C1). IR (KBr): 2189 cm−1 (w¯N3). Calc. for
C60H58B4N3O2P5S (1083.3): C, 66.52; H, 5.39; N, 3.87.
Anal. Found: C, 66.58; H, 5.45; N, 3.78%.
Previously dried in vacuo NaN3 (0.25 g, 4.38 mmol)
was added to the stirred solution of unpurified 4 (2.63
g, 3.86 mmol) in acetone (16 ml). The reaction mixture
was stirred overnight at r.t., and the precipitate of NaCl
was removed by centrifugation and filtration. The solu-
tion was evaporated to dryness and 5 was isolated by
chromatography of the residue on silica gel (pentane–
ether (1:1) as eluent) as a very viscous colorless oil
(yield 1.2 g, 45%).
4.6. Synthesis of compound 8
A solution of triphenylphosphine (0.203 g, 0.774
mmol) in CH2Cl2 (17 ml) was added dropwise slowly to
a stirred solution of 5 (0.532 g, 0.774 mmol) in CH2Cl2
(6 ml) at r.t. The reaction mixture was stirred overnight
and the solvent was removed in vacuo. Compound 8
was isolated by chromatography of the residue on silica
gel (pentane–ether as eluent, the ratio was changed
gradually from (1:1) to (1:3)) as a very viscous colorless
oil (yield 0.547 g, 76.7%).
Compound 5: 31P{1H}-NMR (CDCl3): l 22.3 (br s,
1
P1), 59.5 (s, P%). H-NMR (CDCl3): l 1.2 (br s, 6H,
0
BH3) 7.09–7.67 (m, 28H, C6H3, C6H5). 13C{1H}-NMR
(CDCl3): l 120.84 (d, JCP%0=4.4 Hz, C%2), 126.22 (d,
3
5JCP%0=2.3 Hz, C%4), 127.37 (d, 1JCP1=58.8 Hz, Ci),
128.14 (dd, JCP1=11.5 Hz, JCP%0=6 Hz, C2), 128.89
Compound 8: 31P{1H}-NMR (CDCl3): l 14.4 (d,
2
3
(d, JCP1=10.2 Hz, Cm), 129.76 (s, C%3), 131.64 (s, Cp),
2JP0P%0=28.8 Hz, P0), 21.7 (br s, P1), 52.6 (d, JP%0P0
=
3
2
132.91 (d, JCP1=10.1 Hz, Co), 133.41 (dd, JCP1=52
28.8 Hz, P%). H-NMR (CDCl3): l 1.2 (br s, 6H, BH3),
2
1
1
0
Hz, JCP1=10.3 Hz, C3), 134.38 (t, JCP1=8.9 Hz, C4),
7.55–6.98 (m, 43H, C6H3, C6H5). 13C{1H}-NMR
3
2
149.46 (d, JCP%0=8.3 Hz, C%1), 150.08 (dt, JCP%0=8.7
(CDCl3): l 121.41 (d, JCP%0=5.1 Hz, C%30), 124.25 (s,
2
2
3
Hz, JCP1=13.08 Hz, C1). IR (KBr): 2189 cm−1 (w¯N3).
