Synthesis and core and surface reactivity of phosphorus-based dendrons

Article abstract of DOI:10.1002/ejic.200400016

A series of phosphorus-containing dendrons is synthesized starting from a unique precursor (EtO)₂P(O)CH=CHC₆H₄PPh ₂ (3-G₀), whose X-ray crystal structure shows an extended planarity between both phosphorus. Staudinger reactions with functionalized azides on the phosphino group are the first step for the growth of the dendrons, which is continued using a divergent method. Several types of reactions are performed on dendrons of several sizes, either at the level of the core or of the surface. The specific addition of methyl triflate to P=S and trimethylsilyl triflate to P=O at the level of the core affords a dicationic species. A ¹³C NMR spectroscopic study indicates to what extent the charges are delocalized. Phosphanes are grafted on the surface of a second-generation dendron, and used for the complexation of PdCI₂. Both compounds possess five different types of phosphorus atoms, which helps in characterizing them by ³¹P NMR spectroscopy. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejic.200400016

FULL PAPER
Synthesis and Core and Surface Reactivity of Phosphorus-Based Dendrons
[a]
[a]
[a]
[a]
´
´
´
Rosa-Marıa Sebastian, Laurent Griffe, Cedric-Olivier Turrin, Bruno Donnadieu,
Anne-Marie Caminade,*[a] and Jean-Pierre Majoral*[a]
Keywords: Azides / Dendrimers / Dendrons / N,P ligands / Phosphorus
A series of phosphorus-containing dendrons is synthesized
starting from a unique precursor (EtO)2P(O)CH=CHC6H4PPh2 study indicates to what extent the charges are delocalized.
core affords a dicationic species. A 13C NMR spectroscopic
(3-G0), whose X-ray crystal structure shows an extended
planarity between both phosphorus. Staudinger reactions
with functionalized azides on the phosphino group are the
first step for the growth of the dendrons, which is continued
using a divergent method. Several types of reactions are per-
formed on dendrons of several sizes, either at the level of the
core or of the surface. The specific addition of methyl triflate
to P=S and trimethylsilyl triflate to P=O at the level of the
Phosphanes are grafted on the surface of a second-genera-
tion dendron, and used for the complexation of PdCl2. Both
compounds possess five different types of phosphorus atoms,
which helps in characterizing them by 31P NMR spectro-
scopy.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2004)
Introduction
characterization. We report in this paper the synthesis and
characterization of a series of dendrons having a phosphon-
ate at the core and up to five different types of phosphorus
atoms in the structure; these are clearly distinguishable by
31P NMR spectroscopy. Furthermore, these compounds
possess a versatile reactivity at every step of the synthesis,
as will be illustrated by three very different examples.
Dendrons[1] are dendritic wedges that differ from classical
dendrimers[2] by the presence of a functional group at the
level of the core. Such compounds can be built using either
a convergent[3] or a divergent[4] process, and they have
found applications as building blocks for the rapid synthesis
of dendrimers[5] or for the coating of the surface of various
materials, for example.[6] The nature of the function located
at the core is of crucial importance when synthesizing den-
drons, particularly if a divergent process is used. Indeed,
this function is present from the beginning of the synthesis
and hence it must be compatible with the whole synthetic
process while remaining available for further reactions after
the growth of the dendron. Due to the wide range of uses
and applications of phosphonates in organic synthesis, bi-
ology and materials chemistry,[7] we decided to graft a phos-
phonate at the core, linked through a potentially conjugated
linkage, which may act as a probe for sensing further reac-
tivity.
We have already reported the divergent synthesis of phos-
phorus-containing dendrons[4,8,9] and dendrimers,[10] and
shown that 31P NMR spectroscopy is an extraordinarily
useful tool for characterizing such compounds. However,
when the chemical structure is similar at each layer, a par-
tial overlap of signals may occur.[11] We and others have
shown that using two[12] or three[13,14] types of chemical en-
vironment around the phosphorus atoms allows an easier
Results and Discussion
The method used for grafting the phosphonate at the
core consists of the HornerϪWadsworthϪEmmons reac-
tion[15] of tetraethylmethylene gem-diphosphonate 1 with
diphenylphosphino benzaldehyde 2 in the presence of NaH
that we have already applied to the surface of dendrimers[16]
(Scheme 1). The reaction creates a CϭC bond connecting
the phosphonate to the aryl group. The resulting vinyl pho-
sphonate derivative 3-G0 was isolated in quantitative yield.
The expected E-configuration of the alkene bond is shown
1
3
in the H NMR spectrum by the large value of the JH,H
coupling constant (17.2 Hz). Single crystals of 3-G0 were
obtained by slow evaporation of a solution in CH2Cl2 and
allowed the determination of its structure by X-ray diffrac-
[a]
Laboratoire de Chimie de Coordination CNRS
205, Route de Narbonne, 31077 Toulouse Cedex 4, France
Fax: ϩ33-(0)5-61553003
E-mail: caminade@lcc-toulouse.fr
majoral@lcc-toulouse.fr
Scheme 1
Eur. J. Inorg. Chem. 2004, 2459Ϫ2466
DOI: 10.1002/ejic.200400016
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A.-M. Caminade, J.-P. Majoral et al.
FULL PAPER
tion. The ORTEP drawing is shown in Figure 1 and con-
firms the E-configuration of the CϭC bond. All atoms
from P2 to O3 are in a plane (Rms deviation 0.0685), indi-
cating an extended conjugation of 11 atoms.
Figure 2. Variation of the chemical shifts (13C NMR) for all carbon
atoms located from P(O) to P for four compounds (3-G0, 3-G1, 11-
G1, and 12-G1)
To continue the growth of the dendron, our classical
method of synthesis of dendrimers[18,19] was applied start-
ing from the aldehydes of 3-G1, and using the phosphorhy-
drazide 5 to generate dendron 3-G2. Then, the nucleophilic
substitution of Cl with hydroxybenzaldehyde sodium salt
afforded compound 6-G2. It is noteworthy that none of
these reactions has an influence on the vinylphosphonate
group located at the core, as shown by 31P NMR spec-
troscopy, with the presence of the singlet of the PϭO group
(δ ϭ 18.2 ppm) together with the singlet of the PϭS end
groups (δ ϭ 60.7 ppm) and both doublets corresponding to
the PϭNϪPϭS linkage (δ ϭ 13.7 and 51.8 ppm, respec-
tively).
˚
Figure 1. ORTEP drawing of 3-G0; selected bond lengths (A) and
angles (°): P1ϪO1 1.4605(16), P1ϪO2 1.5754(15), P1ϪO3
1.5794(16), P1ϪC1 1.775(2), C1ϪC2 1.322(3), P2ϪC6 1.8328(19),
P2ϪC13 1.839(2), P2ϪC19 1.8421(19); P1ϪC1ϪC2 125.04(17),
C1ϪC2ϪC3 126.25(19)
Compound 3-G0 is the starting material for the synthesis
of various dendrons. Indeed, the presence of a phosphane
allows it to undergo Staudinger reactions with func-
tionalized azides such as compound 4, which affords the
first generation dendron 3-G1 (Scheme 2). As expected,[17]
the PϭNϪPϭS linkage created by the reaction is charac-
terized in the 31P NMR spectrum by two doublets at δ ϭ
Thus, the growth of the dendron could have been pursued
to higher generations, as we have already shown with den-
drons containing other types of functions at the core,[4,8,9,20]
but we prefer to show the versatility and adaptability of this
method of synthesis at every step, including starting from
3-G0. Indeed, other types of functionalized azides can be
used, as shown by the reaction with compound 7 affording
8-G1 (Scheme 3). Here also, the Staudinger reaction induces
2
14.4 (PϭN) and 50.2 (PϭS) ppm with JP,P ϭ 31 Hz. In
the 13C NMR spectrum a dramatic shielding of the signals
corresponding to the carbons linked to the phosphorus that
undergoes the reaction is observed (∆δ ϭ Ϫ9.31 ppm for
C
ipsoPPh2; ∆δ ϭ Ϫ10.65 ppm for CipsoPC6H4) together with
1
a very important increase of the JC,P coupling constant.
