Monobranched and hyperbranched dendrimers based on cyclophosphazene containing nitrile and phosphine donors and their Fe and Ru organometallic derivatives

Article abstract of DOI:10.1016/j.poly.2003.12.018

The series of complexes [N₃P₃(OC₆H ₅)₅X·ML_n]PF₆, X=OC ₆H₄CH₂CN, N(CH₃)(CH ₂)₂CN or OC₆H₄PP

Full text of DOI:10.1016/j.poly.2003.12.018

Polyhedron 23 (2004) 1027–1035
www.elsevier.com/locate/poly
Monobranched and hyperbranched dendrimers based
on cyclophosphazene containing nitrile and phosphine donors
and their Fe and Ru organometallic derivatives
*
ꢀ
Carlos Dıaz , Miguel Barbosa, Zaida Godoy
Departamento de Quꢀımica, Facultad de Ciencias, Universidad de Chile, Las Palmeras 3425, Casilla 653, Santiago, Chile
Received 25 July 2003; accepted 28 December 2003
Abstract
The series of complexes [N3P3(OC6H5)5XÅMLn]PF6, X ¼ OC6H4CH2CN, N(CH3)(CH2)2CN or OC6H4PPh2, and [N3P3(X)6 ꢀ
(MLn)6](PF6)6, X ¼ OC6H4CH2CN or N(CH3)(CH2)2CN with MLn ¼ CpFe(dppe) and CpRu(PPh3)2 have been synthesized by
reaction of the corresponding cyclophosphazene ligands: N3P3(OC6H5)5OC6H4CH2CNL1, N3P3(OC6H5)5N(CH3)(CH2)2CNL2,
N3P3(OC6H5)5OC6H4PPh2L3, N3P3(OC6H4 CH2CN)6L4 and N3P3(N(CH3)(CH2)2CN)6L5 with the respective organometallic
CpFe(dppe)I and CpRu(PPh3)2Cl in CH3OH as solvent and in presence or of NH4PF6. The new compounds were characterized by
elemental analysis and IR, UV–Visible and multinuclear NMR spectroscopy. Cyclic voltammetry studies indicate that the cyclo-
phosphazene dendrimers act as insulators between the organometallic centers.
ꢀ 2004 Elsevier Ltd. All rights reserved.
Keywords: Dendrimers; Cyclophosphazene; Metal–nitrile complexes; Iron complexes
1. Introduction
components in molecular electronic and as a photo-
chemical molecular devices for solar energy conversion,
information storage and in catalysis [6]. In general
metal-containing dendrimers can be classified in two
ways: according to the nature of the dendrimer and
acording to the nature of the metal. With regarding to
the nature of the dendrimer three categories can be
distinguished: (see Scheme 1):
Dendrimers chemistry is a rapid developing field of
research [1]. Dendrimers offer the prospect of novel ma-
terial with advantageous properties allowing them to
serve, as soluble catalysts [2], dendritic boxes [3], and
other supramolecular dendritic arrangements. Since
€
the initial report on this class of molecules by Vogtle
in 1978 [4] many different structural classes of den-
dritic macromolecules have been reported. Two main
classes of dendrimers can be distinguished: the classi-
cal organic dendrimers [1] and the emergent inorganic
dendrimers [5].
(a) Dendrimers with coordination centers at the core.
(b) Dendrimers with coordination centers through all
layers and
(c) Dendrimers with coordination centers on the periph-
ery.
The incorporation of transition-metal complexes in
both organic and inorganic dendrimers lead to new and
interesting materials with specific properties such as the
capability to absorb visible light, to give luminescence
and to undergo reversible multielectron redox processes
[6]. Such species, in fact could find applications as
On the other hand, with regard to the nature of the
metal, dendrimers can be clasified in (i) those that the
metal fragments are coordination units and (ii) those
that the metal fragments are organometallic units.
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 coordination or orga-
nometallic derivatives on the surface have been reported
* Corresponding author. Tel.: +56-2-6787396; fax: +56-2-2713888.
ꢀ
E-mail address: cdiaz@uchile.cl (C. Dıaz).
0277-5387/$ - see front matter ꢀ 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2003.12.018

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C. Dıaz et al. / Polyhedron 23 (2004) 1027–1035
1028
2. Results and discussion
2.1. Synthesis of the ligands
The synthesized ligands are shown in Scheme 2. As
expected the synthesis of the dendrimers L1, L3 and L4
was made by the divergent strategy [1], by reaction of
N3P3Cl6 or N3P3(OC6H5)5Cl with HO–6H4CH2CN in
acetone and in presence of the K2CO3 [9,10]. The li-
gands L2 and L5 were prepared by a similar strategy by
reaction of the amine HN(CH3)CH2CH2CN with
N3P3Cl6 or N3P3(OC6H5)5Cl using triethylamine as
HCl abstractor. As commonly observed for N3P3
(OC6H5)6ꢁn(C6H5)n or N3P3(OC6H5)6ꢁ(NHR)n deriva-
tives, the products L1, L3, L4 and L5 were obtained as
yellow or white oil, while L2 was obtained as a white
solid. All the new compounds were fully characterized
by elemental analisis (or mass spectra for L1 and L4) as
well as IR, UV–Visible and 1H 31P and 13C NMR
spectroscopy. The compounds exhibits the typical IR
bands of the N3P3(OC6H5)6ꢁn(C6H5)n ring [11]: m(C-OP)
arounds 1200 cmꢁ1, m(PN) around 1100 cmꢁ1 and m(P-
OC) around 1000 cmꢁ1. Additionally the expected,
m(CN) bands for L1 , L2, L4 and L5 were observed in the
range 2245–2228 cmꢁ1, see Table 1.