C%), 127.93 (d, 1JCP1=57.8 Hz, Ci1), 128.14 (dd, 2JCP1
=
3
4
0

120
A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
3
1
11.3 Hz, JCP%0=4.9 Hz, C21), 128.4 (dd, JCP0=106 Hz,
3JCP%0=4 Hz, Ci0), 128.57 (d, 3JCP0=12.1 Hz, Cm0 ),
128.81 (s, C%03), 128.86 (d,2JCP1=10.0 Hz, Cm1 ), 131.52
NMR (CDCl3): l 121.36 (d, 3JCP%1=5.1 Hz, C%12),
121.52 (d, 3JCP%0=5.3 Hz, C%02), 124.15 (br s, C%41), 124.23
1
(br s, C%40), 127.21 (br d, JCP1=107.2 Hz, C31), 128.14
1
1
(d, JCP2=54.4 Hz, C2i ), 128.30 (dd, JCP0=106.7 Hz,
1
3
(s, Cp1), 131.85 (dd, JCP1=53.2 Hz, JCP1=9.8 Hz, C31),
3JCP%0=3.3 Hz, Ci0), 128.67 (d, JCP0=11.6 Hz, Cm0 ),
3
2
132.51 (s, C0p), 132.61 (d, JCP0=10.9 Hz, Co0), 133.01
3
128.8 (br s, C%30, C%13), 128.84 (d, JCP2=9.6 Hz, Cm2 ),
2
2
(d, JCP1=9.9 Hz, Co1), 134.41 (t, JCP1=8.3 Hz, C41),
1
3
128.98 (br d, JCP1=103.1 Hz, Ci1), 128.99 (d, CCP1
=
151.51 (d, JCP%0=8.4 Hz, C%4), 152.5 (dt, JCP%0=8.5
Hz, 3JCP1=13.1 Hz, C11). Calc. for C54H49B2NO2P4S
(921.6): C, 70.38; H, 5.35; N, 1.52. Anal. Found: C,
70.53; H, 5.44; N, 1.43%.%
2
2
1
9.8 Hz, Cm1 ), 131.41 (s, C2p), 131.76 (dd, JCP2=55.3 Hz,
3JCP2=10.2 Hz, C23), 132.66 (br d, JCP=11.8 Hz, Co0),
2
2
132.69 (br s, Cp0, C1p), 132.98 (d, JCP1=9.8 Hz, Co1),
2
133.06 (d, JCP2=9.7 Hz, Co2), 134.5 (br m, C14, C24),
2
2
151.55 (d, JCP%1=8.5 Hz, C%11), 151.68 (d, JCP%0=7.4
4.7. Synthesis of compound 9-G1
3
2
Hz, C%10), 152.42 (dt, JCP1=16 Hz, JCP%0=8 Hz, C11),
152.44 (dt, 3JCP2=13.5 Hz, 2JCP%1=7.6 Hz, C21), (C21
and C22 not detected). Calc. for C126H111B4N3O6P10S3
(2212.4): C, 68.40; H, 5.05; N, 1.89. Anal. Found: C,
68.03; H, 4.86; N, 1.75%.
A
solution
of
1,4-diazabicyclo-[2,2,2]-octane
(DABCO) (0.130 g, 1.20 mmol) in toluene (2 ml) was
added to a stirred solution of 8 (0.521 g, 0.566 mmol) in
toluene (5 ml). The reaction mixture was stirred
overnight at r.t. and the solvent was removed in vacuo.
Compound 9-G1 was isolated by chromatography on
silicagel (ether–pentane (1:1) as eluent) as a very vis-
cous colorless oil (yield 0.27 g, 53%).
4.9. Synthesis of polymer 11
NEt3 (0.23 ml, 1.66 mmol) was added to a stirred
solution of the azide 5 (0.275 g, 0.4 mmol) in THF (15
ml). The reaction was monitored by 31P-NMR spec-
troscopy. After 2 days the signal at 58.46 ppm (N3PꢀS
group) disappeared and 2.3 ml of NEt3 were added to
achieve the deprotection of the phosphino groups. The
reaction mixture was stirred for 6 days up to the
complete disappearance of the signal of protected phos-
phino groups at 21.6 ppm. The volatile components
were carefully removed in vacuo, and the residue was
washed first with Et2O, then with a mixture THF–pen-
tane and with ether. Compound 11 was obtained as a
very viscous colorless oil (yield 0.137 g, 54%).
Compound 9-G1: 31P{1H}-NMR (CDCl3): l −4.8 (s,
2
2
P1), 13.6 (d, JP0P%0=29 Hz, P0), 52.3 (d, JP%0P0=29
Hz, P%). 1H-NMR (CDCl3): l 6.93–7.57 (m, C6H5,
0
C6H3). 13C{1H}-NMR (CDCl3): l 121.41 (d, JCP%0
=
3
2
5.2 Hz, C%20), 123.7 (br s, C%04), 126.87 (dd, JCP1=18.7
3
3
Hz, JCP%0=4.6 Hz, C21), 128.26 (d, JCP1=7.2, H2, Cm1 ),
128.38 (d, 3JCP0=13.7 Hz, C0m), 128.5 (dd, 1JCP0=106.7
3
Hz, JCP%0=4.4 Hz, C0i ), 128.52 (s, C1p), 128.74 (s, C%30),
4
2
132.25 (d, JCPO=2.4 Hz, Cp0), 132.59 (d, JCP0=10.8
Hz, Co0), 133.52 (d, 2JCP1=19.8 Hz, Co1), 134.35 (t,
2JCP1=20.6 Hz, C41), 136.44 (d, JCP1=10.9 Hz, Ci1),
1
1
3
138.74 (dd, JCP1=12.3 Hz, JCP1=4.2 Hz, C31), 151.49
(d, 2JCP%0=8.2 Hz, C%01), 152.23 (dt, 2JCP%0=7.6 Hz,
3JCP1=9.6 Hz, C11). Calc. for C54H43NO2P4S (893.9): C,
72.55; H, 4.84; N, 1.56. Anal. Found: C, 72.32; H, 4.65;
N, 1.45%.