More interestingly, the Staudinger reaction also induces
changes for the vinyl linkage, where the signal correspond-
ing to the ϭCH linked to C6H4 is shielded, whereas the
signal corresponding to (O)P-CHϭ is deshielded (∆δ ϭ
ϩ3.44 ppm), confirming a conjugation through the aro-
matic and vinyl linkages (Figure 2).
the appearance of two doublets in the 31P NMR spectrum
2
at δ ϭ 12.8 (PϭN) and 71.2 (PϭS) ppm with JP,P
ϭ
17.2 Hz. Obviously, the presence of NH2 groups opens the
way to a tremendous number of reactions, in particular con-
densations with functionalized aldehydes. As an illustration,
the carbohydrate derivative 9 (helicin) was condensed with
8-G1. The condensation induces an important shielding in
the 31P NMR spectrum for the signal corresponding to the
PϭS group, from δ ϭ 71.2 ppm for 8-G1 to δ ϭ 62.5 ppm
1
for 10-G1. A careful examination of the H and 13C NMR
spectra of 10-G1 shows that several signals corresponding
to the helicin and hydrazone moieties are split into two
series of signals in a 1:1 ratio; for example, the NCH3
groups give two doublets at δ ϭ 33.89 and 34.04 ppm. Such
splitting might be ascribed to E and Z isomers of the hydra-
zone bond (CϭN) with one E and one Z bond for each
molecule of 10-G1. Phosphorhydrazone bonds are generally
in the E configuration, thus the formation of a Z isomer
might be due to the occurrence of hydrogen bonds, which
forces one hydrazone linkage to be in the Z form, as pre-
viously noticed on the surface of dendrimers.[21] Due to the
carbohydrate moieties, 10-G1 is soluble in water, whereas all
the other dendrons described in this paper are not.
Scheme 2
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Phosphorus-Based Dendrons
FULL PAPER
Scheme 4
Scheme 3
charge on PϭO should hamper further addition of cations
to this group. The reaction monitored by 31P NMR spec-
troscopy shows a deshielding of the signal corresponding to
the PϭO group (∆δ ϭ 4 ppm) whereas no change is ob-
served for the other signals. The dicationic species 12-G1
was obtained quantitatively. The 13C NMR spectrum of 12-
G1 shows only modifications for the vinyl group, with a
shielding of the carbon linked to phosphorus (∆δ ϭ
Ϫ9 ppm) and a deshielding of the other carbon (∆δ ϭ
5 ppm) (Figure 2). Thus, the delocalization of the second
positive charge only has an influence on the (O)PϪCHϭ
CH linkage.
The last example illustrating the versatile reactivity of
this series of dendrons concerns 3-G2. Its P(S)Cl2 end-
groups can be reacted with various functionalized phenols
such as 13, which affords dendron 14-G2 (Scheme 5). These
phosphanyl end-groups are used because they are potential
N,P ligands. Indeed, we have shown previously that the cor-
responding Pd complexes linked to the surface of dendri-
mers efficiently catalyze Stille coupling reactions.[26] The
palladium complex 15-G2 is readily obtained by reaction
with [PdCl2(COD)]. Here again the 31P NMR spectrum
gives very informative data for the characterization. Fig-
We also tested another type of reactivity with compound
3-G1 — alkylation reactions — with the aim of detecting to
what extent the positive charge could be delocalized.[22] One
equivalent of the strong alkylating reagent methyl trifluoro-
methanesulfonate was added to 3-G1 (Scheme 4). We have
already shown that this reagent is able to alkylate the sulfur
atom included in a PϭNϪPϭS linkage,[13,17,23] but such a
reaction has never been performed in the presence of a pho-
sphonate group, although we have reported the specific al-
kylation of PϭS in macrocycles bearing phosphane oxide
groups.[24] The 31P NMR spectrum of the resulting com-
pound 11-G1 shows without any ambiguity that the alky-
lation occurs exclusively at the PϭS group. Indeed, a ∆δ
value of Ϫ27 ppm was measured for the signal correspond-
ing to PϭS, whereas it is only Ϫ1 ppm for the PϭO group,
on going from 3-G1 to 11-G1. Both signals corresponding
to PϭN (δ ϭ 22.2 ppm) and PϭS (δ ϭ 23.1 ppm) are close;
the assignment of the chemical shift was made by proton-
coupled 31P NMR spectroscopy, which gives a coupling
constant of 18.2 Hz for the signal at δ ϭ 23.1 ppm
(PϪSϪMe). The positive charge is delocalized to some ex-
tent onto the adjacent PϭN group (∆δ ϭ ϩ8 ppm). In view
of the extended planarity seen in the X-ray structure of 3-
G0, and the modification of the 13C NMR spectra on going
from 3-G0 to 3-G1, the charge might even be delocalized all
the way along the chain up to the phosphonate group. The
13C NMR spectrum shows a deshielding of the signal corre-
sponding to (O)P-CHϭ, which should correspond to a par-
tial positive charge on this atom (Figure 2, rhombuses).
However, the absence of a variation of the chemical shift
corresponding to PϭO seems to preclude an extension of
the delocalization up to it, and is in agreement with the
structure of 3-G0 obtained by X-ray diffraction in which the
oxygen of PϭO lies outside the main plane.
This assumption was reinforced by checking the reactiv-
ity of trimethylsilyl trifluoromethanesulfonate with 11-G1,
since we have already shown that it is able to react with
phosphane oxides.[25] Indeed, the presence of a positive Scheme 5
Eur. J. Inorg. Chem. 2004, 2459Ϫ2466
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A.-M. Caminade, J.-P. Majoral et al.
FULL PAPER
ure 3 shows the spectrum of 15-G2, with five different types have given three very different examples concerning modifi-
of phosphorus atoms clearly distinguishable, and in the ex- cation of the solubility, alkylation with delocalization of the
pected ratio.
charges, and grafting of N,P ligands as end-groups, along
with a preliminary study of their complexation properties.
Obviously, many other examples of reactions can be envis-
aged, in particular concerning the use of phosphonates for
the grafting of dendrons on the surface of various materials.
Indeed, it is known that phosphonates are able to react,
for instance, with alumina[27] and titania particles.[28] Thus,
compound 15-G2 could be used as precursor of hetero-
geneous catalysts.
Experimental Section
General Remarks: All manipulations were carried out with stand-
ard high vacuum and dry-argon techniques. The solvents were
freshly dried and distilled (THF and diethyl ether over sodium/
benzophenone; pentane and CH2Cl2 over phosphorus pentoxide;
toluene over sodium); they were degassed prior to use in the case
1
of experiments using trivalent phosphorus derivatives. H, 13C and
31P NMR spectra were recorded with Bruker AC 200, AC 250,
DPX 300 or AMX 400 spectrometers. References for NMR chemi-
1
cal shifts are 85% H3PO4 for 31P NMR and SiMe4 for H and 13C
NMR spectroscopy. The attribution of the 13C NMR signals was
performed by using Jmod, two dimensional HMBC, and HMQC,
Broad Band or CW 31P decoupling experiments when necessary.