The 31P NMR spectra of the ligands L1, L4 and L5
exhibit the typical singlet signal expected for these sys-
tems while that the 31P NMR spectra for L2 and L3
show one triplet and one doublet corresponding to a
AB2 systems. These values are shown in Table 2.
For the ligands L1, L3 and L4, their 13C spectra ex-
hibit all the expected signals for the groups (OC6H5),
(OC6H4X) and P(C6H5)2 (accordingly correspond see
Section 3). Thus the signal of the CN and CH2 groups
were observed around 117 and 24 ppm, respectively.
Full data are shown in Section 3.
Scheme 1. Schematic representation of three class of metallodendri-
mers.
[5–8]. In spite of that dendrimers based on cyclophos-
phazenes have been reported [5], relatively few metal [9]
and organometallic [5,8,10] derivatives have been re-
ported. We have recently reported some organometallic
derivatives of partially branched cyclophosphazene de-
rivatives [10] and some single transition metal chlorides
derivatives [9].
In continuation of our studies, we aimed to investi-
gate the electronic communication between the metallic
centers in dendrimers containing six organometallics
groups in the peripheral (ligands L4 and L5, see Scheme 2)
as well as the influence of the X spacer and the nature of
the metal, on the electronic transfer between the phos-
phorus (ring) atom and the metallic center (ligands
L1–L3).
This communication reports the synthesis and char-
acterization of new inorganic dendrimers based on cy-
clophosphazene having nitrile and phosphine donor
groups and containing their Fe and Ru organometallic
derivatives on the surface.
2.2. Synthesis of the organometallic derivatives
2.2.1. Iron and ruthenium derivatives of ligands L1, L4
Using a previously reported methodology [10], the
iron and ruthenim organometallic derivatives of the ni-
trile ligand L1 and L4 were prepared by reaction of the
respective dendrimer ligands with the organometallic
CpFe(dppe)I and CpRu(PPh3)2Cl respectively, in
methanol as solvent and using NH4PF6 as halide abs-
tractor:
(1) [CpFe(dppe)(L1)][PF6]
(2) [CpRu(PPh3)2(L1)][PF6]
(3) [[CpFe(dppe)]6 (L4)][PF6]6
(4) [[CpRu(PPh3)2]6(L4)][PF6]6
Compounds were characterized by elemental analy-
1
ses, IR, H 31P, and 13C NMR as well as UV–Visible
and cyclic voltammetric methods. The IR spectra of the
complexes exhibit the expected bands due to m(N@P)
and m(CN) modes of the free ligand as well as the m(PF6)
Scheme 2. Formulas for the ligands.

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C. Dıaz et al. / Polyhedron 23 (2004) 1027–1035
1029
Table 1
Selected Ir bands for of the ligands L1–L5 and of their Fe and Ru complexes 1–11
m(PO–C6H5)
m(PN)
m(P–OC6H5)
m(CN)
C5H5
C6H5
Ligands
L1
L2
1259
1177
1177
1117
2245
2247
L3
L4
1271
1265
1273
1212,1170
1171
1192
1154
1100
1125
2247
2252
L5
Complexes
(1)
(2)
1268
1258
1273
1187
1266
1267
1285
1253
1268
1273
1241
1177,1161
1177
1096
2280
2129
2252
2270
711
696
690
696
705
680
696
696
692
696
698
1091
1099
1089
1090
1093
1120
1096
1089
(3)
(4)
1192,1145
1187
1145
1176
1161
1163
(5)
(6)
1195,1177
1197,1176
(7)
(8)
1177
1178
1192
1164
1161
1160
1145
1094
2280
2280
2252
2270
(9)
(10)
(11)
1097
Table 2
Formulas and 31P NMR data for the ligands L1–L5 and of their Fe and Ru complexes 1–11
31P(JP-P,Hz)
(dppe)
PPh3
PPh2
Ligands
L1 N3P3(OC6H5)5OC6H4CH2CN
L2 N3P3(OC6H5)5 N(CH3)CH2)2CN
L3 N3P3(OC6H5)5OC6H4PPh2
L4 N3P3(OC6H4CH2CN)6
L5 N3P3(N(CH3)(CH2)2CN)6
11.66s
18.11t; 2.79d (82.9)
18.1t; 2.78d(81.4)
11.89 (s)
)10.47 (s)
18.5 (s)
Complexes
(1) [CpFe(dppe)(L1)][PF6]
(2) [CpRu(PPh3)2(L1)][PF6]
(3) [CpFe(dppe)]6(L4)][PF6])6
(4) [CpRu(PPh3)2]6(L4)][PF6]
(5) [CpFe(dppe)(L3)][PF6]
(6) [CpRu(PPh3)2(L3)][PF6]
(7) [CpFe(dppe)PPh2C6H4OH][PF6]
(8) [CpFe(dppe)(L2][PF6]
(9) [CpRu(PPh3)2(L2)][PF6]
(10) [CpFe(dppe)]6(L5)][PF6]6
(11) [CpRu(PPh3)2]6(L5)][PF6]6
11.42
10.89
100.25
100.20
92.4
44.0
42.26
34.6
11.30
11.50
17.6t; 2.76d(79.3)
18.1t; 2.48d(78.6)
24.0
24.8
4.6
93
86
18.1t; 2.78d (82.98)
18.09t; 2.77d (82.5)
18.54
37.8
93.6
18.0
34.93
An heptuplet signal at )148 ppm corresponding to PF6 anion was also observed.
