Transition metal containing dendrimers based on cyclophosphazene units

Article abstract of DOI:10.1016/S0277-5387(02)00852-5

The series of complexes [N₃P₃(OC₆H₅)₅ OC₆H₄CH₂CN·MCl_n] PF₆, N₃P₃(OC₆H₄CH₂ CN)₆·(MCl_n)₆] (PF₆)₆, [N₃P₃(OC₆H₅)₅ OC₆H₄CH₂CN·MCl_n-1]Cl and [N₃P₃(OC₆H₄CH₂ CN)₆·(MCl_n-1)₆]Cl₆, MCl_n = MnCl₂, FeCl₃, COCl₂, NiCl₂, CuCl₂ have been synthesized by reaction of the corresponding cyclophosphazene ligands: N₃P₃(OC₆H₅)₅ OC₆H₄CH₂CN (L₁) and N₃P₃(OC₆H₄CH₂ CN)₆ (L-₂) with the respective salts MCl_n, in CH₃OH as solvent and in presence or absence of NH₄PF₆. The new compounds were characterized by elemental analysis and IR, UV-Vis and EPR spectroscopy as well as electrochemical methods. The reaction of CuCl₂ with the ligand L₁ affords the copper (I) complex. [N₃P₃(OC₆H₅)₅ OC₆H₄CH₂CN·CU]PF₆ instead the expected Cu(II) complex, which was characterized by multinuclear NMR. For comparison, the complex [N₃P₃(OC₆H₅)₅ OC₆H₄CH₂CN·ZnCl]PF₆ was also prepared. The hexametalladendrimers of iron exhibits a six-electron reduction while that the correspondent monometalladendrimers exhibit a single one-electron reduction. Upon coordination vCN increase in a similar way to crystal field effects dependence with the metal.

Full text of DOI:10.1016/S0277-5387(02)00852-5

Polyhedron 21 (2002) 909Á915
/
www.elsevier.com/locate/poly
Transition metal containing dendrimers based on cyclophosphazene
units
Carlos D´ıaz *, M.L. Valenzuela
Departamento de Qu´ımica, Facultad de Ciencias, Universidad de Chile, Las Palmeras 3425, Casilla 653, Santiago, Chile
Received 2 April 2001; accepted 8 January 2002
Abstract
The series of complexes [N3P3(OC6H5)5OC6H4CH2CN×
MnCl2, FeCl3, CoCl2, NiCl2, CuCl2 have been
synthesized by reaction of the corresponding cyclophosphazene ligands: N3P3(OC6H5)5OC6H4CH2CN (L1) and
/
MCln]PF6, N3P3(OC6H4CH2CN)6×
/
(MCln)6](PF6)6, [N3P3(OC6H5)5-
OC6H4CH2CN×MClnꢀ1]Cl and [N3P3(OC6H4CH2CN)6×(MClnꢀ1)6]Cl6, MCln ꢁ
/
/
/
N3P3(OC6H4CH2CN)6 (L2) with the respective salts MCln in CH3OH as solvent and in presence or absence of NH4PF6. The
new compounds were characterized by elemental analysis and IR, UVÁ
methods. The reaction of CuCl2 with the ligand L1 affords the copper (I) complex. [N3P3(OC6H5)5OC6H4CH2CN×
the expected Cu(II) complex, which was characterized by multinuclear NMR. For comparison, the complex
[N3P3(OC6H5)5OC6H4CH2CN×ZnCl]PF6 was also prepared. The hexametalladendrimers of iron exhibits a six-electron reduction
/
Vis and EPR spectroscopy as well as electrochemical
/Cu]PF6 instead
/
while that the correspondent monometalladendrimers exhibit a single one-electron reduction. Upon coordination nCN increase in a
similar way to crystal field effects dependence with the metal. # 2002 Published by Elsevier Science Ltd.
Keywords: Dendrimers; Cyclophosphazene; MetalÁnitrile complexes
/
1. Introduction
[6]. Such species; in fact could find applications as
component in molecular electronic and as a photoche-
mical molecular devices for solar energy conversion and
information storage [6]. Metal-containing dendrimers
can be classified in to three categories, see Fig. 1:
Dendrimers chemistry is a rapid developing field of
research [1]. Dendrimers offer the prospect of novel
material with advantageous properties allowing them to
serve, as soluble catalysts [2], dendritic boxes [3], and
other supramolecular dendritic arrangements. Since the
A) Dendrimers with coordination centers at the core.
B) Dendrimers with coordination centers through all
initial report on this class of molecules by Vogtle in
¨
layers.
C) Dendrimers with coordination centers on the per-
iphery.