The numbering used for the NMR assignments is depicted in Fig-
ure 4. Compounds 2,[29] 4,[30] 7,[30] and 13[26] were synthesized as
reported previously.
Phosphane 3-G0:
A
solution of (EtO)2P(O)CH2P(O)(OEt)2
(0.500 g, 1.680 mmol) in THF (5 mL) was added to a suspension
of NaH (0.043 g, 1.680 mmol) in THF (15 mL). After stirring for
10 min a clear solution was obtained. A solution of CHOC6H4PPh2
(0.490 g, 1.68 mmol) in THF (5 mL) was then added dropwise. The
resulting mixture was stirred overnight, then H2O (10 mL) was ad-
ded. The resulting mixture was concentrated under vacuum to elim-
inate THF, then CH2Cl2 (10 mL) was added. The organic phase
was recovered, and the water phase was washed twice with CH2Cl2.
The organic layers were combined and the solvents evaporated to
dryness to afford a pale yellow powder. 3-G0 was purified by col-
umn chromatography on silica gel (eluent: ethyl acetate) to afford
a white powder in 99% yield (0.700 g). Translucent crystals suitable
for X-ray diffraction were obtained after a slow evaporation of a
solution in CH2Cl2. 1H NMR (CDCl3): δ ϭ 1.30 (t, 3JH,H ϭ 7.1 Hz,
Figure 3. 31P NMR spectrum and chemical structure of 15-G2
Conclusion
We have shown in this paper that compound 3-G0 is a
multifunctional diphosphorus derivative, readily usable as
the core of various dendrons. These dendrons contain up
to five different types of phosphorus groups, which act as
sensitive labels that are able to detect subtle and remote
chemical modification, as shown by 31P NMR spectroscopy.
These dendrons also possess a versatile reactivity both at
the level of the core and of the end groups that is adaptable
3
6 H, CH3), 4.09 (dt, JH,H ϭ 7.1, 3JH,P ϭ 14.3 Hz, 4 H, CH2), 6.25
3
2
(t, JH,H ϭ JH,P ϭ 17.5 Hz, 1 H, ϭCH-P0), 7.21Ϫ7.46 (m, 14 H,
depending on the type of use desired. As an illustration, we HArom), 7.51 (d, 3JH,H ϭ 17.5 Hz, 1 H, CHϭCH-P0) ppm. 13C{1H}
Figure 4. Numbering used for NMR spectroscopy
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Eur. J. Inorg. Chem. 2004, 2459Ϫ2466

Phosphorus-Based Dendrons
NMR (CDCl3): δ ϭ 16.42 (d, JC,P ϭ 6.0 Hz, CH3), 61.84 (d, stirred overnight at room temperature. This solution was centri-
FULL PAPER
3
1
2JC,P ϭ 5.7 Hz, CH2), 114.68 (d, JC,P ϭ 191.2 Hz, ϭCH-P0),
fuged then evaporated to dryness. The resulting powder was washed
3
3
3
127.60 (d, JC,P ϭ 7.3 Hz, C0 ), 128.62 (d, JC,P ϭ 6.0 Hz, C0m),
with THF/pentane (1:10) to afford 6-G2 as a white powder in 90%
128.98 (s, C0p), 133.79 (d, 2JC,P ϭ 21.2 Hz, C0o), 133.83 (d, 2JC,P ϭ yield (0.087 g). H NMR (CDCl3): δ ϭ 1.32 (t, JH,H ϭ 7.1 Hz, 6
1
3
2
3
4
1
3
16.3 Hz, C0 ), 134.93 (d, JC,P ϭ 23.4 Hz, C0 ), 136.50 (d, JC,P
ϭ
H, CH2-CH3), 3.38 (d, JH,P ϭ 11.0 Hz, 6 H, N-CH3), 4.11 (dt,
10.1 Hz, C0 ), 140.50 (d, JC,P ϭ 13.5 Hz, C0 ), 148.07 (d, JC,P
ϭ
3JH,H ϭ 7.1, JH,P ϭ 15.0 Hz, 4 H, CH2), 6.35 (t, JH,H ϭ JH,P
ϭ
i
1
1
1
3
3
2
7.6 Hz, CHϭCH-P0) ppm. 31P{1H} NMR (CDCl3): δ ϭ Ϫ5.2 (s, 17.2 Hz, 1 H, ϭCH-P0), 7.19 (dd, JH,H ϭ 8.7, JH,P ϭ 1.4 Hz, 4
3
4
H, H-C1 ), 7.37 (dd, 3JH,H ϭ 8.5, 4JH,P ϭ 1.4 Hz, 8 H, H-C2 ), 7.57
2
2
P1), 19.5 (s, P0) ppm. C24H26O3P2 (424.41): calcd. C 67.92, H 6.17;
found C 67.96, H 6.19.
3
3
3
(d, JH,H ϭ 8.7 Hz, 4 H, H-C1 ), 7.85 (d, JH,H ϭ 8.5 Hz, 8 H, H-
3
C2 ), 7.40Ϫ7.74 (m, 17 H, HArom, CHϭN, CHϭCH), 9.92 (s, 4 H,
Dendron 3-G1: CH2Cl2 (10 mL) was added to a powdered mixture
of 3-G0 (0.302 g, 0.712 mmol) and the azide N3P(S)(OC6H4CHO)2
(0.247 g, 0.712 mmol). A rapid evolution of nitrogen was observed.
The solution was stirred overnight then evaporated to dryness to
afford 3-G1 as a pale yellow powder in 98% yield (0.520 g). A strict
1:1 ratio must be respected between 3-G0 and the azide, because
numerous washings of 3-G1 did not allow the elimination of the
unreacted starting materials. 1H NMR (CDCl3): δ ϭ 1.30 (t,
CHO) ppm. 13C{1H} NMR (CDCl3): δ ϭ 16.27 (d, 3JC,P ϭ 6.1 Hz,
2
2
CH2ϪCH3), 32.56 (d, JC,P ϭ 13.1 Hz, N-CH3), 62.05 (d, JC,P
5.7 Hz, CH2), 117.48 (d, JC,P ϭ 190.2 Hz, ϭCH-P0), 122.01 (br.
d, JC,P ϭ 4.0 Hz, C1 , C2 ), 127.28 (d, JC,P ϭ 13.5 Hz, C0 ),
ϭ
1
3
2
2
3
3
3
1
3
i
127.98 (s, C1 ), 128.01 (dd, JC,P ϭ 106.5, JC,P ϭ 5.0 Hz, C0 ),
128.49 (d, 3JC,P ϭ 14.0 Hz, C0m), 130.15 (dd, 1JC,P ϭ 108.0, 3JC,P ϭ
1
4
3
4
3.9 Hz, C0 ), 130.40 (s, C1 ), 131.26 (s, C2 ), 132.65 (s, C2 ), 132.68
(d, JC,P ϭ 11.0 Hz, C0o), 132.72 (s, C0p), 133.20 (d, JC,P
ϭ
2
2
3
3JH,H ϭ 7.1 Hz, 6 H, CH3), 4.09 (dt, JH,H ϭ 7.1, 3JH,P ϭ 14.6 Hz,
2
3
4
3
15.0 Hz, C0 ), 138.51 (d, JC,P ϭ 21.0 Hz, C0 ), 140.08 (d, JC,P
16.0 Hz, CHϭN-N), 146.72 (d, JC,P ϭ 6.0 Hz, CHϭCH-P0),
ϭ
3
2
4 H, CH2), 6.35 (t, JH,H ϭ JH,P ϭ 17.2 Hz, 1 H, ϭCH-P0), 7.26
2
2
(d, 3JH,H ϭ 8.0 Hz, 4 H, H-C1 ), 7.37Ϫ7.66 (m, 14 H, HArom), 7.55
2
1
2
1
153.12 (d, JC,P ϭ 10.2 Hz, C1 ), 156.85 (d, JC,P ϭ 9.8 Hz, C2 ),
3
3
(d, JH,H ϭ 17.2 Hz, 1 H, CHϭCH-P0), 7.73 (d, JH,H ϭ 8.0 Hz, 4
190.92 (s, CHO) ppm. 31P{1H} NMR (CDCl3): δ ϭ 13.7 (d, 2JP,P ϭ
H, H-C1 ), 9.86 (s, 2 H, CHO). 13C{1H} NMR (CDCl3): δ ϭ 16.39
3
2
29.2 Hz, P1), 18.2 (s, P0), 51.8 (d, JP,P ϭ 29.2 Hz, PЈ1), 60.7 (s, P2)
3
2
(d, JC,P ϭ 5.9 Hz, CH3), 62.07 (d, JC,P ϭ 5.9 Hz, CH2), 118.12
ppm. C68H62N5O13P5S3 (1408.3): calcd. C 57.99, H 4.44, N 4.97;
found C 58.11, H 4.47, N 4.94.