band. Values are displayed in Table 1. Characteristic
splitting of the m(N@P) bands due to coordination of
metal halide to CN groups for dendrimer L1 and L4
have been observed recently [9a]. A similar but lesser
effect was observed for complexes (1)–(4). Thus, this
splitting pattern appears to be typical of metal coordi-
nation [9,10]. The complexes (1)–(4) exhibit the expected
31P signal for the N3P3 ring namely a singlet sligtly
shifted to lower values by coordination effects. This
small decrese in the 31P chemical shift is typical of co-
ordination of organometallic fragments [10]. On the
other hand the 31P signal of the dppe ligand ligated to
CpFe fragment for the complexes (1) and (3) was ob-
served as normal at 100 ppm while the signal of PPh3
coordinated to the fragment CpRu was normally ob-
served at 44 and 42 ppm. The PF6 anion was normally
observed as a septuplet around )148 ppm. From the 13
C
NMR spectrum of complexes, it can be clearly corrob-
orated the presence of the groups (OC6H5), (OC6H4X)
X ¼ CH2CN , PPh2, of the ligands as well as the typi-
cal signals of the fragments P(C6H5)3 and C5H5 (see
Section 3).

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C. Dıaz et al. / Polyhedron 23 (2004) 1027–1035
1030
Thus, these data compare well with those of the
The compounds were characterized by elemental
1
nitrile mononuclear model complexes {CpFe(dppe)-
NCR][PF6]} [12], as well as other cyclophosphazene
organometallic derivatives [10].
analyses, IR, H, 31P, as well as UV–Visible and cyclic
voltammetric methods. The IR spectra of complexes
exhibit the expected bands due to m(N@P) and m(CN)
modes of the free ligand as well as the m(PF6) band.
Values are displayed in Table 1, The characteristic
spliting of m(N@P) upon coordination was also ob-
served. A decrease of the m(CN) band upon coordination
suggest the link of the ligand through the CN group
instead of the N(CH3) group of the ligand. The com-
plexes (8)–(11) exhibit the expected 31P signal for the
N3P3 ring, namely, a singlet (for (10) and (11)) or a
triplet and doublet signals (for (8) and (9)) at sligthly
shifted lower values by coordination effects. As previ-
ously mentioned this small decrease of the 31P chemical
shift is typical of organometallic fragments coordination
[10]. On the other hand, the 31P signal of the dppe ligand
ligated to CpFe fragment for the complexes (8) and (10)
was normally observed at 92.4 and 93.6 ppm, respec-
tively. The signal of PPh3 coordinated to the fragment
CpRu was observed at 34.6 and 34.9 ppm for (9) and
(11), respectively. The PF6 anion was normally observed
as a septuplet around )142 ppm. Relatively fast de-
composition of the samples in solution precludes the
measurements of good 13C NMR spectrum for the
complexes.
As previously reported [10c] the 31P chemical shift
parameter D ¼ jd 31P(free ligand) ) d 31P(complex)j in
the systems similar to the organometallic derivatives
(1), (2), (5), (6), (8) and (9) is a measure of the elec-
tron transfer between the phosphorus atom and the
metal atom. From 31P NMR data shown in Table 2 it
can be viewed that the D parameter is greater for the
ruthenium derivatives than for the iron complexes.
Thus this parameter does not correlates with the dis-
tance of the X spacer as found in another similar
systems [10c].
2.2.2. The iron and ruthenium derivatives of the ligand L3
Following a previously reported procedure [13], the
complexes:
(5) [CpFe(dppe)(L3)][PF6]
(6) [CpRu(PPh3)2(L3)][PF6]
were synthesized from the reaction of the respective
organometallic with L3 in methanol as solvent and using
NH4PF6 as halide abstractor. As model, we have also
prepared the new complex:
(7) [CpFe(dppe)PPh2C6H4OH][PF6]
by reaction of the known PPh2C6H4OH [8d] with the
iron organometallic.
The new complexes (5)–(6) were characterized by el-
emental analyses, IR, 1H and 31P NMR, UV–Visible
and cyclic voltammetric methods. IR and NMR data for
the complexes are not unusual and they are displayed in
Tables 1–3 and in Section 3. It is interesting to mention
the m(OH) of (7) at 3420 cmꢁ1 and the 31P signal of the
PPh2 group at 4.6 ppm significantly shifted from the free
value )10 ppm. Similar shifting for the complexes (5)
and (6) were observed. As observed for another cyclo-
phosphazenes and polyphosphazenes containing phos-
phines [8d] a small fraction of phosphine phosphorus as
O ¼ PPh2 was detected by the signals at 28.63 and 26.61
ppm for 5 and 6, respectively.