1978, [4], and many different structural classes of
dendritic macromolecules have been reported. Two
main classes of dendrimers can be distinguished: the
classical organic dendrimers [1] and the emergent
inorganic dendrimers [5].
The incorporation of transition-metal complexes in
both organic and inorganic dendrimers lead to new and
interesting material with specific properties such as the
capability to absorb visible light, to give luminescence
and to undergo reversible multielectron redox processes
Although dendrimers with coordination centers on
the periphery have been reported [1,2,6] for those with
the dendrimer, core being organic, few examples of
inorganic dendrimers with metal derivatives on the
surface have been reported [5Á8]. This communication
/
reports the synthesis and characterization of new
inorganic dendrimers based on cyclophosphazene con-
taining single metal complexes on the surface. We have
recently reported some organometallic derivatives of
partially branched cyclophosphazene derivatives [9,10].
* Corresponding author. Tel.: ꢂ
3888.
E-mail address: cdiaz@uchile.cl (C. D´ıaz).
/
56-2-678-7396; fax: ꢂ56-2-271-
/
0277-5387/02/$ - see front matter # 2002 Published by Elsevier Science Ltd.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 0 8 5 2 - 5

910
C. D´ıaz, M.L. Valenzuela / Polyhedron 21 (2002) 909Á915
/
2.2. IR and crystal field correlations
The IR spectra of complexes 1Á
expected bands due to n(NꢁP) and n(CN) modes of
the ligand [11] as well as the n(PF6) band [9,10] for
complexes 1Á11. Characteristic splitting of the n(NꢁP)
/16 exhibit the
/
/
/
bands due to coordination was observed in all the series
of complexes. This splitting pattern appears to be typical
of metal coordination [9,10], as shown in Fig. 2, for
ligand L2 in their Fe and Zn complexes. Two intense and
broad bands around 3479 and 3159 cmꢀ1 correspond-
ing to n(OH2)as and n(OH2)s, respectively, as well as a
medium intensity band around 1658 cmꢀ1 correspond-
ing to d(OH2) are consistent with the presence of a high
degree of hydration for almost all the complexes. The IR
spectra are collected in Table 2. Coordination of metal
to ligands L1 and L2 produce an enhancing of the nCN
Fig. 1. Schematic representation of three classes of metallodendrimers.
2. Results and discussion
2.1. Synthesis
The synthesized complexes are showed in Table 1. As
expected the synthesis of the dendrimers L1 and L2 was
made by the divergent strategy [1], by reaction of
band which suggest a considerable s(RCN)0s(metal)
/
N3P3Cl6 with HOꢀ
presence of the K2CO3 [9,10]. The metallic derivatives
1Á17 were obtained by reaction of the respective
dendrimer ligands with MCln in methanol as solvent
(see Table 1). NH4PF6 as halide abstractor was used for
/
C6H4CH2CN in acetone and in
contribution to the NÁ Á Ámetal bond. Similar tendency
has been observed for organometallic derivatives of
ligands L1 and L2 [9,10]. The strengthening of the CN
/
preparation of complexes 1Á/11. Compounds were
characterized by elemental analyses, IR, UVÁ
/Vis and
EPR spectroscopy as well cyclic voltammetry. The
paramagnetism of the complexes precludes a NMR
characterization, except diamagnetic complexes 5 and
11 which were characterized by multinuclear NMR
spectroscopy. Some complexes are highly hygroscopic
as revealed by its elemental analyses as well as their IR
spectrum (see Section 4).
Table 1
Formulas of the complexes 1Á
Complex Metal
[N3 P3 (OC6 H5 )5 OC6 H4 CH2 CN×MCln ]PF6
/
17
n
/
1
2
3
4
5
Mn
1
2
1
1
1
Fe
Co
Ni
Cu
[N3 P3 (OC6 H4 CH2 CN)6 ×
/
(MCln )6 ](PF6 )6
6
Mn
Fe
1
2
1
1
0
1
7
8
Co
Ni
9
10
11
Cu
Zn
[N3 P3 (OC6 H5 )5 OC6 H4 CH2 CN×MCln ]Cl
/
12
13
14
15
16
Mn
Fe
1
2
1
1
1
Co
Ni
Cu
[N3 P3 (OC6 H4 CH2 CN)×
/
(MCl2 )6 ](Cl)6
17
Fe
2
Fig. 2. IR spectra of ligand L2 and their complexes of Fe and Zn.