1
3
2
(d, JC,P ϭ 189.6 Hz, ϭCH-P0), 122.03 (d, JC,P ϭ 4.1 Hz, C1 ),
1
3
i
3
127.19 (dd, JC,P ϭ 106.0, JC,P ϭ 3.8 Hz, C0 ), 127.63 (d, JC,P
ϭ
13.5 Hz, C0 ), 128.84 (d, 3JC,P ϭ 13.7 Hz, C0m), 129.85 (dd, 1JC,P ϭ
3
Dendron 8-G1: Dichloromethane (1 mL) was added to a mixture of
3
1
3
4
113.0, JC,P ϭ 3.5 Hz, C0 ), 131.16 (s, C1 ), 132.60 (s, C1 ), 132.64
powdered 3-G0 (0.100 g, 0.236 mmol) and azide
7 (0.046 g,
(d, JC,P ϭ 11.7 Hz, C0o), 133.01 (s, C0p), 133.27 (d, JC,P
ϭ
2
2
0.236 mmol), to dissolve both reagents. The resulting solution was
stirred for three days at room temperature. The solvent was evapo-
rated to afford 8-G1 in quantitative yield as a white powder
2
3
4
2
11.6 Hz, C0 ), 138.95 (d, JC,P ϭ 24.3 Hz, C0 ), 146.49 (d, JC,P
ϭ
2
1
6.6 Hz, CHϭCH-P0), 156.79 (d, JC,P ϭ 9.4 Hz, C1 ), 190.96 (s,
CHO) ppm. 31P{1H} NMR (CDCl3): δ ϭ 14.4 (d, 2JP,P ϭ 31.0 Hz,
P1), 18.0 (s, P0), 50.2 (d, 2JP,P ϭ 31.0 Hz, PЈ1) ppm. C38H36NO7P3S
(743.69): calcd. C 61.37, H 4.88, N 1.88; found C 61.56, H 4.91,
N 1.79.
3
(0.140 g). 1H NMR (CDCl3): δ ϭ 1.28 (t, JH,H ϭ 7.0 Hz, 6 H,
3
CH2ϪCH3), 2.66 (d, JH,P ϭ 11.9 Hz, 6 H, N-CH3), 3.56 (br. s, 4
3
3
H, NH2), 4.06 (dt, JH,H ϭ 7.0, JH,P ϭ 14.5 Hz, 4 H, CH2), 6.31
3
2
(t, JH,H ϭ JH,P ϭ 17.2 Hz, 1 H, ϭCH-P0), 7.36Ϫ7.84 (m, 15 H,
H
Arom, CHϭCH-P0) ppm. 13C{1H} NMR (CDCl3): δ ϭ 16.36 (d,
Dendron 3-G2: A solution of H2NNMeP(S)Cl2 in CHCl3 (1.12 mL,
0.260 mmol) was added to a solution of 3-G1 (0.088 g, 0.118 mmol)
in THF (10 mL). The resulting solution was stirred for 4 hours
then evaporated to dryness to afford an oil. This oil was washed
three times with CH2Cl2/pentane then evaporated to dryness to af-
ford 3-G2 as a pale yellow powder in 81% yield (0.102 g). 1H NMR
3JC,P ϭ 5.9 Hz, CH2ϪCH3), 39.37 (d, JC,P ϭ 6.0 Hz, N-CH3),
2
62.00 (d, 2JC,P ϭ 5.7 Hz, CH2), 117.50 (d, 1JC,P ϭ 190.5 Hz, ϭCH-
3
3
3
P0), 127.53 (d, JC,P ϭ 13.1 Hz, C0 ), 128.70 (d, JC,P ϭ 12.2 Hz,
1
i
1
C0m), 129.40 (br. d, JC,P ϭ 110.0 Hz, C0 ), 129.90 (d, JC,P
ϭ
110.0 Hz, C0 ), 132.54 (s, C0p), 132.62 (d, JC,P ϭ 10.2 Hz, C0o),
1
2
2
2
3
4
133.30 (d, JC,P ϭ 11.5 Hz, C0 ), 138.46 (d, JC,P ϭ 23.7 Hz, C0 ),
3
(CDCl3): δ ϭ 1.34 (t, JH,H ϭ 6.9 Hz, 6 H, CH2ϪCH3), 3.46 (d,
146.85 (d, JC,P ϭ 6.7 Hz, CHϭCH-P0) ppm. 31P{1H} NMR
2
3JH,P ϭ 7.0 Hz, 6 H, N-CH3), 4.13 (dt, JH,H ϭ 6.9, JH,P
ϭ
3
3
2
(CDCl3): δ ϭ 12.8 (d, JP,P ϭ 17.2 Hz, P1), 18.2 (s, P0), 71.2 (d,
3
2
14.2 Hz, 4 H, CH2), 6.35 (t, JH,H ϭ JH,P ϭ 17.2 Hz, 1 H, ϭCH-
2JP,P ϭ 17.2 Hz, PЈ1) ppm. C26H36N5O3P3S (591.59): calcd. C
P0), 7.21 (d, 3JH,H ϭ 7.8 Hz, 4 H, H-C1 ), 7.58 (d, JH,H ϭ 7.8 Hz,
2
3
52.79, H 6.13, N 11.84; found C 52.85, H 6.19, N 11.75.
3
4 H, H-C1 ), 7.44Ϫ7.65 (m, 17 H, HArom, CHϭN, CHϭCH) ppm.
13C{1H} NMR (CDCl3): δ ϭ 16.26 (d, 3JC,P ϭ 6.4 Hz, CH2ϪCH3),
31.68 (d, 2JC,P ϭ 13.9 Hz, N-CH3), 62.09 (d, 2JC,P ϭ 5.8 Hz, CH2),
Dendron 10-G1: DMF (2 mL) was added to a mixture of powdered
8-G1 (0.130 g, 0.219 mmol) and helicin 9 (0.125 g, 0.439 mmol).