2.2.3. Iron and ruthenium derivatives of the ligands L2 and
L5
These compounds were synthesized using the usual
methodology for preparing iron–nitrile and ruthenium–
nitrile complexes [10,12]:
(8) [CpFe(dppe)(L2)][PF6]
(9) [CpRu(PPh3)2(L2)][PF6]
(10) [[CpFe(dppe)]6 (L5)][PF6]6
(11) [[CpRu(PPh3)2]6(L5)][PF6]6
2.2.4. UV–Visible spectra of the complexes
The UV–Visible spectrum of the complexes is domi-
nated by both, the organometallic chromophore and by
the nature of the CN or PPh2 groups linked to the metal.
Iron complexes having the CpFe(dppe) moiety exhibits
well defined absorption maxima arounds 450 nm de-
pending of the N or P donor interaction [10,12,13]. Less
intense shoulders arounds 526 and 600 nm have been
assigned to the metal–ligand charge transfer transitions
(MLCT) [12]. Fig. 1 exhibits the UV–Visible spectrum
of (8). Data are shown in Section 3. On the contrary the
ruthenium containing dendrimers (9) and (11) exhibits a
tail beginning around 500 nm, of a more intense ab-
sorption band centered at 350 nm. Thus these absorp-
tion patterns are typical of [CpFe(dppe)NCR][PF6],
[10,12] of [CpFe(dppe)PPh2-R][PF6] [13], [CpRu(PPh3)2
NCR][PF6] [10,12] and [CpRu(PPh3)2PPh2-R][PF6] [13]
complexes.
Table 3
Electrochemical data for complexes 1–11
E1=2 (V)
DE (V)
1
2
0.81
0.53
0.11
0.06
3
0.81
0.50
0.14
0.06
4
5
0.88
0.10
6
0.570
0.884
0.775
0.613
0.767
0.590
0.088
0.092
0.080
0.073
0.263
0.091
7
8
9
10
11
Potential referenced against Ag/AgCl, at 100 mV sꢁ1 scan rate, in a
0.1 mol dmꢁ1 n-Bu4N[PF6].

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C. Dıaz et al. / Polyhedron 23 (2004) 1027–1035
1031
Fig. 1. UV–Visible spectrum for (8) in CH2Cl2 solution at room
temperature.
Fig. 2. Cyclic voltammogram of complexes (1) and (3) on a graphite
electrode (v ¼ 100 mV sꢁ1) of a CH2Cl2(n-Bu4NþPFꢁ6 solution) con-
taining: complex (1), (2.11 · 10ꢁ3M) curve upper, and complex (3),
(3.4 · 10ꢁ4M) curve lower.
2.2.5. Cyclic voltammetry studies
There are few reports of electrochemical studies on
cyclophosphazene metal complexes [8–10], Cyclic vol-
tammetry for these type of systems provides some in-
sight into the communication degree between the metal
centers along the cyclophosphazene [4]. For all the
studied complexes one single oxidation wave was ob-
served. In Fig. 2, the cyclic voltammogram of complex
(1) having one fragment CpFe(dppe) (symbolized [Fe] in
the figure) is compared with that containing six iron
group the complex (3). As shown in Fig. 2, similar CV
(similar intensities and shapes) are obtained, being the
concentration of the dendrimer (1) six times more larger
than the complex (3), which indicated that their oxida-
tion wave involves the transfer of six electrons at the
same potential. Then, the six CpFe(dppe) groups behave
as six electroactive non-interacting redox centers around
the periphery of the cyclosphosphazene ring.
As is usually observed for this type of organometallic
compounds [8–10], only quasi-reversible waves were
observed in all the cases. From Table 3 it can be ob-
served that the potential values clearly depend on the
p-acceptor capacity of the group linked to the organo-
metallic fragment. For the fragment CpFe(dppe) the
most p-acceptor phosphorus induce the highest electron
witdrawing effect provoking the most highest potential
value, ꢂ0.88 V. Consistent with this, the weakest p-ac-
ceptor ligand nitrile, decrease their potential values in an
amount which depend on the nature of the spacer (X in
the Scheme 2). In the CpRu(PPh3)2 series the opposite
tendency was observed. In this case, inductive effects of
the group spacer increasing in the order –C6H4O >
N(CH2)2 could explain the observed order of the
potential.
3. Experimental
3.1. General considerations
Infrared spectra were recorded on a FT-Bruker-66V
spectrophotometer in Nujol. NMR spectra were re-
corded on a Bruker AMX 300 spectrometer in chloro-
form-d1 with TMS (H) d ¼ 0:0 ppm as internal standard
or 85% H3PO4 and downfield positive to the reference as
external standard for the 31P measurements.
UV–Visible absorption spectra were recorded using a
Varian DMS-90 spectrophotometer with 1 cm optical
path cuvettes in CH2Cl2 solutions. Elemental analyses
were performed on Fisons-Carlo Erba EA 1108, appa-
ratus by CEPEDEQ, Universidad de Chile.
Mass spectra were recorded with a ICP-MS Fisons
VG Plasma Quad mass spectrometers.