C. D´ıaz, M.L. Valenzuela / Polyhedron 21 (2002) 909Á
/915
911
Table 2
Selected IR data for complexes 1Á
2.3. Cyclic voltammetry studies
/17
There are few reports of electrochemical studies on
any cyclophosphazene metal complexes [8b,8c]. Cyclic
voltammetry provides some insight into the origin of the
very different oxidation state distribution in the com-
plexes. Only the complexes 2, 5, 7 and 10 were
Complexes
n(CN)
n(Pꢁ
/
N)
n(PF6)
1
2
2362
2345
2294
2305
2345
2264
2345
2296
2303
2381
2252
2247
2264
2210
2246
2245
2293
11798
1174
1178
1179
1178
1174
1160
1112
1179
1166
1166
1178
1178
1178
1178
1178
1076
832
841
841
839
835
841
851
850
834
848
3
4
5
electrochemically active. Complexes 12Á17 were not
/
6
measured owing their oily nature. Data are shown in
Table 3. As observed for other [RCN][MLn] complexes
7
8
[14a] with MꢁMn,Co and Ni, it shows any wave in
/
9
10
11
12
13
14
15
16
17
their voltammogramm in the studied range. The cyclic
voltammogram recorded for complexes 2 and 7 are
shown in Fig. 3. Analysis of the cyclic voltammetric
responses for these complexes with scan rate varying
from 50 to 200 mV sꢀ1 showed an irreversible one-
electron transfer for the Fe(III)/Fe(II) couple which is
located around 0.50 and 0.44 V for complexes 2 and 7,
respectively. These data are consistent with the one
reduction wave at 0.47 V for the complex [Cl3Fe(m-
NC)Mn(CO)(dppm)2] [14a]. N3P3(OC6H5)6 and
N3P3Cl(OC6H5)5 does not exhibit redox process in the
847
b
b
b
b
b
b
in KBr pellet, in cmꢀ1
Cl is the counterion.
.
a
b
bond upon coordination can be due to the shift of
electron density from the antibonding HOMO of the
cyanide ligand to the orbitals of metal. Thus we have
range of potentials ꢀ
stituted phosphazenes with CN groups also exhibit
redox reduction activity below ꢀ1.8 V [8b].
/
2.00
/
ꢂ2.0 V [8b]. Similar sub-
/
found that the difference nCN complexꢀnCN ligand
/
/
follow a dependence typical of crystal field stabilization
energies effects (understood as covalency effects across
the 3d series) [12,13].
The presence of a single reduction peak (although
irreversible) indicates that the six irons are reduced to
the same potential which suggests that the six redox iron
Table 3
Electrochemical, UVÁ
/
Vis and EPR data for complexes 1Á
/
17
a
b
c
Complexes
Electrochemical E8 (V) DEp
UVÁ
/Vis
EPR giso
2.01
2.05
d
1
2
872
410(2300); 366(4300); 248(9900)
0.50(i)
d
f
i
3
d
f
i
4
g
f
h
5
ꢀ0.48(i)
/
d
6
2.00
2.01
7
0.47(i)
d
405(3000); 314(8900); 233(2250)
592; 522
584(102); 798(21)
i
8
d
9
2.07
10
11
12
13
14
15
16
17
0.28(0.229); ꢀ
/
0.025(i); ꢀ
/
0.05(i); ꢀ
/
0.30(0.66)
586(202)
f
2.18, 2.03
h
d
e
e
e
e
e
e
g
e
e
e
e
525
408; 673
750
2.04
2.02
a
In methanol solution.
In methanol solution at room temperature; in nm.
In solid state.
b
c
d
e
f
Electrochemically inactive, see text.
Not measured.
Not detected. Absorption above 400 nm.
Absorption continue without a maximal.
Diamagnetic sample.
g
h
i
EPR silent sample in the measured conditions.

912
C. D´ıaz, M.L. Valenzuela / Polyhedron 21 (2002) 909Á915
/
Fig. 4. Cyclic voltammogram of complex 11.
Second and subsequent scans lead to an enhancing of
the oxidation peak and the appearance of another
reduction and three additional oxidation peaks. Simul-
taneously with this a strong characteristic stripping peak
appeared which is probably due to the reoxidation of an
unknown Cu(II)/Cu(III) electrodeposited planar species.
According to literature data [8], the irreversible wave at
0.025, ꢀ
/
0.05 and ꢀ0.30 V can be assigned tentatively to
/
a Cu(I)/Cu(0), Cu(II)/Cu(0), and Cu(II)/Cu(I) processes,
respectively.