The resulting solution was stirred overnight then evaporated to dry-
ness. 10-G1 was isolated as an oil in quantitative yield (0.250 g). A
strict stoichiometric amount of reagents must be used since it is
difficult to eliminate the unreacted helicin. 1H NMR ([D8]THF):
1
3
117.28 (d, JC,P ϭ 190.7 Hz, ϭCH-P0), 121.89 (d, JC,P ϭ 5.0 Hz,
2
3
3
1
C1 ), 127.49 (d, JC,P ϭ 13.6 Hz, C0 ), 128.00 (dd, JC,P ϭ 107.0,
3JC,P ϭ 4.0 Hz, C0 ), 128.24 (s, C1 ), 128.61 (d, JC,P ϭ 13.1 Hz,
i
3
3
4
1
3
C0m), 130.09 (s, C1 ), 130.15 (dd, JC,P ϭ 110.0, JC,P ϭ 4.0 Hz,
1
2
C0 ), 132.56 (d, JC,P ϭ 10.4 Hz, C0o), 132.67 (s, C0p), 133.18 (d,
3
3
δ ϭ 1.40 (t, JH,H ϭ 7.0 Hz, 6 H, CH2ϪCH3), 3.28 (d, JH,P
ϭ
2
3
4
2JC,P ϭ 11.4 Hz, C0 ), 138.44 (dd, JC,P ϭ 23.3, JC,P ϭ 2.9 Hz,
3
8.7 Hz, 3 H, N-CH3), 3.30 (d, JH,P ϭ 8.7 Hz, 3 H, N-CH3),
4
3
2
C0 ), 141.08 (d, JC,P ϭ 18.7 Hz, CHϭN-N), 146.76 (d, JC,P
ϭ
3
3.41Ϫ3.92 (m, 12 H, CH2 and CH helicin), 4.19 (dt, JH,H ϭ 7.0,
2
1
5.5 Hz, CHϭCH-P0), 153.35 (d, JC,P ϭ 14.8 Hz, C1 ) ppm.
3JH,P ϭ 15.0 Hz, 4 H, CH2OP), 4.74Ϫ5.11 (m, 10 H, OH, HC1 ),
7
31P{1H} NMR (CDCl3): δ ϭ 13.5 (d, JP,P ϭ 30.5 Hz, P1), 18.3 (s,
2
3
6.64 (t, JH,H
ϭ
2JH,P ϭ 17.2 Hz, 1 H, ϭCH-P0), 6.88 (m, 2 H,
2
P0), 51.6 (d, JP,P
ϭ 30.5 Hz, PЈ1), 63.4 (s, P2) ppm.
C40H42Cl4N5O5P5S3 (1065.7): calcd. C 45.08, H 3.97, N 6.57; found
C 44.89, H 3.91, N 6.51.
3
4
5
HC1 ), 7.22 (m, 4 H, HC1 , HC1 ), 7.56Ϫ8.11 (m, 19 H, HArom
,
CHϭCH-P0) ppm. 13C{1H} NMR ([D8]THF): δ ϭ 17.80 (d,
3JC,P ϭ 5.9 Hz, CH2ϪCH3), 33.89 (d, JC,P ϭ 9.8 Hz, N-CH3),
2
2
2
Dendron 6-G2: Powdered hydroxybenzaldehyde sodium salt
(0.043 g, 0.301 mmol, an excess) was added to a solution of 3-G2
34.04 (d, JC,P ϭ 9.8 Hz, N-CH3), 63.41 (d, JC,P ϭ 5.7 Hz,
CH2OP), 63.72 (s, CH2OH), 72.20 (s, C1 °), 75.87 (s, C1 ), 79.01 (s,
1
8
(0.073 g, 0.069 mmol) in THF (5 mL). The resulting mixture was C1 or C111), 79.42 (s, C1 or C1 ), 104.28 (s, C1 ), 104.70 (s, C1 ),
9
11
9
7
7
Eur. J. Inorg. Chem. 2004, 2459Ϫ2466
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2463

A.-M. Caminade, J.-P. Majoral et al.
FULL PAPER
5
1
119.24 (s, C1 ), 119.61 (d, JC,P ϭ 188.8 Hz, ϭCH-P0), 119.74 (s, sulting mixture was stirred overnight then centrifuged, and the
5
3
3
2
C1 ), 124.13 (s, C1 ), 124.30 (s, C1 ), 127.43 (s, C1 ), 129.21 (d,
solution was evaporated to dryness. The resulting powder was
3JC,P ϭ 13.2 Hz, C0 ), 129.42 (s, C1 ), 129.86 (s, C1 ), 130.20 (d, washed with THF/pentane to eliminate unreacted 7. Compound
3
1
4
i
1
3JC,P ϭ 12.5 Hz, C0m), 132.18 (br. d, 1JC,P ϭ 108.3 Hz, C0 ), 132.24
14-G2 was obtained as a white powder in 63% yield (0.081 g). H
(d, JC,P ϭ 14.2 Hz, CHϭN), 132.44 (d, JC,P ϭ 110.0 Hz, C0 ), NMR (CDCl3): δ ϭ 1.33 (t, 3JH,H ϭ 7.1 Hz, 6 H, CH2ϪCH3), 3.33
3
1
1
3
3
3
133.94 (s, C0p), 134.98 (d, 2JC,P ϭ 10.8 Hz, C0o), 133.50 (d, 2JC,P ϭ (d, JH,P ϭ 10.5 Hz, 6 H, N-CH3), 4.12 (dt, JH,H ϭ 7.1, JH,P
ϭ
2
3
4
2
3
2
10.6 Hz, C0 ), 140.47 (d, JC,P ϭ 23.6 Hz, C0 ), 148.86 (d, JC,P
ϭ
14.8 Hz, 4 H, CH2), 6.37 (t, JH,H ϭ JH,P ϭ 17.1 Hz, 1 H, ϭCH-
6.7 Hz, CHϭCH-P0), 157.37 (s, C1 ), 157.52 (s, C1 ) ppm. 31P{1H} P0), 6.86 (d, JH,H ϭ 8.1 Hz, 8 H, H-C2 ), 6.92 (m, 4 H, H-C3 ),
6
6
3
3
3
2
3
2
NMR ([D8]THF): δ ϭ 14.6 (d, JP,P ϭ 26.6 Hz, P1), 24.0 (s, P0), 7.15 (d, JH,H ϭ 8.1 Hz, 8 H, H-C2 ), 7.23Ϫ7.78 (m, 73 H, HArom
,
2
3
4
62.5 (d, JP,P ϭ 26.6 Hz, PЈ1) ppm. C52H64N5O15P3S (1124.08):
CHϭN, CHϭCH), 8.15 (br. dd, JH,H ϭ 6.9, JH,P ϭ 4.1 Hz, 4 H,
H-C3 ), 9.02 (d, JH,P ϭ 5.1 Hz, 1 H, CHϭN-C) ppm. 13C{1H}
6
4
calcd. C 55.56, H 5.74, N 6.23; found C 55.47, H 5.71, N 6.31.
3
NMR (CDCl3): δ ϭ 16.28 (d, JC,P ϭ 6.0 Hz, CH2ϪCH3), 32.96
Cationic Dendron 11-G1: Methyl trifluoromethanesulfonate (50 µL,
0.470 mmol) was added dropwise to a solution of 3-G1 (0.350 g,
0.470 mmol) in CH2Cl2 (10 mL) at 0 °C. The reaction mixture was
stirred for 10 minutes at 0 °C and 20 minutes at room temperature
and then evaporated to dryness. The crude residue was washed with
pentane to afford 11-G1 as a sticky yellow oil in 95% yield (0.405 g).