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C. Dıaz et al. / Polyhedron 23 (2004) 1027–1035
1032
Electrochemical measurements were made on a Parc
mmol); HN(CH3)(CH2)2CN 0.154 ml; (1.65 mmol),
NEt3 0.229 ml; (1.65 mmol) were refluxed in benzene (35
ml) for 72 h. The solution was evaporated in vacuo and
the yellow pale oil residue was poured into water and was
extracted with dichloromethane. The extract was dried
over sodium sulphate and filtered trough celite and the
same solvent evaporated under vacuum to give a white
solid. Anal. Calc. for C34H27O5N5P3: C, 59.76; H, 4.68;
N, 10.25; P, 13.01. Found: C, 57.67; H, 4.25; N, 6.96; P,
13.61%. 1H NMR (CD2Cl2): 7.3–7.0 (m, C6H5), 2.56 (d,
CH3 JPNH ¼ 11 Hz), 2.99 (m, CH2), 2.03 (t, CH2). 13C
NMR (CDCl3, ppm): 150.59, 129.82, 125.49, 121.35 (P-
model 370 electrochemistry system, using a three elec-
trode device, employing a carbon glassy working elec-
trode, platinum wire counter electrode and saturated
calomel reference electrode. Solutions were 10ꢁ3 M in
the complex and 0.1 M in [NBu4]PF6 as supporting
electrolyte. Under the same experimental conditions,
E1=2 for the ferrocene–ferrocenium complex was 0.64 V
with peak separations of about 0.060 V (internal stan-
dard). Reactions were carried out under nitrogen using
standard Schlenk-tube techniques. Diethylether and n-
hexane were dried over sodium and distilled.
N3P3Cl6, HO–C6H4–CH2CN, HNCH3CH2CH2CN,
NH4PF6 and CpRu(PPh3)2Cl were purchased from Al-
drich. CpFe(dppe)I was prepared by a previously re-
ported method [9,10]. N3P3(O–C6H5)5Cl was prepared
using a previously reported method [10b].
OC6H5),
118.54(CN),
45.56(CH2),
34.158CH2),
17.14(CH3).). UV/Vis(CH2Cl2): k ¼ 261 nm.
3.2.1.4. Synthesis of N3P3(N(CH3)(CH2)2CN)6 (L5).
g, (14.38 mmol);
A
mixture of N3P3Cl6
5
HN(CH3)(CH2)2CN 8.068 ml (86.31 mmol), in NEt3
11.96 ml; (86.31 mmol) were refluxed in bencene (50 ml)
for 10 h. The pale yellow solution was filtered and the
solvent evaporated in vacuo. The oil residue was redis-
solved in a n-hexane/dichloromethane mixture. Purifi-
cation of the product mixture was made by
chromatography using neutral alumna. Elution with a n-
hexane/dichloromethane mixture and collection of the
transparent fraction followed by evaporation under
vacuum afford a ligth yellow oil, which was dried under
reduce pressure. Anal. Calc. for C24H42N15P3; C, 45.51;
H, 6.63; N, 33.18; P, 14.30. Found: C, 43.24; H, 6.71; N,
3.2. Preparation of ligand and complexes
3.2.1. Ligands
3.2.1.1. Synthesis of N3P3(O–C6H5)5(O–C6H4–CH2–
CN) (L1). A mixture of N3P3(O–C6H5)5Cl 2.3 g, (3.62
mmol); HO–C6H4–CH2–CN 0.5 g; (3.75 mmol), K2CO3
0.97 g; (7.02 mmol) and [Bu4N]Br 1.7 g; (5.27 mmol) was
refluxed in acetone (40 ml) for 20.17 h. The solution was
filtered through celite and the solvent evaporated in
vacuo. The red oil residue was extracted with toluene to
give a red solution. n-Hexane was added to obtain a
ligth red oil, which was washed with n-hexane and dried
under reduce pressure. Mass spectrum (m=e) 732 Mþ.
Calc. (732); 691 (Mþ-CH3CN)-1H NMR (CDCl3): 7.1–
6.9 (m, OC6H5), 6.83–6.73 (m OC6H4), 3.71, 3.53 (s,
CH2). 13C NMR (CDCl3, ppm): 150.91, 129.9, 125.46,
121.24, 117.87 (OC6H4X), 150.91, 129.21, 121.24, 117.87
(P(OC6H5)), 116.95 (CN), 24.19 (CH2). UV/
Vis(CH2Cl2): k ¼ 232 nm.
1
28.03; P, 14.69%. H NMR (CDCl3): 2.78 (m CH2CN),
2.69(s, CH3), 2.6(m CH2N). 13C NMR (CDCl3): 118.47
(CN), 45.71 (CH2), 33.58 (CH2), 17.60(CH3).
3.2.1.5. Synthesis of N3P3(O–C6H5)5(O–C6H4–PPh2)
(L3). A mixture of N3P3(O–C6H5)5Cl 0.3052 g, (0.48
mmol); HO–C6H4–PPh2 0.1214 g; (0.849 mmol), Cs2CO3
0.294 g; (0.9 mmol) were refluxed in acetone (30 ml) for
2 h. The solution was filtered through celite and the
solvent evaporated in vacuo. The yellow pale oil residue
was extracted with toluene to give a red solution. n-
Hexane was added to obtain a ligth red oil, which was
washed with n-hexane and dried under reduce pressure.