Compound 11: 31P{1H}-NMR (CDCl3): l −4.9 (s,
P1), −4.7 (s, P1), 13 (m, P), 52 (m, P%). 1H-NMR
(CDCl3): l 6.8–8.5 (m, C6H5, C6H3). MW: 3000.
4.10. Synthesis of polymer 11%
4.8. Synthesis of dendrimer 10-G1
A solution of DABCO (0.251 g, 2.24 mmol) in
toluene (2 ml) was added to the solution of the azide 5
(0.717 g, 1.044 mmol) in toluene (20 ml) and the
reaction mixture was stirred overnight at r.t. The reac-
tion mixture was filtrated, and the solvent was removed
in vacuo. The residue was washed three times by repre-
cipitation with pentane from toluene and two times by
MeCN and was dried in vacuo to give polymer 11% as a
very viscous colorless oil (yield 0.26 g, 43%).
A solution of 9-G1 (0.27 g, 0.3 mmol) in CH2Cl2 (17
ml) was added dropwise very slowly to a stirred solu-
tion of azide 5 (0.44 g, 0.64 mmol) in CH2Cl2 (6 ml).
The reaction mixture was stirred overnight. An addi-
tional portion of 5 (0.066 g) in CH2Cl2 (2 ml) was
added to accelerate and complete the reaction; the
reaction mixture was stirred for 1 day. The solvent was
removed in vacuo. Chromatography on silica gel with
the gradual increase of the eluent’s polarity from
CHCl3–CH2Cl2 mixture (9:1) to pure CH2Cl2 gave
10-G1 (yield 0.15 g, 22%) as a very viscous colorless oil.
Compound 10-G1: 31P{1H}-NMR (CDCl3): l 13.5 (d,
2JP1P%1=29.4 Hz, P1), 14.6 (d, 2JP0P%0=28.2 Hz, P0).
Compound 11%: 31P{1H}-NMR (CDCl3): l −4.9
(20%) and −4.7 (80%) (2s, P1), 13 (m, P), 52 (m, P%).
1H-NMR (CDCl3): l 6.5-8.6 (m, C6H5, C6H3). MW:
3800.
4.11. Synthesis of compound 13
2
21.7 (br s, P2), 52.6 (d, JP%0P0=28.2 Hz, P%0), 52.7 (d,
1
2JP%1P1=29.4 Hz, P%). H-NMR (CDCl3): l 1.2 (br s,
A solution of Ph3P (0.187 g, 0.729 mmol) in CH2Cl2
(6 ml) was added dropwise very slowly to a stirred
1
12H, BH3), 6.81–7.82 (m, 99H, C6H5, C6H3). 13C{1H}-

A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
121
1
solution of azidobis(4-borane-diphenylphosphinophe-
noxy)thiophosphate (12) (0.501 g, 0.729 mmol) in
CH2Cl2 (6 ml) at r.t. The reaction mixture was stirred
overnight, then filtrated and evaporated to dryness. The
residue was washed twice with pentane–THF. Com-
pound 13 was obtained as a white powder (yield 0.657
g, 98%). M.p.: 107 °C (dec.).