Fig. 3. Cyclic voltammogram of complexes 1 and 7.
centers are non-interacting. Considering that the solu-
tions have a concentration of 1.04ꢃ
10ꢀ3 M for 2 and
7.76ꢃ
10ꢀ4 M for 7 and assuming that the complex 2 is
a monomeric unit, and the complex 7 can be considered
as their polymer (nꢁ6), containing six non-interacting
redox unit, then the electron number transferred in the
reduction of 7 with respect to the electron transferred in
2 (one electron) can be estimated by the equation [14b]:
2.4. UVÁVis
/
/
/
As found for FeCl3 and other iron-chloride deriva-
tives [13]; the UVÁVis spectra of the complexes 2 and 7
exhibit intense ligandÁmetal charge transfer bands
around 360 and 400 nm, which obscure completely the
very weak spin-forbidden dÁd bands. The complexes do
/
/
/
/
not exhibit absorption above 500 nm. Data are shown in
Table 3. Intensity and position for the charge transfer
ꢀ
im=Cm Mm
ꢁ
0:272
ip=Cp Mp
np ꢁ
(1)
transition are similar to those found for similar chloroÁ
iron complexes [12,13]. The other complexes exhibit the
expected dÁd transition for the respective octahedral
/
/
where ip and im are the current intensity for the polymers
and the monomer, respectively, Mp and Mm are the
molecular weight. Eq. (1) gives a value np:
ions [12,13]. Absorption for the Mn and Co complexes
are very weak; those for Cu(II) are broad probably due
to a tetragonal distortion [13a].
/
6 for
complex 7.
On the other hand the cyclic voltammogram of the
copper complex 10 exhibits a rather complex pattern of
signals. Observed waves (see Fig. 4) can be interpreted
tentatively as redox processes occurring on a copper(II)
atom similar for the six position of the ligand instead of
redox processes affecting each one of the Cu(II) centers.
In this latter case a communication between the copper
2.5. EPR spectra
Complexes 1, 2, 6, 7, 9, 10, 13 and 17 exhibits intense
signals both in solid as well as in dichloromethane
solution. Data are displayed in Table 3. Complexes 3, 4,
8, 14 and 15 are EPR silent in the measured conditions.
On the other hand, the diamagnetic complexes 5 and 11
as expected, does not exhibit EPR signal. The para-
magnetic complexes 2 and 7 exhibit the typical EPR
signal of Fe(III) complexes [13]. The Fe(III) ion is a
centers should cause the oxidationÁreduction to occur
/
at slightly different potentials observing several near
waves [14b]. In the first cycle of the scan a single one
wave at 0.28 V versus SCE was observed. Comparing
with literature data for similar system [8] this wave can
be tentatively assigned to the Cu(II)/Cu(III) couple.
6
ground state S (6A1g in the complexes) and is not split
within an octahedral or even a lower symmetry ligand

C. D´ıaz, M.L. Valenzuela / Polyhedron 21 (2002) 909Á
/915
913
field [15]. In addition, there can been no splitting by
spinÁorbital interaction. Then a single isotropic reso-
nance line at gꢁ2 should be always observed. Hyper-
fine interaction of the unpaired electron with the 14N
nucleus (Iꢁ1) of the cyanide group was not observed,
although the broad, signal in solid state could contain
some unresolved splitting. On the other hands, the g
values (Table 3) near 2 for complexes 2 and 7 and this
corresponds to high spin Fe(III) complexes, because low
sible applications to solubilize conventionally insoluble
inorganic compounds (as MXn salts) in organic sol-
vents. Although the redox properties of the complexes 7
and 10 are irreversible, they are reduced or oxidized at
the same potential which suggest a possible application
as molecular battery. Experiments to coordinate other
transition metals with possible reversible redox proper-
ties are in progress. To our knowledge complexes 2 and
7 are the first iron(III) containing cyclophosphazene
dendrimers [19].
/
/
/
spin Fe(III) complexes exhibit higher g values [16Á18].
/
The EPR spectrum of complex 10 exhibits the signal
splitting typical of a tetragonal distortion of the copper
complex. As observed for other similar complexes [13],
compounds 3, 4 and 8 are EPR silent.
4. Experimental
Experimental procedures and IR, UVÁVis, ESR and
/
2.6. Reaction of L1 with CuCl2 in presence of NH4PF6
electrochemical measurements were performed as pre-
viously reported [9,10]. The ligands N3P3(O-
C6H5)5OC6H4CH2CN and N3P3(OC6H4CH2CN)6 were
Reaction of L1 with CuCl2 in MeOH and in presence
of NH4PF6 affords the Cu(I) complex [N3P3(O-
C6H5)5OC6H5CH2CNCu][PF6] instead of the expected
Cu(II) complex. The diamagnetic white complex was
characterized by elemental analysis, multinuclear NMR
as well as cyclic voltammetric methods. The complex 5
exhibits the expected 31P signal for the N3P3 ring namely
a singlet at 11.64 ppm. The PF6 anion was observed as a
prepared as described previously [9,10]. MnCl2×
/
4H2O,
FeCl3×
/
6H2O, CoCl2×
/
6H2O, NiCl2×
/
6H2O, CuCl2×2H2O
/
and NH4PF6 were used as received. Solvents were dried
and purified by standard procedures.