Anal. Calc. for C48H39O6N3P4: C, 65.67; H, 4.78; N, 4.78;
P, 13.9. Found: C, 64.28; H, 4.26; N, 4.26; P, 14.14%. 1H
NMR (CD3Cl): 7.1–7.3 (m OC6H5), 7.0–6.9 (m, C6H4),
3.75 (s, CH2). 13C NMR (CDCl3, ppm): 151.06, 134.96,
133.47, 125.2, 121.22, 115.87 (OC6H4X) 135.74, 133.47,
129.46, 128.76 (–PPh2), 150.17, 128.41, 124.88, 120.97
(P–OC6H5). UV/Vis(CH2Cl2): k ¼ 230 nm.
3.2.1.2. Synthesis of N3P3(O–C6H4–CH2–CN)6 (L4). A
mixture of N3P3Cl6 0.26 g, (0.75 mmol); HO–C6H4–
CH2–CN 0.8 g; (6 mmol), K2CO3 1.54 g; (11.14 mmol)
and [Bu4N]Br 1.5 g; (4.65 mmol) was refluxed in acetone
(30 ml) for 51 h. The red solution was filtered through
celite and the solvent evaporated in vacuo. The red oil
residue was dried in vacuum and extracted with di-
chloromethane and filtered through celite and dried to
obtain a ligth red oil, which was dried under reduce
pressure. Mass spectrum (m=e) 927 Mþ Calc. (927), 886
(Mþ-CH3CN). 1H NMR (CD2Cl2): 7.21–6.93 (m,
OC6H4) 1.63, 1.43(s, CH2). 13C NMR (CDCl3): 129.73,
125.63, 121.79, 118.54 (OC6H4X): 117.36 (CN), 24.43
(CH2). UV/Vis(CH2Cl2): k ¼ 234 nm.
3.2.2. Complexes
3.2.2.1. Synthesis of [N3P3(O–C6H5)5(O–C6H4–CH2–
CN) ꢀ Fe(Cp)dppe]PF6 (1). A mixture of N3P3(O–
C6H5)5(O–C6H4–CH2–CN) 0.23 g (0.31 mmol), and
3.2.1.3. Synthesis of N3P3(OC6H5)5N(CH3)(CH2)2CN
(L2). A mixture of N3P3(O–C6H5)5Cl 1.05 g, (1.65

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C. Dıaz et al. / Polyhedron 23 (2004) 1027–1035
1033
CpFe(dppe)I 0.2 g (0.31 mmol) in methanol (20 ml), in
presence of NH4PF6 0.2 g (1.23 mmol) was stirred for
21 h at room temperature. The solvent was removed
under reduced pressure and the residue extracted with
CH2Cl2 and filtered through celite and concentrated to
ꢂ10 ml. A n-hexane/diethylether 4:1 mixture was added
and the red powdered precipitate was twice washed
with the same solvent mixture and dried under reduced
pressure.
Yield: 0.25 g, 49%. Anal. Calc. for C69H60F6O6N4-
P6Fe: C, 61.99; H, 5.00; N, 4.01; P, 13.32. Found: C,
62.9; H, 4.7; N, 3.9; P, 12.32%. 1H NMR (CD3Cl):
7.73(m), 7.75(m), 7.35(m), 7.26(m), 7.18(m OC6H5),
6.98(m), 6.77(m OC6H4), 4.3 (s, C5H5), 3.7 (CH2P),
1.27 (CH2C). 13C NMR (CDCl3): 156.7, 129.95,
125.3, 121.3, 116.45 (OC6H4X), 156.7; 129,6, 120.18,
116.45 P(OC6H5), 137, 133.19, 133.13, 132.56, 131.68,
131.55 131.55, 127.97 (P(C5H5)), 79.3 (C5H5), 29.26
(CH2CN), 20.13.3 (CH2P). UV/Vis(CH2Cl2): k ¼ 366
and 466 nm.
54.76; H, 5.7; N, 2.64%. 1H NMR (CD3Cl): 7.3(m),
7.25(m), 7.13(m), 6.97(m), (OC6H4X /PC6H5),
5.33(sC5H5), 1.01(CH2). 13C NMR(CDCl3): 156,
129.96, 125.49; 121.73 129.54, 121.73 (OC6H4X): 133.13,
133.07, 131.63, 130.91 (P(OC6H5)), 79.54 (C5H5); 24.22
(CH2CN), 20.45, 23.66 (CH2P). UV/Vis(CH2Cl2):
k ¼ 340 and 440 nm.
3.2.2.4. Synthesis of [N3P3(O–C6H4–CH2–CN)6 ꢀ (Ru-
(Cp)(PPh3)26][PF6]6 (4). A solution of CpRu(PPh3)2-
Cl 0.2 g (0.27 mmol) in CH3OH (30 ml) was stirred with
[N3P3(O–C6H4–CH2–CN)6 0.085 g. (0.09 mmol) in the
presence of NH4PF6 0.25 g (1.5 mmol) at room tem-
perature for 74 h. The solvent was removed under re-
duced pressure and the yellow–orange residue extracted
with CH2Cl2 (15 ml) and filtered through celite. Then
reduced in volume and n-hexane/dithylether 4:1 mixture
was added. The yellow solid precipitate was twice wa-
shed with the same mixture and dried.
Yield: 0.41 g, 97%. Anal. Calc. for C102H86F36O6-
N9P21Ru6; C, 59.34; H, 4.34; N, 2.0. Found: C, 58.79;
H, 4.48; N, 2.12%. 1H NMR (CD3Cl): 6.6–7.68(m
C6H4), 4.36 (s,C5H5). 13C NMR (CDCl3):156, 129.13,
127,85 (OC6H4X): 134.14, 133.57, 132.38, 132.25,
128.96, 128.80, 127.85 (P(OC6H5)), 81.04 (C5H5), 24.0
(CH2).