2JP%1P1=29.1 Hz, P%). H-NMR (CDCl3): l 1.3 (br s,
1
12H, BH3), 7.18–7.65 (m, 99H, C6H4, C6H5). 13C{1H}-
3
3
NMR (CDCl3): l 121.89 (br dd, JCP%=5 Hz, JCP
=
1
10.4 Hz, C21, C22), 123.33 (br d, JCP1=110.2 Hz, C14),
1
1
124.11 (d, JCP2=60.2 Hz, C42), 128.15 (dd, JCP0=108
3
1
Hz, JCP%0=3.7 Hz, C0i ), 128.43 (dd, JCP1=107.9 Hz,
3JCP%1=3.1 Hz, C1i ), 128.82 (br d, JCP=10.9 Hz, Cm0 ,
3
Compound 13: 31P{1H}-NMR (CDCl3): l 14.4 (d,
1
Cm1 , Cm2 ), 129.3 (d, JCP2=49.6 Hz, Ci2), 131.31 (br s,
2
2JP0P%0=29.1 Hz, P0), 19.9 (br s, P1), 50.1 (d, JP%0P0
=
2
Cp2), 132.72 (d, JCP=10.7 Hz, C0o, C1o), 132.81 (s, C0p,
1
29.1 Hz, P%). H-NMR (CDCl3): l 1.5 (br s, 6H, BH3),
2
2
Cp1), 133.09 (d, JCP2=9.7 Hz, Co2), 134.33 (d, JCP1
=
0
7.19–7.61 (m, 43H, C6H5, C6H4). 13C{1H}-NMR
2
15.8 Hz, C31), 134.54 (d, JCP2=10.56 Hz, C32), 154.61
(d, 2JCP%1=8.1 Hz, C11), 155.65 (dd, 2JCP%0=8.4 Hz,
4JCP1=2.1 Hz, C12). Calc. for C126H111B4N3O6P10S3
(2212.4): C, 68.40; H, 5.05; N, 1.89. Anal. Found: C,
68.28; H, 4.97; N, 1.78%.
3
3
(CDCl3): l 121.93 (dd, JCP1=10.8 Hz, JCP%0=5 Hz,
1
1
C21), 124.07 (d, JCP%0=60.2 Hz, C41), 128.3 (dd, JCP0
=
3
3
108.8 Hz, JCP0=3.5 Hz, Ci0), 128.74 (d, JCP0=13.5
Hz, Cm0 ), 128.77 (d, 3JCP1=9.7 Hz, Cm1 ), 129.3 (d,
1JCP1=55.3 Hz, C1i ), 131.25 (s, Cp1), 132.73 (d, JCP0
=
2
2
11.07 Hz, Co0), 132.82 (s, C0p), 133.1 (d, JCP1=9.8 Hz,
4.14. Synthesis of dendrimer 14-G2
2
2
Co1), 134.49 (d, JCP1=10.9 Hz, C31), 154.57 (d, JCP%0
=
7.1 Hz, C11). Calc. for C54H49B2NO2P4S (921.57): C,
70.38; H, 5.35; N, 1.52. Anal. Found: C, 70.25; H, 5.28;
N, 1.48%.
Compound 14-G2 was obtained from 15-G1 (0.728 g,
0.329 mmol) and DABCO (0.162 g, 1.44 mmol) in
toluene (10 ml), analogously to 14-G1. Compound 14-
G2 was purified by two-time reprecipitation with ether
from toluene. An additional portion of 14-G2 was
obtained by chromatography on silicagel of the concen-
trated filtrate from washings (toluene–ether (9:1)).
Compound 14-G2 was obtained as a white powder
(yield 0.48 g, 67.7%). M.p.: 102–106 °C.
4.12. Synthesis of dendrimer 14-G1
A solution of DABCO (0.182 g, 1.62 mmol) in
toluene (2 ml) was added to a stirred solution of 13
(0.677 g, 0.735 mmol) in toluene (7 ml). The reaction
mixture was stirred for 2 days, then the solvent was
removed in vacuo. Column chromatography of the
residue on silica gel with toluene as eluent gave 14-G1
(yield 0.45 g, 69%) as a white powder. M.p.: 59–62 °C.