4.1. Preparation of the complexes
septuplet at ꢀ
/
142 ppm. The 13C NMR spectrum of
4.1.1. [MCln(L1)]PF6
complex exhibit among other, the typical signal of CN
at 121.13 ppm. Full data are displayed in Section 4.
Thus, these data compare well with the NMR multi-
The ligand N3P3(OC6H5)5OC6H4CH2CN (1) 0.2 g
(0.27 mmol) and MnCl2 0.07 g (0.35 mmol) were stirred
in a Schlenk in CH3OH (20 ml) and in presence of the
NH4PF6 0.12 g (0.74 mmol), for 24 h at room
temperature (r.t.). From the slight pink solution the
solvent was removed by rotary evaporation. The pale
pink solid was dissolved in CH2Cl2 and filtered through
celite. The solvent was removed under vacuum and the
nuclear
[N3P3(OC6H5)5OC6H5CH2CN×
with organometallic derivatives [9,10]. The single oxida-
tion peak observed at ꢀ0.48 V can be tentatively
assigned to the Cu(I)/Cu(II) processes.
data
for
the
diamagnetic
complex
/ZnCl][PF6] as well as
/
solid was washed several times with a n-hexanoÁ
/
2.7. Preparation of [N3P3(OC6H5)5OC6H4CH2CN×
/
diethylether mixture. The resulting cream solid was
vacuum dried. Analysis, Found: C 31.97; H 6.27; N
ZnCl][PF6]
4.19. Calc. for C38H31F6O6N4P4Cl2: Mn×
/
CH2Cl2, C
For comparison purpose we have also prepared the
[N3P3(OC6H5)5OC6H5CH2CNZnCl][PF6]
which was characterized by multinuclear NMR. The
31P NMR spectra exhibits the N3P3 signal at 15.4 ppm, a
value at slightly high field than the Cu(I) complex due to
32.17; H 6.27; N 3.9%.
complex
The ligand N3P3(OC6H5)5OC6H4CH2CN (2) 0.13 g
(0.1775 mmol) and FeCl3 0.0617 g (0.2282 mmol) were
stirred in a Schlenk in CH3OH (15 ml) and in presence
of the NH4PF6 0.072 g (0.44 mmol), for 24 h at r.t.
From the orange solution, the solvent was removed by
rotary evaporation. The orange solid was dissolved in
CH2Cl2 and filtered though celite. The solvent was
removed under vacuum and the oily solid was broken by
the most low p-back-bonding Zn0
/
ligand with respect
ligand. Consistent with this, the 13C
to that of the Cu0
/
NMR signal of the CN group in the Zn complex also
appears at highest field with respect to the Cu(I)
complex. Other data are observed normally, see Section
4.
washing several times with a n-hexanoÁdiethylether
/
mixture. The resulting orange solid was vacuum dried.
Analysis, Found: C 43.52; H 3.50; N 3.80. Calc. for
C38H31F6O6N4P4Cl2Fe.CH2Cl2, C 42.98; H 3.03; N
5.1%.
3. Conclusions
The ligand N3P3(OC6H5)5OC6H4CH2CN (3) 0.15 g
(0.21 mmol) and CoCl2 0.06 g (0.25 mmol) were stirred
together with NH4PF6 0.08 g (0.49 mmol) in CH3OH
(15 ml) at r.t. for 24 h. Similar procedure as 1 affords a
The dendrimers L1 and L2 can coordinate one and six
transition atoms, respectively, at the periphery. Forma-
tions of metallodendrimers 1Á17 open interesting pos-
/

914
C. D´ıaz, M.L. Valenzuela / Polyhedron 21 (2002) 909Á915
/
cream solid. Yield: 0.32 g, 62%. Analysis, Found: C
49.50; H 4.15; N 4.14. Calc. for C38H31F6O6N4P4Cl2Co,
C 48.35; H 3.93; N 4.02%.