3.2.2.2. Synthesis of [N3P3(O-C6H5)5(O-C6H4-CH2-
CN) ꢀ Ru(Cp)(PPh3)2]PF6 (2). A solution of CpRu-
(PPh3)2Cl 0.14 g (0.19 mmol) in CH3OH (20 ml) was
stirred with [N3P3(O–C6H5)5(O–C6H4–CH2–CN) 0.22 g
(0.3 mmol) in the presence of NH4PF6 0.2 g (1.22 mmol)
at room temperature for 23 h. The solvent was removed
under reduced pressure and the residue extracted with
CH2Cl2 (15 ml) and filtered through celite. Then reduced
in volume and n-hexane/dithylether 4:1 mixture was
added. The yellow solid precipitate was twice washed
with the same mixture and dried.
3.2.2.5. Synthesis of [N3P3(O–C6H5)5(O–C6H4–PPh2) ꢀ
Fe(Cp)dppe)]PF6 (5). A mixture of N3P3(O–C6H5)5-
(O–C6H4–PPh2) 0.2478 g (0.28 mmol), and CpFe(dppe)I
0.182 g (0.254 mmol) in methanol (20 ml), in presence of
NH4PF6 0.0937 (0.575 mmol) was stirred for 19 h at
room temperature. The solvent was removed under re-
duced pressure and the residue extracted with CH2Cl2
and filtered through celite and concentrated to ꢂ10 ml.
A n-hexane/diethylether 4:1 mixture was added and the
red powdered precipitate was twice washed with the
same solvent mixture and dried under reduced pressure.
Yield: 0.25 g, 49%. Anal. Calc. for C79H68F6O6N3-
P6FeÅCH2Cl2; C, 58.68; H, 4.28; N, 2.3; P, 13.9. Found:
C, 58.81; H, 4.53; N, 1.9, P, 14.14%. 1H NMR (CD3Cl):
8.6–8.3 (m PC6H5), 7.4,7.8 (m OC6H5), 7.25–
7.18 (P(C6H5)3), 6.93, 6.91 (mOC6H4P)4. 9(sC5H5),
3.5(m.b.CH2). UV/Vis(CH2Cl2): 239, 268, 448 and 526
nm(sh), 602 nm(sh).
Yield: 0.41 g, 97%. Anal. Calc. for C79H66F6O6N4P6-
Ru: C, 60.46; H, 4.20; N, 3.0. Found: C, 60.5; H, 6.3; N,
1
3.57%. H NMR (CD3Cl): 7.3, 7.42 (P(C5H5)), 6.94–
6.83, 6.72, 6.64, (OC6H4X), 4.43 (s, C5H5), 1.13(CH2).
13C NMR (CDCl3): 156, 133.58, 129.14, 123.38, 121.44
(OC6H4X), 156, 128.7, 119.44, 116.44 (P(OC6H5)),
134.11, 133.58, 130.56, 130.38, 129.73, 127.33 (P(C5H5)).
115.22 CN; 81.47 (C5H5); 24,12 (CH2CN); 19.99,13.66
CH2P.
3.2.2.3. Synthesis of [N3P3(O–C6H4–CH2–CN)6 ꢀ (Fe-
(Cp)dppe)6][PF6]6 (3). A mixture of N3P3(O–C6H4–
CH2–CN)6 0.21 g (0.23 mmol), and CpFe(dppe)I 0.17 g
(0.26 mmol) in methanol (30 ml), in presence of NH4PF6
0.2 g (1.23 mmol) was stirred for 24 h at room tem-
perature. The solvent was removed under reduced
pressure and the residue extracted with CH2Cl2 and
filtered through celite and concentrated to ꢂ10 ml. n-
Hexane was added and the red powdered precipitate was
twice washed with the same solvent and dried under
reduced pressure.
3.2.2.6. Synthesis of [N3P3(O–C6H5)5(O–C6H4–PPh2) ꢀ
(Ru(Cp)(PPh3)2)]PF6 (6). A mixture of N3P3(O–
C6H5)5(O–C6H4–PPh2 0.2478 g (0.28 mmol) and (Ru-
(Cp)(PPh3)2Cl 0.182 g (0.254 mmol) in methanol
(20 ml), in presence of NH4PF6 0.0937 (0.575 mmol) was
stirred for 19 h at room temperature. The solvent was
removed under reduced pressure and the residue ex-
tracted with CH2Cl2 and filtered through celite and
Yield: 0.25, g. 49%. Anal. Calc. for C234H210
F36O6N9P21Fe6: C, 54.37; H, 4.03; N, 2.05. Found: C,

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C. Dıaz et al. / Polyhedron 23 (2004) 1027–1035
1034
concentrated to ꢂ10 ml. A n-hexane/diethylether 4:1
mixture was added and the red powdered precipitate
was twice washed with the same solvent mixture and
dried under reduced pressure.
CpRu(PPh3)2Cl 0.2155 g (0.297 mmol) in CH3OH (20
ml) was stirred with [N3P3(O–C6H5)5(O–C6H4–CH2–
CN) 0.2 g (0.29 mmol) in the presence of NH4PF6
0.098 g (0.67 mmol) at room temperature for 23 h.