(d, 2JC,P ϭ 13.1 Hz, N-CH3), 61.94 (d, 2JC,P ϭ 5.5 Hz, CH2), 117.53
(d, 1JC,P ϭ 189.0 Hz, ϭCH-P0), 121.84 (br. s, C1 , C2 , C2 ), 127.18
2
2
3
3
3
3
3
(d, JC,P ϭ 13.3 Hz, C0 ), 127.85 (s, C1 ), 127.99 (d, JC,P
ϭ
i
1
3
14.2 Hz, C0m), 128.01 (dd, JC,P ϭ 106.0, JC,P ϭ 6.0 Hz, C0 ),
128.17 (d, JC,P ϭ 3.9 Hz, C3 ), 128.52 (d, JC,P ϭ 7.1 Hz, C3m),
3
6
3
128.79 (br. s, C3 , C3p), 130.10 (dd, JC,P ϭ 108.0, JC,P ϭ 3.6 Hz,
5
1
3
1H NMR (CD2Cl2): δ ϭ 1.30 (t, JH,H ϭ 7.0 Hz, 6 H, CH3), 2.63
3
1
4
4
2
C0 ), 130.77 (s, C3 ), 130.90 (s, C1 ), 132.58 (d, JC,P ϭ 11.0 Hz,
(d, 3JH,P ϭ 18.2 Hz, 3 H, P1-S-CH3), 4.16 (dt, 3JH,H ϭ 7.2, 3JH,P ϭ
2
2
C0o), 132.70 (s, C0p), 133.30 (d, JC,P ϭ 15.3 Hz, C0 ), 133.44 (s,
3
2
14.5 Hz, 4 H, CH2), 6.55 (t, JH,H ϭ JH,P ϭ 17.0 Hz, 1 H, ϭCH-
P0), 7.24Ϫ8.07 (m, 23 H, HArom, CHϭCH-P0), 9.95 (s, 2 H, CHO)
3
2
1
C3 ), 133.88 (d, JC,P ϭ 19.9 Hz, C3o), 136.24 (d, JC,P ϭ 8.7 Hz,
i
2
1
3
C3 ), 138.46 (d, JC,P ϭ 20.4 Hz, C3 ), 138.53 (d, JC,P ϭ 21.0 Hz,
C0 ), 138.84 (d, JC,P ϭ 17.3 Hz, C3 ), 139.07 (br. d, JC,P
ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 14.23 (d, JC,P ϭ 5.3 Hz, S-
2
4
1
2
3
ϭ
CH3), 16.62 (d, 2JC,P ϭ 5.8 Hz, CH3), 63.20 (br. s, CH2), 121.28 (q,
2
13.5 Hz, CHϭN-N), 146.68 (d, JC,P ϭ 6.5 Hz, CHϭCH-P0),
1JC,F ϭ 323.5 Hz, CF3), 121.81 (d, JC,P ϭ 4.9 Hz, C1 ), 122.15 (d,
3
2
2
1
4
2
148.54 (d, JC,P ϭ 5.9 Hz, C2 ), 148.55 (s, C2 ), 152.92 (d, JC,P
ϭ
1JC,P ϭ 186.2 Hz, ϭCH-P0), 124.17 (dd, JC,P ϭ 107.4, JC,P
ϭ
1
3
10.2 Hz, C1 ), 158.62 (d, 3JC,P ϭ 20.9 Hz, CHϭN-C) ppm. 31P{1H}
1
i
1
4.4 Hz, C0 ), 126.03 (dd, 1JC,P ϭ 101.7, 3JC,P ϭ 5.8 Hz, C0 ), 129.18
2
NMR (CDCl3): δ ϭ Ϫ13.1 (s, P3), 13.5 (d, JP,P ϭ 30.5 Hz, P1),
3
3
3
(d, JC,P ϭ 12.8 Hz, C0 ), 130.31 (d, JC,P ϭ 13.5 Hz, C0m), 132.39
2
18.3 (s, P0), 51.8 (d, JP,P ϭ 30.5 Hz, PЈ1), 63.5 (s, P2) ppm.
C140H118N9O9P9S3 (2445.5): calcd. C 68.76, H 4.86, N 5.16; found
C 68.64, H 4.82, N 5.11.
(s, C1 ), 132.62 (d, JC,P ϭ 11.7 Hz, C0o), 133.32 (d, JC,P
ϭ
4
3
2
2
2
4
12.0 Hz, C0 ), 135.24 (d, JC,P ϭ 2.9 Hz, C0p), 135.46 (s, C1 ),
4
141.07 (d, 3JC,P ϭ 26.4 Hz, C0 ), 146.42 (br. s, CHϭCH-P0), 153.55
2
1
(d, JC,P ϭ 10.9 Hz, C1 ), 190.82 (s, CHO) ppm. 31P{1H} NMR
Complexed Dendron (15-G2):
A solution of 14-G2 (0.200 g,
2
0.082 mmol) in CH2Cl2 (25 mL) was added slowly dropwise during
2 hours to a solution of [PdCl2(COD)] (0.093 g, 0.327 mmol) in
CH2Cl2 (25 mL). The resulting solution was stirred for 3 hours
more then evaporated to dryness. The residue was washed with
THF/pentane (1:10) to afford 15-G2 as a pale yellow powder in 85%
(CD2Cl2): δ ϭ 16.9 (s, P0), 22.2 (d, JP,P ϭ 20.5 Hz, P1), 23.1 (d,
2JP,P ϭ 20.5 Hz, PЈ1) ppm. C40H39F3NO10P3S2 (907.79): calcd. C
52.92, H 4.33, N 1.54; found C 53.21, H 4.42, N 1.48.
Dicationic Dendron (12-G1): Trimethylsilyl trifluoromethanesulfon-
ate (85 µL, 0.470 mmol) was added dropwise to a solution of 11-
G1 (0.420 g, 0.470 mmol) in CH2Cl2 (10 mL) at 0 °C. The reaction
mixture was stirred for 10 minutes at 0 °C and 30 minutes at room
temperature and then evaporated to dryness. The crude residue was
washed with pentane to afford 12-G1 as a sticky yellow oil in 89%
1
3
yield (0.219 g). H NMR (CD2Cl2): δ ϭ 1.30 (t, JH,H ϭ 7.0 Hz, 6
3
H, CH2ϪCH3), 3.31 (d, JH,P ϭ 10.7 Hz, 6 H, N-CH3), 4.07 (m, 4
3
H, CH2), 6.41 (t, JH,H
ϭ
2JH,P ϭ 17.2 Hz, 1 H, ϭCH-P0), 7.07
3
3
3
(m, 4 H, H-C3 ), 7.16 (d, JH,H ϭ 8.8 Hz, 8 H, H-C2 ), 7.28 (d,
2
3JH,H ϭ 8.8 Hz, 8 H, H-C2 ), 7.40Ϫ7.80 (m, 73 H, HArom, CHϭN,
1
6
4
yield (0.473 g). H NMR (CD2Cl2): δ ϭ 0.10 (s, 9 H, SiMe3), 1.47
CHϭCH), 7.93 (m, 4 H, H-C3 ), 8.21 (d, JH,P ϭ 5.1 Hz, 1 H,
3
3
CHϭN-C) ppm. 13C{1H} NMR (CD2Cl2): δ ϭ 16.79 (d, JC,P
ϭ
3
(t, JH,H ϭ 7.0 Hz, 6 H, CH3), 2.62 (d, JH,P ϭ 18.2 Hz, 3 H, P1-
S-CH3), 4.40 (dt, 3JH,H ϭ 7.2, 3JH,P ϭ 14.6 Hz, 4 H, CH2), 6.73 (t,
2
5.9 Hz, CH2ϪCH3), 33.58 (d, JC,P ϭ 13.1 Hz, N-CH3), 62.59 (d,
3JH,H
ϭ
2JH,P ϭ 17.0 Hz, 1 H, ϭCH-P0), 7.24Ϫ8.07 (m, 23 H,
2JC,P ϭ 6.0 Hz, CH2), 118.58 (d, JC,P ϭ 189.1 Hz, ϭCH-P0),
1
HArom and CHϭCH-P0), 10.03 (s, 2 H, CHO) ppm. 13C{1H} NMR
2
2
2
2
121.94 (d, JC,P ϭ 3.8 Hz, C2 ), 122.45 (d, JC,P ϭ 5.3 Hz, C1 ),
2
122.23 (d, 1JC,P ϭ 49.4 Hz, C3 ), 125.09 (s, C2 ), 125.69 (d, JC,P
ϭ
2
3
1
(CD2Cl2): δ ϭ 1.93 (s, SiMe3), 14.21 (d, JC,P ϭ 5.3 Hz, S-CH3),
2
2
i
3
3