Compound 14-G1: 31P{1H}-NMR (CDCl3): l −6.2
Compound 14-G2: 31P{1H}-NMR (CDCl3): l −6.4
2
2
(s, P2), 13.2 (d, JP1P%1=29.4 Hz, P1), 14.8 (d, JP%0P0
=
28.9 Hz, P0) 49.9 (d, 2JP%0P0=28.9 Hz, P%), 50.8 (d,
0
1
2JP%1P1=29.4 Hz, P%). H-NMR (CDCl3): l 6.95–7.65
1
2
2
(m, C6H4, C6H5). 13C{1H}-NMR (CDCl3): l 121.77 (br
(s, P1), 13.6 (d, JP0P%0=29.5 Hz, P0). 50.9 (d, JP%0P0
=
1
3
3
dd, JCP%=5.5 Hz, JCP=7.4 Hz, C21, C22), 123.64 (dd,
29.5 Hz, P%). H-NMR (CDCl3): l 7.14–7.67 (m, C6H4,
0
C6H5). 13C{1H}-NMR (CDCl3): l 121.64 (dd, JCP1=7
3
1JCP1=110.9 Hz, 3JCP%1=3.8 Hz, C41), 128.16 (dd,
3
3
Hz, JCP%0=5.9 Hz, C21), 128.35 (d, JCP1=7 Hz, Cm1 ),
1JCP0=105.8 Hz, 3JCP%0=3.5 Hz, Ci0), 128.53 (d,
3
3
128.45 (dd, JCP0=106.6 Hz, JCP%0=3 Hz, Ci0), 128.49
1
3JCP2=7 Hz, Cm2 ), 128.73 (s, Cp2), 128.76 (dd, JCP1
=
(d, 3JCP0=12.7 Hz, C0m), 128.56 (s, Cp1), 131.77 (d,
3
3
105.9 Hz, JCP%1=3.6 Hz, Ci1), 128.84 (d, JCP=13.4
1JCP1=10.4 Hz, C14), 132.49 (s, Cp0), 132.66 (d, JCP0
=
3
1
Hz, Cm0 , Cm1 ), 132.05 (d, JCP2=9.9 Hz, C42), 132.60 (s,
2
11.2 Hz, Co0), 133.46 (d, JCP1=19.1 Hz, Co1), 133.73 (d,
Cp0, Cp1), 132.78 (br d, 2JCP=11.8 Hz, C0o, Co1), 133.61 (d,
2JCP1=20.8 Hz, C31), 137.16 (d, JCP1=10.3 Hz, Ci1),
1
2JCP2=19.5 Hz, Co2), 134.36 (d, JCP1=12.1 Hz, C31),
2
2
152.72 (d, JCP%0=10 Hz, C11). Calc. for C54H43NO2P4S
134.92 (d, 2JCP2=20.6 Hz, C23), 137.38 (d, 1JCP2=10Hz,
(893.90): C, 72.55; H, 4.84; N, 1.56. Anal. Found: C,
72.48; H, 4.73; N, 1.49%.
2
2
Ci2), 152.88 (d, JCP%1=9.6 Hz, C12), 155.54 (dd, JCP%0
=
for
10.2
Hz,
4JCP1=3.7
Hz,
C11).
Calc.
C126H99N3O6P10S3 (2157.1): C, 70.15; H, 4.62; N, 1.94.
Anal. Found: C, 69.98; H, 4.75; N, 1.88%.
4.13. Synthesis of dendrimer 15-G1
Compound 15-G1 was obtained from 14-G1 (0.439 g,
0.492 mmol) and 12 (0.7 g, 1.02 mmol) in CH2Cl2,
analogously to 13. Compound 15-G1 was purified by
two-time reprecipitation with ether from THF. Com-
pound 15-G1 was isolated as a white powder (yield 0.72
g, 67%). M.p.: 124–130 °C (dec.).
4.15. Synthesis of dendrimer 15-G2
Compound 15-G2 was obtained from 14-G2 (0.284 g,
0.126 mmol) and 12 (0.362 g, 0.527 mmol) in degassed
CH2Cl2, analogously to 15-G1. Compound 15-G2 was
purified by two-time reprecipitation with ether from
THF. Compound 15-G2 was obtained as a white pow-
der (yield 0.42 g, 69%). M.p. 154–160 °C.
Compound 15-G1: 31P{1H}-NMR (CDCl3): l 14.1 (d,
2JP1P%1=29.1 Hz, P1), 14.9 (d, 2JP0P%0=28.7 Hz, P0),
2
19.8 (br s, P2), 49.9 (d, JP%0P0=28.7 Hz, P%), 50.1 (d,
0

122
A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
Compound 15-G2: 31P{1H}-NMR (CDCl3): l 14.0 (d,
(6 ml) was added dropwise very slowly to a stirred
solution of the azide 7 (0.472 g, 0.436 mmol) in CH2Cl2
(6 ml) at r.t. The reaction mixture was stirred overnight
at r.t., filtrated and the solvent was removed in vacuo.
The residue was washed twice by reprecipitation with
ether from THF and dried overnight in vacuo to give
16-G3 as a white powder (yield 0.61 g, 95%). M.p.:
142–146 °C (dec.).