The ligand N3P3(OC6H5)5OC6H4CH2CN (4) 0.16 g
(0.22 mmol) and NiCl2 0.07 g (0.29 mmol) were stirred
in a Schlenk in CH3OH (15 ml) and in presence of the
NH4PF6 0.08 g (0.49 mmol), for 24 h at r.t. From the
pale green solution the solvent was removed by rotary
evaporation. The pale green solid was dissolved in a
Schlenk in CH3OH (20 ml) and in presence of the
NH4PF6 0.31 g (1.90 mmol), for 24 h at r.t. From the
pink solution, the solvent was removed by rotary
evaporation. Similar procedure as 7 affords a blue solid.
Yield: 0.32 g, 62%. Analysis, Found: C 24.05; H 4.24; N
6.33. Calc. for C48H36F36O6N9P9Cl6Co6, C 24.27; H
1.51; N 5.30%.
The ligand N3P3(OC6H4CH2CN)6 (9) 0.18 g (0.19
mmol) and NiCl2 0.28 g (1.18 mmol) were stirred in a
Schlenk in CH3OH (20 ml) and in presence of the
NH4PF6 0.38 g (2.33 mmol), for 24 h at r.t. Similar
procedures as 8 affords a green solid. Yield: 0.32 g, 62%.
Analysis, Found: C 25.71; H 4.50; N 3.59. Calc. for
C48H36F36O6N9P9Cl6Ni6, C 25.35; H 1.78; N 5.21%.
The ligand N3P3(OC6H4CH2CN)6 (10) 0.16 g (0.17
mmol) and CuCl2 0.25 g (0.91 mmol) were stirred in a
Schlenk in CH3OH (20 ml) and in presence of the
NH4PF6 0.34 g (2.07 mmol), for 24 h at r.t. The green
solution was treated similar to 9 to give a green solid.
Yield: 0.32 g, 62%. Analysis, Found: C 15.65; H 3.26; N
4.71. Calc. for C48H36F36O6N9P9Cl6Cu6, C 15.99; H
3.01; N 4.41%.
CH2Cl2Ámethanol mixture and filtered through celite.
/
The solvent was removed under vacuum and the paste/
oil solid was broken by washing several times with
dichloromethane and vacuum dried. Undetermined
amounts of water preclude good analysis.
The ligand N3P3(OC6H5)5OC6H4CH2CN (5) 0.12 g
(0.16 mmol) and CuCl2 0.03 g (0.18 mmol) were stirred
in a Schlenk in CH3OH (15 ml) and in presence of the
NH4PF6 0.06 g (0.37 mmol), for 24 h at r.t. From the
pale yellow solution the solvent was removed by rotary
evaporation. The solid was dissolved in CH2Cl2 and
filtered through celite. From the clear solution, the
solvent was removed under vacuum and the white solid
was washed several times with a n-hexanoÁ
mixture and vacuum dried. Yield: 0.32 g, 62%. Analysis,
Found: 51.62; 9.23; 4.18. Calc. for
C38H31F6O6N4P4ClCu×CH2Cl2, C 51.53; H 4.39; N
5.46%.
1H NMR(CD2Cl2, d ppm) 7.3Á
3.6(s), CH2. 31P NMR (CD2Cl2, d ppm) 11.64(s) N3P3,
142(h) PF6. 13C NMR (CD2Cl2, d ppm) 129.94,
/
diethylether
The ligand N3P3(OC6H4CH2CN)6 (11) 0.1 g (0.11
mmol) and ZnCl2 0.09 g (0.66 mmol) were stirred in a
Schlenk in CH3OH (20 ml) and in presence of the
NH4PF6 0.21 g (1.29 mmol), for 24 h at r.t. From the
white solution the solvent was removed by rotary
evaporation. The white solid was dissolved in 30 ml
C
H
N
/
/
6.8(m), aromatic,
methanolÁCH2Cl2 (1:2) mixture and filtered through
/
ꢀ
/
celite. The solvent was removed under vacuum and the
oil solid was broken by washing several times with a 10
129.68, 125.48, 116.35. 35(m) aromatic, 121.13(s) CN,
24.21(s) CH2.
ml n-hexanoÁdiethylether (1:2) mixture. The resulting
/
white solid was vacuum dried. Yield: 0.32 g, 62%.
Analysis, Found: C 33.50; H 5.80; N 6.63. Calc. for
C48H36F36O6N9P9Cl6Zn6, C 33.05; H 3.72; N 4.45%.
4.1.2. [(MCln)6(L2)][PF6]6
The ligand N3P3(OC6H4CH2CN)6 (6) 0.14 g (0.15
mmol) and MnCl2 0.18 g (0.91 mmol) were stirred in a
Schlenk in CH3OH (20 ml) and in presence of the
NH4PF6 0.3 g (1.84 mmol), for 24 h at r.t. Similar
procedure as 2 affords a white solid. Yield: 0.32 g, 62%.