61.1 Hz, C3 ), 128.20 (d, JC,P ϭ 13.7 Hz, C0 , C0m), 128.64 (br. s,
16.19 (d, JC,P ϭ 5.8 Hz, CH3), 66.97 (d, JC,P ϭ 5.4 Hz, CH2),
1
1
3
6
1
3
i
113.32 (d, JC,P ϭ 194.2 Hz, ϭCH-P0), 120.58 (q, JC,F ϭ 323 Hz,
C1 , C3 ), 128.72 (dd, JC,P ϭ 106.0, JC,P ϭ 3.5 Hz, C0 ), 129.26
3
2
1
(s, C3 ), 129.58 (d, 3JC,P ϭ 13.0 Hz, C3m), 131.50 (dd, 1JC,P ϭ 106.0,
5
CF3), 121.77 (d, JC,P ϭ 4.8 Hz, C1 ), 123.56 (dd, JC,P ϭ 106.9,
3JC,P ϭ 4.1 Hz, C0 ), 126.67 (dd, JC,P ϭ 107.5, JC,P ϭ 4.0 Hz,
i
1
3
3JC,P ϭ 4.0 Hz, C0 ), 131.63 (s, C1 ), 133.12 (d, JC,P ϭ 5.5 Hz,
1
4
4
1
3
3
3
C3p), 133.32 (s, C3 ), 133.69 (d, JC,P ϭ 13.2 Hz, C0o), 133.79 (s,
4
2
C0 ), 129.85 (d, JC,P ϭ 13.8 Hz, C0 ), 130.33 (d, JC,P ϭ 13.6 Hz,
3
2
C0m), 132.41 (s, C1 ), 132.62 (d, JC,P ϭ 11.9 Hz, C0o), 133.26 (d,
C0p), 134.00 (d, JC,P ϭ 16.0 Hz, C0 ), 134.40 (s, C3 ), 134.68 (d,
2
2
3
2JC,P ϭ 12.0 Hz, C0 ), 135.31 (d, JC,P ϭ 3.0 Hz, C0p), 135.52 (s,
2
4
2JC,P ϭ 10.9 Hz, C3o), 137.14 (d, JC,P ϭ 15.9 Hz, C3 ), 139.23 (d,
2
1
4
3
4
2
4
3
3JC,P ϭ 21.0 Hz, C0 ), 140.83 (d, JC,P ϭ 12.8 Hz, CHϭN-N),
C1 ), 139.78 (d, JC,P ϭ 28.6 Hz, C0 ), 151.19 (d, JC,P ϭ 8.9 Hz,
2
1
2
4
CHϭCH-P0), 153.52 (d, JC,P ϭ 10.9 Hz, C1 ), 190.83 (s, CHO)
146.99 (d, JC,P ϭ 6.4 Hz, CHϭCH-P0), 149.77 (s, C2 ), 150.34 (d,
ppm. 31P{1H} NMR (CD2Cl2): δ ϭ 22.0 (d, JP,P ϭ 20.7 Hz, P1),
2
2JC,P ϭ 5.9 Hz, C2 ), 153.59 (d, JC,P ϭ 9.8 Hz, C1 ), 166.7 (d,
3JC,P ϭ 9.1 Hz, CHϭN-C) ppm. 31P{1H} NMR (CD2Cl2): δ ϭ 15.6
1
2
1
23.2 (d, 2JP,P
ϭ
20.7 Hz, PЈ1), 23.6 (s, P0) ppm.
2
2
C44H48F6NO13P3S3Si (1130.1): calcd. C 46.77, H 4.28, N 1.24;
found C 46.94, H 4.32, N 1.15.
(d, JP,P ϭ 29.1 Hz, P1), 19.7 (s, P0), 33.0 (s, P3), 53.2 (d, JP,P
ϭ
29.1 Hz, PЈ1), 64.8 (s, P2) ppm. C140H118Cl8N9O9P9Pd4S3 (3154.8):
calcd. C 53.30, H 3.77, N 4.00; found C 53.38, H 3.82, N 4.02.
Dendron 14-G2: THF (8 mL) was added to a powdered mixture of
3-G2 (0.055 g, 0.0516 mmol), compound 13 (0.086 g, 0.227 mmol,
slight excess) and Cs2CO3 (0.150 g, 0.454 mmol, excess). The re-
X-ray Crystallographic Study: Data collection was performed on a
Stoe Imaging Plate Diffraction System (IPDS), equipped with an
2464
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2459Ϫ2466

Phosphorus-Based Dendrons
FULL PAPER
2
3
Oxford Cryosystems Cryostream Cooler. Device and using a graph-
ite-monochromated Mo-Kα radiation (λ ϭ 0.71073A), at T ϭ
than those of the Csp atoms and 50% for the Csp atoms to which
they are connected, excepted hydrogens atoms labelled H(1) and
˚
160 K. Further details are provided in Table 1. Final unit-cell pa- H(2) attached to the C(1) and C(2) carbons atoms, respectively,
rameters were obtained by means of a least-squares refinement of
a set of 8000 well-measured reflections, and crystal decay was
monitored during the data collection by measuring 200 reflections
by exposure. No significant fluctuations of the intensities were ob-
served during measurement.
which were refined isotropically. Methyl groups were refined with
the torsion angle as a free variable. All non-hydrogen atoms were
refined anisotropically, and in the last cycles of refinement weight-
ing schemes were used. The weights were calculated from the fol-
lowing formula: W ϭ 1/[σ2(Fo ) ϩ (aP)2 ϩ bP] where P ϭ (Fo
ϩ
2
2
2
2Fc )/3. Criteria for a satisfactory complete analysis were the ratios
of root-mean-square shift standard deviation being less than 0.1
and no significant features in the final difference Fourier maps.
Drawings of the molecules were produced with the program OR-
TEP3[34] with 50% probability displacement ellipsoids for non-hy-
drogen atoms.
Table 1. Crystal data, data collection and structure refinement
Empirical formula
Molecular mass
Wavelength
Crystal system, space group
Unit cell dimensions
C24H26O3P2
424.39
˚
CCDC-228136 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge
at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ 44-1223-336-033; E-
mail: deposit@ccdc.cam.ac.uk].
0.71073A
¯
triclinic, P1
a ϭ 15.435(2) A
˚
˚
b ϭ 8.6930(11) A
c ϭ 16.326(3) A
˚
α ϭ 90.179(17)°
β ϭ 92.141(18)°
γ ϭ 90.067(16)°
2189.1(5) A
4, 1.288 mg/m3
0.221 mmϪ1
896
3
˚
Volume
Z, calculated density
Absorption coefficient
F(000)
[1]
G. R. Newkome, C. N. Moorefield, F. Vögtle, Dendrimers and
Dendrons, Wiley-VCH, Weinheim (Germany), 2001.