2JP2P%2=29.6 Hz, P2), 14.4 (d, 2JP1P%1=29.0 Hz, P1),
2
14.8 (d, JP0P%0=29.1 Hz, P0), 19.8 (br s, P3), 49.8 (d,
2JP%1P1=29 Hz, P%), 49.9 (d,2JP%0P0=29.1 Hz, P%) 50.1
1
0
(d, 2JP%2P2=29.6 Hz, P%). 1H-NMR (CDCl3): l 1.2 (br s,
2
24H, BH3), 7.16–7.61 (m, 211H, C6H5, C6H4).
13C{1H}-NMR (CDCl3): l 121.56–121.97 (m, C12, C22,
C32), 123.15 (br d, 1JCP1=110.1 Hz, C41), 123.28 (dd,
1JCP2=110.3 Hz, 3JCP%2=3.5 Hz, C42), 124.05 (d,
1JCP3=60.3 Hz, C34), 128.02 (dd, 1JCP0=108 Hz,
3JCP%0=3.5 Hz, Ci0), 128.21 (dd, 1JCP1=108.2 Hz,
3JCP%1=3.5 Hz, C1i ), 128.36 (dd, 1JCP2=108 Hz,
Compound 16-G3: 31P{1H}-NMR (CDCl3): l 14.1 (d,
2JP2P%2=29.0 Hz, P2), 14.2 (d, 2JP1P%1=28.6 Hz, P1),
2
2
14.8 (d, JP0P%0=27.2 Hz, P0), 15.2 (d, JP3P%3=28.1 Hz,
2
P3), 21.0 (br s, P4), 49.4 (d, JP%2P2=29.0 Hz, P%), 49.7
2
3
2
2
1 0
3JCP%2=3.3 Hz, Ci2), 128.74 (d, JCP=13.5 Hz, C0m, Cm1 ,
(d, JP%1P1=28.6 Hz, P%), 49.9 (d, JP%0P0=27.2 Hz, P%),
3
1
2
1
Cm2 ), 128.80 (d, JCP3=10.3 Hz, Cm3 ), 129.26 (d, JCP3
=
53.1 (d, JP%3P3=28.1 Hz, P%). H-NMR (CDCl3): l 1.2
3
2
47.2 Hz, Ci3), 131.28 (s, C3p), 132.67 (d, JCP=11.7 Hz,
(br s, 96H, BH3), 7.00–7.60 (m, 579H, C6H5, C6H4,
2
Co0, Co1, Co2), 132.90 (s, C0p, C1p, Cp2), 133.06 (d, JCP3=9.9
C6H3). 13C{1H}-NMR (CDCl3): l 121.57–121.88 (m,
2
1
Hz, Co3), 134.30 (d, JCP=14 Hz, C13, C23), 134.51 (d,
C21, C22, C23), 123.0 (br d, JCP3=108 Hz, C43), 123.27 (br
2JCP3=11.4 Hz, C33), 154.53 (d, 2JCP%2=8.3 Hz, C13),
d, JCP=110.1 Hz, C41, C24), 128.06 (d, JCP4=57.7 Hz,
1
1
2
4
155.57 (dd, JCP=9.7 Hz, JCP=3.2 Hz, C11, C21). Calc.
for C270H235B8N7O14P22S7 (4794.2): C, 67.64; H, 4.94;
N, 2.04. Anal. Found: C, 67.55; H, 4.89; N, 1.98%.
Ci4), 128.10 (dd, 1JCP3=108 Hz, 3JCP%3=3 Hz, Ci3),
1
3
128.3 (br m, C24), 128.40 (dd, JCP=110 Hz, JCP%=3
3
Hz, Ci1, Ci2), 128.70 (d, JCP=11.4 Hz, C0m, C1m, Cm2 ,
Cm3 ), 128.87 (d, 3JCP4=9.9 Hz, C4m), 131.48 (s, Cp4),
1
2
4.16. Synthesis of dendrimer 14-G3
131.95 (br d, JCP4=50 Hz, C34), 132.57 (br d, JCP
=
9.9 Hz, Co0, C1o, C2o, Co3, Cp0, Cp1, C2p, C3p), 133.00 (d,
Compound 14-G3 was obtained from 15-G2 (0.42 g,
0.0876 mmol) and DABCO (0.122 g, 1.09 mmol) in
toluene for 3 days, analogously to 14-G1. Compound
14-G3 was purified by two-time reprecipitation with
ether from toluene and dried in vacuo. Compound
14-G3 was obtained as a white powder (yield 0.4 g,
97%). M.p.: 118–120 °C.