Analysis, Found: C 24.03; H 4.41; N 4.41. Calc. for
C48H36F36O6N9P9Cl6Mn6, C 24.51; H 1.53; N 5.36%.
The ligand N3P3(OC6H4CH2CN)6 (7) 0.14 g (0.15
mmol) and FeCl3 0.25 g (0.91 mmol) were stirred in a
Schlenk in CH3OH (20 ml) and in presence of the
NH4PF6 0.3 g (1.81 mmol), for 24 h at r.t. From the
orange solution, the solvent was removed by rotary
evaporation. The orange solid was dissolved in 30 ml
31P NMR (CD2Cl2, d ppm) 15.41(s), N3P3, ꢀ
138(h)
/
PF6. 13C NMR (CD2Cl2, d ppm) 130.29, 128.73,
122.26(s) aromatic, 120.7(s) CN, 24.53(s) CH2.
4.1.3. [(MClnꢀ1)(L1)][Cl]
The ligand N3P3(OC6H5)5OC6H4CH2CN (12) 0.17 g
(0.23 mmol) and MnCl2 0.07 g (0.35 mmol) were stirred
in a Schlenk in CH3OH (10 ml) for 24 h at r.t. From the
brown solution the solvent was removed by rotary
evaporation. The brown oil was dissolved in 30 ml
CH2Cl2 and filtered through celite. The solvent was
removed under vacuum and the oil was washed with a
methanolÁ/CH2Cl2 (1:2) mixture and filtered through
10 ml n-hexanoÁdiethylether (1:2) mixture. The result-
/
celite. The solvent was removed under vacuum and the
oily solid was broken by washing several times with a 10
ing green oil was vacuum dried.
The ligand N3P3(OC6H5)5OC6H4CH2CN (13) 0.17 g
(0.23 mmol) and FeCl3 0.08 g (0.30 mmol) were stirred
in a Schlenk in CH3OH (15 ml) for 24 h at r.t. The
orange solution was treated similar to 12 to give an
orange oil.
ml n-hexanoÁdiethylether (1:2) mixture. The resulting
/
orange solid was vacuum dried. Yield: 0.32 g, 62%.
Analysis, Found: C 14.35; H 3.39; N 4.48. Calc. for
C48H36F36O6N9P9Cl12Fe6, C 15.24; H 4.65; N 3.33%.
The ligand N3P3(OC6H4CH2CN)6 (8) 0.15 g (0.16
mmol) and CoCl2 0.23 g (0.97 mmol) were stirred in a
The ligand N3P3(OC6H5)5OC6H4CH2CN (14) 0.17 g
(0.23 mmol) and CoCl2 0.08 g (0.35 mmol) were stirred

C. D´ıaz, M.L. Valenzuela / Polyhedron 21 (2002) 909Á
/915
915
[4] E. Buhleier, W. Wehnen, F. Vogtle, Synthesis (1978) 155.
¨
[5] I.P. Majoral, A.M. Caminade, Chem. Rev. 99 (1999) 845.
in a Schlenk in CH3OH (10 ml) for 24 h at r.t. From the
pink solution, the solvent was removed by rotary
evaporation. The blue oil was dissolved in 30 ml
CH2Cl2 and filtered through celite. The solvent was
removed under vacuum and the oil solid was washed
[6] V. Balzani, S. Campagna, G. Denti, A. Juris, S. Serroni, M.
Venturi, Acc. Chem. Res. 31 (1998) 26.
[7] G.J. Mccubbin, F.J. Stoddart, T. Welton, A.J.P. White, D.J.
Williams, Inorg. Chem. 37 (1998) 3753.
[8] (a) R. Schneider, C. Kollner, I. Welbey, A. Togni, J. Chem. Soc.,
¨
with a 10 ml n-hexanoÁdiethylether (1:1) mixture. The
/
Chem. Commun. (1999) 2415;
resulting blue oil was vacuum dried. Analysis, Found: C
51.82; H 6.3; N 4.7. Calc. for C38H31O6N4P3Cl2Co, C
52.0; H 4.2; N 3.7%.
(b) M. Gleria, R. Bertani, G. Facchim, F. Noe, R.A. Michelin, M.
Mazzon, A.J.L. Pombeiro, M.F.C.G. Da Silva, I.L.F. Machado,
J. Inorg. Organomet. Polym. 6 (1996) 145;
The ligand N3P3(OC6H5)5OC6H4CH2CN (15) 0.10 g
(0.14 mmol) and NiCl2 0.04 g (0.17 mmol) were stirred
in a Schlenk in CH3OH (10 ml) for 24 h at r.t. The green
solution was treated similar to 14 to give a green oily.