[2]
´
J. M. J. Frechet, D. A. Tomalia, Dendrimers and other Dendritic
Crystal size
Crystal colour and form
Tube power
0.42 ϫ 0.17 ϫ 0.08 mm
colourless plate
1.50 kW
Polymers, Wiley Europe, Chichester, 2001.
[3]
[4]
´
C. J. Hawker, J. M. J. Frechet, J. Am. Chem. Soc. 1990, 112,
7638Ϫ7647.
Tube voltage
Tube current
50 kV
30 mA
V. Maraval, R. Laurent, B. Donnadieu, M. Mauzac, A. M.
Caminade, J. P. Majoral, J. Am. Chem. Soc. 2000, 122,
2499Ϫ2511.
Collimator size
Detector distance
2θ range
0.8 mm
70.0 mm
3.3Ϫ52.1°
12.453Ϫ0.809 A
[5]
[6]
[7]
[8]
[9]
´
K. L. Wooley, C. J. Hawker, J. M. J. Frechet, J. Am. Chem. Soc.
˚
1991, 113, 4252Ϫ4261.
d(hkl) range
´
D. C. Tully, J. M. J. Frechet, Chem. Commun. 2001,
ϕ movement mode
rotation
1229Ϫ1239.
ϕ start
0.0°
P. Savignac, B. Iorga, Modern Phosphonate Chemistry, CRC
Press, 2003.
ϕ end
ϕ increment
Number of exposures
Irradiation/exposure
Measurement duration
θ range for data collection
Index ranges
200.2°
1.1°
´ ˆ ´
V. Maraval, D. Prevote-Pinet, R. Laurent, A. M. Caminade, J.
182
P. Majoral, New J. Chem. 2000, 24, 561Ϫ566.
2.00 min
19 h
2.64Ϫ23.26°
Ϫ17 Յ h Յ 17
V. Maraval, R. M. Sebastian, F. Ben, R. Laurent, A. M. Cami-
nade, J. P. Majoral, Eur. J. Inorg. Chem. 2001, 1681Ϫ1691.
J. P. Majoral, A. M. Caminade, Chem. Rev. 1999, 99, 845Ϫ880.
M. L. Lartigue, B. Donnadieu, C. Galliot, A. M. Caminade, J.
P. Majoral, J. P. Fayet, Macromolecules 1997, 30, 7335Ϫ7337.
M. L. Lartigue, N. Launay, B. Donnadieu, A. M. Caminade,
J. P. Majoral, Bull. Soc. Chim. Fr. 1997, 134, 981Ϫ988.
[10]
[11]
Ϫ9 Յ k Յ 9
Ϫ18 Յ l Յ 18
[12]
[13]
[14]
Reflections collected/unique
Completeness to 2θ ϭ 46.52
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Weighting scheme
12240/3099 [R(int) ϭ 0.0592]
98.2%
Full-matrix least-squares on F2
3099/0/272
C. Galliot, C. Larre, A. M. Caminade, J. P. Majoral, Science
´
1997, 277, 1981Ϫ1984.
1.032
G. M. Salamonczyk, M. Kuznikowski, E. Poniatowska, Tetra-
hedron Lett. 2002, 43, 1747Ϫ1749.
1/[σ2(F2o) ϩ (0.0509P)2 ϩ 1.396P]
where P ϭ (F2o ϩ 2Fc2)/3
R1 ϭ 0.0377, wR2 ϭ 0.0979
R1 ϭ 0.0413, wR2 ϭ 0.1011
[15]
[16]
B. E. Maryanoff, A. B. Reitz, Chem. Rev. 1989, 89, 863Ϫ927.
Final R indices [I Ͼ 2σ(I)]
R indices (all data)
Largest diff. peak and hole
´ ˆ ´
D. Prevote, S. Le Roy-Gourvennec, A. M. Caminade, S. Mas-
son, J. P. Majoral, Synthesis 1997, 1199Ϫ1207.
Ϫ3
˚
[17]
[18]
(0.705 and Ϫ0.364) e·A
´
C. Larre, A. M. Caminade, J. P. Majoral, Angew. Chem. 1997,
109, 614Ϫ617; Angew. Chem. Int. Ed. Engl. 1997, 36, 596Ϫ599.
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Chem. 1994, 106, 1682Ϫ1684; Angew. Chem. Int. Ed. Engl.
1994, 33, 1589Ϫ1592.
[19]
[20]
[21]
[22]
[23]
N. Launay, A. M. Caminade, J. P. Majoral, J. Am. Chem. Soc.
1995, 117, 3282Ϫ3283.
V. Maraval, R. Laurent, S. Merino, A. M. Caminade, J. P. Ma-
joral, Eur. J. Org. Chem. 2000, 3555Ϫ3568.
R. M. Sebastian, G. Magro, A. M. Caminade, J. P. Majoral,
Tetrahedron 2000, 56, 6269Ϫ6277.
The structure was solved by means of direct methods using the
program SIR92[31] and subsequent difference Fourier maps, then
refined by least-squares procedures on F2 by using the program
SHELXL-97.[32] Atomic scattering factors were taken from the In-
ternational Tables for X-ray Crystallography.[33]
All hydrogen atoms were located in difference Fourier maps, but
introduced in the refinement as fixed contributors by using a riding
model with an isotropic thermal parameter fixed at 20% higher
G. Magro, B. Donnadieu, A. M. Caminade, J. P. Majoral,
Chem. Eur. J. 2003, 9, 2151Ϫ2159.
´
C. Larre, B. Donnadieu, A. M. Caminade, J. P. Majoral, J. Am.
Eur. J. Inorg. Chem. 2004, 2459Ϫ2466
www.eurjic.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2465

A.-M. Caminade, J.-P. Majoral et al.
FULL PAPER
[30]
[31]
[32]
Chem. Soc. 1998, 120, 4029Ϫ4030.
J. Mitjaville, A. M. Caminade, R. Mathieu, J. P. Majoral, J.
Am. Chem. Soc. 1994, 116, 5007Ϫ5008.
A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, J.
Appl. Crystallogr. 1993, 26, 343Ϫ350.
G. M. Sheldrick, SHELX97 Ϫ Programs for Crystal Structure
Analysis (Release 97-2). Institut für Anorganische Chemie der
Universität, Tammannstrasse 4, 3400 Göttingen, Germany,
1998.
International Tables for X-ray Crystallography, Vol IV, Kynoch
press, Birmingham, England, 1974.
[24]
F. Gonce, A. M. Caminade, J. P. Majoral, Tetrahedron Lett.
1991, 32, 203Ϫ206.
J. P. Majoral, M. Badri, A. M. Caminade, M. Delmas, A. Ga-
set, Inorg. Chem. 1991, 30, 344Ϫ346.
M. Koprowski, R. M. Sebastian, V. Maraval, M. Zablocka, V.
[25]
[26]
Cadierno-Menendez, B. Donnadieu, A. Igau, A. M. Caminade,
J. P. Majoral, Organometallics 2002, 21, 4680Ϫ4687.
[27]
[33]
[34]
G. Guerrero, P. H. Mutin, A. Vioux, J. Mater. Chem. 2001,
11, 3161Ϫ3165.
[28]
G. Guerrero, P. H. Mutin, A. Vioux, Chem. Mater. 2001, 13,
4367Ϫ4373.
G. P. Schiemenz, H. Kaack, Justus Liebigs Ann. Chem. 1973,
9, 1480Ϫ1493.
L. J. Farrugia, J. Appl. Crystallogr. 1997, 30, 565.
Received January 10, 2004
[29]
Early View Article
Published Online April 26, 2004
2466
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2004, 2459Ϫ2466