2JCP4=9.7 Hz, Co4), 134.06 (d, 2JCP3=12.1 Hz, C33),
2
2
134.25 (t, JCP4=12.0 Hz, C44), 134.34 (d, JCP=11.4
3
3
Hz, C31, C32), 152.09 (dt, JCP4=11.9 Hz, JCP%3=10.1
Hz, C14), 155.52–155.65 (m, C11, C12, C31), (Ci0 not de-
tected). Calc. for C750H675B32N15O30P62S15 (13 126): C,
68.62; H, 5.18; N, 1.60. Anal. Found: C, 68.54; H, 5.12;
N, 1.52%.
Compound 14-G3: 31P{1H}-NMR (CDCl3): l −6.3
2
2
(s, P3), 13.0 (d, JP2P%2=29.5 Hz, P2), 14.3 (d, JP1P%1
=
4.18. Synthesis of dendrimer 17-G4
2
29.2 Hz, P1), 14.7 (d, JP0P%0=28.7 Hz, P0), 49.8 (d,
2JP%1P1=29.2 Hz, P%), 49.9 (d, 2JP%0P0=28.7 Hz, P%),
DABCO (0.147 g, 1.31 mmol) was added to a solu-
tion of 16-G3 (0.359 g, 0.027 mmol) in a toluene–
CH2Cl2 mixture (5:1) (7 ml). The solution was stirred
overnight at r.t. and evaporated. Degassed toluene (4
ml) was added to the residue and the precipitate was
removed by filtration. Compound 17-G4 was isolated by
reprecipitation with ether from the filtrate and addi-
tionally washed by reprecipitation with ether from tolu-
ene. Compound 17-G4 was obtained as a white powder
(yield 0.28 g, 80%). M.p. 125–128 °C.
1
0
50.9 (d, 2JP%2P2=29.5 Hz, P%). 1H-NMR (CDCl3): l
2
7.14–7.59 (m, C6H5, C6H4). 13C{1H}-NMR (CDCl3): l
121.25–121.8 (m, C21, C22, C32), 123.41 (br d, 1JCP=111.7
1
3
Hz, C41, C42), 127.86 (dd, JCP0=106.7 Hz, JCP%0=3.5
1
3
Hz, Ci0), 128.10 (dd, JCP1=105.7 Hz, JCP%1=3.5 Hz,
3
3
Ci1), 128.34 (d, JCP3=6.3 Hz, Cm3 ), 128.42 (d, JCP
=
=
1
3
9.8 Hz, Cm1 , Cm2 ), 128.52 (dd, JCP2=109.6 Hz, JCP%2
3
3.5 Hz, Ci2), 128.53 (s, C3p), 128.65 (d, JCP0=12.4 Hz,
Cm0 ), 131.84 (d, 1JCP3=9.6 Hz, C43), 132.57 (br d, 2JCP
=
2
12 Hz, Co0, Co1, C2o, C0p, C1p, Cp2), 133.41 (d, JCP3=19.6
Compound 17-G4: 31P{1H}-NMR (CDCl3): l −4.9
2
2
2
Hz, Co3), 134.18 (d, JCP=12.5 Hz, C13, C23), 134.72 (d,
(s, P4), 13.4 (d, JP3P%3=29.7 Hz, P3), 14.2 (d, JP2P%2=
2JCP3=20.7 Hz, C33), 137.17 (d, JCP3=11.1 Hz, Ci3),
29.1 Hz, P2), 14.3 (d, JP1P%1=28.9 Hz, P1), 14.8 (d,
1
2
2
2
152.67 (d, JCP%2=9 Hz, C13), 155.28 (d, JCP%1=7.2 Hz,
2JP0P%0=28.8 Hz, P0), 49.5 (d, 2JP%2P2=29.1 Hz, P%),
2
4JCP1=3 Hz, C12), 155.45 (dd, JCP%0=7.2 Hz, JCP0=3
Hz, C11). Calc. for C270H211N7O14P22S7 (4683.5): C,
69.24; H, 4.54; N, 2.09. Anal. Found: C, 69.15; H, 4.48;
N, 2.00%.