The ligand N3P3(OC6H5)5OC6H4CH2CN (16) 0.14 g
(0.82 mmol) and CuCl2 0.05 g (0.29 mmol) were stirred
in a Schlenk in CH3OH (10 ml), for 24 h at r.t. From the
brown solution and using a similar procedure as 15, a
brown oil was obtained. Analysis, Found: C 46.50; H
3.89; N 5.43. Calc. for C38H31O6N4P3Cl2Cu, C 46.59; H
3.39; N 3.83%.
(c) K.R.J. Thomas, V. Parthasarathy Pal, S.R. Scott, R.
Haldford, A.W. Cordes, Inorg. Chem. 32 (1993) 606.
[9] (a) C. D´ıaz, I. Izquierdo, Polyhedron 18 (1999) 1479;
(b) C. D´ıaz, Bol. Soc. Quim 44 (1999) 315.
[10] (a) C. D´ıaz, I. Izquierdo, F. Mendizabal, N. Yutronic, Inorg.
Chim. Acta 294 (1999) 20;
(b) C. D´ıaz, unpublished results
[11] (a) For IR data and discussion of IR spectra of N3P3X6 and
N3P3(OR)6 compound see: S.S. Khishnamurthy, C. Sau, Adv.
Inorg. Chem. Radiochem. 21 (1978) 41;
(b) H.R. Allcock, L.J. Wagner, M.L. Levin, J. Am. Chem. Soc.
105 (1983) 1321;
(c) G.A. Carriedo, F.J.G. Alonso, P.A. Gonzalez, J.R. Menendez,
J. Raman Spectroscopy 29 (1998) 327.
[12] (a) F.A. Cotton, G. Wilkinson, Advanced Inorganic Chemistry,
Wiley, New York, 1980, p. 666;
4.1.4. [(MClnꢀ1)6(L2)][Cl]6
The ligand N3P3(OC6H4CH2CN)6 (17) 0.13 g (0.14
mmol) and FeCl3 0.23 g (0.85 mmol) were stirred in a
Schlenk in CH3OH (15 ml) for 24 h at r.t. From the
orange solution and using a similar procedure as 16, an
orange oil solid was obtained. Analysis, Found: C 29.66;
H 4.6; N 1.87. Calc. for C48H36O6N4P3Cl18Fe6, C 30.15;
H 6.5; N 1.88%.
(b) T.C. Bailar, H.J. Emeleus, R. Nyholm, A.F. Trotman-
Dickenson (Eds.), Comprehensive Inorganic Chemistry (Chapter
40), Pergamon Press, Oxford, 1979, p. 1049.
[13] (a) B.N. Figgis, Introduction to Ligand Fields (chapter 11),
Interscience Publishers, New York, 1996;
(b) H.A.O. Hill, P. Day, Physical Methods in Advanced Inorganic
Chemistry (chapter 7), Interscience Publishers, Wiley, New York,
1968, p. 346.
[14] (a) N.G. Connelly, O.M. Hicks, G.R. Lewis, A. Guy Orpen, A.J.
Wood, J. Chem. Soc., Chem. Commun. (1998) 517;
(b) D. Astruc, Electron Transfer and Radical Processes in
Transition Metal Chemistry (Chapter 2), Wiley, New York,
1995, p. 116.
Acknowledgements
Financial support from FONDECYT, project
1000672 is gratefully acknowledged.
[15] E.A. Korner Von Gustorf, F.W. Grevals, I. Fischer (Eds.), The
Organic Chemistry of Iron, vol. 1, Academic Press, New York,
1978, p. 257.
[16] A.S. Marlin, M.M. Olmstead, P.K. Mascharak, Inorg. Chem. 38
(1999) 3258.
References
[17] M.F. Reynald, D. Shelver, R.L. Kerby, R.B. Park, G.P. Roberts,
J.N. Burstyn, J. Am. Chem. Soc. 120 (1998) 908.
[18] C. D´ıaz, Bol. Soc. Chil. Quim. 44 (1999) 315.
[19] (a) For reviews on the metal complexes of the cyclophophazene
ligands see: V. Chandrasekhar, K.R. Justin Thomas, Applied
Organometallic Chemistry 7 (1993) 1;
[1] (a) G.R. Newkome, E. He, C.H. Moorefield, Chem. Rev. 99
(1999) 1689;
(b) F. Zeng, S.C. Zimmerman, Chem. Rev. 97 (1999) 1681.
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(b) H.R. Allcock, I.L. Desorcie, D.A. Riding, Polyhedron 6
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