49.7 (d, JP%1P1=28.9 Hz, P%), 49.9 (d, JP%0P0=28.8 Hz,
2
4
2
2
1
2
1
P%), 52.6 (d, JP%3P3=29.7 Hz, P%). H-NMR (CDCl3): l
0
3
6.97–7.54 (m, C6H5, C6H4, C6H3). 13C{1H}-NMR
(CDCl3): l 121.3–122.15 (m, C21, C22, C32), 123.30 (br d,
1JCP=113 Hz, C14, C24), 123.48 (br d, JCP3=114.7 Hz,
1
4.17. Synthesis of dendrimer 16-G3
C43), 126.95 (br d, 2JCP4=21 Hz, C24), 128.40 (br d,
1JCP=110 Hz, Ci1, C2i ), 128.43 (d, JCP4=6.1 Hz, Cm4 ),
3
A solution of 14-G3 (0.230 g, 0.049 mmol) in CH2Cl2
128.63 (dd, 1JCP3=106.1 Hz, 3JCP%3=3.6 Hz, Ci3),

A. Balue6a et al. / Journal of Organometallic Chemistry 643–644 (2002) 112–124
123
128.79 (br d, 3JCP=12.3 Hz, Cm0 , C1m, Cm2 , Cm3 , C4p),
(e) G. Schmid, W. Meyer-Zaika, R. Pugin, T. Sawitowski, J.P.
Majoral, A.M. Caminade, C.O. Turrin, Chem. Eur. J. 6 (2000)
1693;
(f) M.K. Boggiano, G.J.A.A. Soler-Illia, L. Rozes, C. Sanchez,
C.O. Turrin, A.M. Caminade, J.P. Majoral, Angew. Chem. Int.
Ed. 39 (2000) 4249;
(g) C.O. Turrin, V. Maraval, A.M. Caminade, J.P. Majoral, A.
Mehdi, C. Reye´, Chem. Mater. 12 (2000) 3848;
(h) R. Go¨ller, J.P. Vors, A.M. Caminade, J.P. Majoral, Tetra-
hedron Lett. 42 (2001) 3587.
2
132.64 (br d, JCP=11 Hz, Co0, Co1, C2o, C3o, C0p, C1p, Cp2,
2
2
Cp3), 133.61 (d, JCP4=19.7 Hz, Co4), 134.10 (t, JCP4
=
2
20 Hz, C44), 134.22 (d, JCP3=10.4 Hz, C33), 134.40 (br
2
1
d, JCP=12.5 Hz, C31, C23), 136.67 (d, JCP4=11 Hz,
Ci4), 138.79 (dd, 1JCP4=9.3 Hz, 3JCP4=5.7 Hz, C34),
2
3
152.09 (dt, JCP%3=8.6 Hz, JCP4=6.3 Hz, C14), 155.2–
155.9 (m, C11, C21, C31), (Ci0 not detected). Calc. for
C
750H579N15O30P62S15 (12 683): C, 71.02; H, 4.60; N,
[5] (a) M. Slany, M. Bardaj´ı, M.J. Casanove, A.M. Caminade,
J.P. Majoral, B. Chaudret, J. Am. Chem. Soc. 117 (1995)
9764;
1.65. Anal. Found: C, 70.89; H, 4.54; N, 1.57%.
(b) M. Slany, AM. Caminade, J.P. Majoral, Tetrahedron Lett.
37 (1996) 9053;
(c) M. Bardaj´ı, M. Kustos, A.M. Caminade, J.P. Majoral, B.
Chaudret, Organometallics 16 (1997) 403;
Acknowledgements
Thanks are due to Daniel Taton and Yves Gnanou
(Bordeaux, France) for SEC analyses, to the Ministe`re
des Affaires Etrange`res for a grant to A.B., and to the
European Community for a grant to S.M.
(d) M. Slany, M. Bardaji, A.M. Caminade, B. Chaudret, J.P.
Majoral, Inorg. Chem. 36 (1997) 1939;
(e) M. Bardaji, A.M. Caminade, J.P. Majoral, B. Chaudret,
Organometallics 16 (1997) 3489;
(f) A.M. Caminade, R. Laurent, B. Chaudret, J.P. Majoral,
Coord. Chem. Rev. 178–180 (1998) 793;
(g) V. Huc, A. Balueva, R.M. Sebastian, A.M. Caminade, J.P.
Majoral, Synthesis (2000) 726;
(h) V. Maraval, R. Laurent, A.M. Caminade, J.P. Majoral,
Organometallics 19 (2000) 4025.
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