The solvent was removed under reduced pressure and
the residue extracted with CH2Cl2 (15 ml) and filtered
through celite. Then reduced in volume and n-hexane/
dithylether 4:1 mixture was added. The yellow solid
precipitate was twice washed with the same mixture
and dried.
Yield: 0.25 g, 49%. Anal. Calc. for C89H74F6O6N3P6-
Ru; C, 62.38; H, 4.73; N, 4.32; P, 10.50. Found: C,
1
63.05; H, 4.73; N, 2.16; P, 10.86%. H NMR (CD3Cl):
7.8–7.7 (OC6H5), 7.2–7.0 (P(C6H5)3), 6.94–6.88
(OC6H4P), 4,9(s, C5H5).). UV/Vis(CH2Cl2): k ¼ 239
nm, 268 nm (sh), 302 nm(sh), 353 nm.
Yield: 0.41 g, 97%. Anal. Calc. for C75H62F6O5N5-
P6Ru: C, 60.46; H, 4.20; N, 4.6; P, 12.12. Found: C,
60.5; H, 6.3; N, 3.5; P, 11.08%. 1H NMR (CD3Cl):
7.8–7.0 (OC6H5), 4.1 (s, C5H5) 1.55 CH3. 13C NMR
(CDCl3): 129.14, 128.70, 121.44 P(OC6H5), 133.58;
130.56; 129.14 128.70 (P(C5H5)), 121.44 (CN), 84.5
(C5H5), 24.12 (CH2). UV/Vis (CH2Cl2): k ¼ 233 and
350 nm.
3.2.2.7. Synthesis of [HO–C6H4–PPh2 ꢀ Fe(Cp)dppe]-
PF6 (7). A mixture of HO–C6H4–PPh2 0.2478 g (0.28
mmol), and CpFe(dppe)I 0.182 g (0.254 mmol) in
methanol (20 ml), in presence of NH4PF6 0.0937 (0.575
mmol) was stirred for 19 h at room temperature. The
solvent was removed under reduced pressure and the
residue extracted with CH2Cl2 and filtered through celite
and concentrated to ꢂ10 ml. A n-hexane/diethylether
4:1 mixture was added and the red powdered precipitate
was twice washed with the same solvent mixture and
dried under reduced pressure.
3.2.2.10. Synthesis of [N3P3(N(CH3)(CH2)2CN)6 ꢀ
(Fe(Cp)dppe)6][PF6]6 (10). A mixture of [N3P3(O–
C6H4–CH2–CN)6 0.0235 g (0.037 mmol) and CpFe(dp-
pe)I 0.1207 g (0.18 mmol) in methanol (20 ml), in
presence of NH4PF6 0.1123 g (0.77 mmol) was stirred
for 12 h at room temperature. The solvent was removed
under reduced pressure and the residue extracted with
CH2Cl2 and filtered through celite and concentrated to
ꢂ10 ml. n-Hexane was added and the red powdered
precipitate was twice washed with the same solvent and
dried under reduced pressure.
Yield: 0.25 g, 49%. Anal. Calc. for C49H44F6-
OP2FeÅCH2Cl2: C, 58.68; H, 4.28; N, 2.3. Found: C,
1
58.81; H, 4.53; N, 1.9%. H NMR (CD3Cl): 6.6–6.7 (m
C6H4) 4.27(s, C5H5). 3.04 (CH2). 13C NMR (CDCl3):
156.7, 129.6 129.95 (OC6H4X) 133.13, 131.62, 130.95,
127.97, 125.3, 121.3 (P(C6H5)2), 120.18 (CN), 79.3
(C5H5), 24.2 (CH2). UV/Vis(CH2Cl2): k ¼ 255, 476 and
617 nm.
Yield: 0.25 g, 49%. Anal. Calc. for C210H216F36O5-
N9P18Fe6: C, 54.37; H, 4.03; N, 5.19; P, 13.79. Found:
C, 54.76; H, 5.7; N, 4.07; P, 13.90%. 1H NMR (CD3Cl):
7.81(m), 7.74(m), 7.58(m), 7.42(m)(PC6H5), 4.36
(s,C5H5), 2.16 (CH3), 0.1 (CH2). UV/Vis(CH2Cl2):
k ¼ 230 and 451 nm.
3.2.2.8. Synthesis of [N3P3(OC6H5)5N(CH3)(CH2)2-
CNFe(Cp)dppe]PF6 (8). A mixture of N3P3(OC6H5)5-
N(CH3)(CH2)CN 0.20 g (0.29 mmol) and CpFe(dppe)I
0.195 g (0.295 mmol) in methanol (20 ml), in presence
of NH4PF6 0.097 (0.67 mmol) was stirred for 19 h at
room temperature. The solvent was removed under re-
duced pressure and the residue extracted with CH2Cl2
and filtered through celite and concentrated to ꢂ10 ml.
A n-hexane/diethylether 4:1 mixture was added and
the red powdered precipitate was twice washed with
the same solvent mixture and dried under reduced
pressure.
Yield: 0.25 g, 49%. Anal. Calc. for C65H56F6O5N5P6-
Fe: C, 61.99; H, 5.00; N, 5.19; P, 13.8. Found: C, 62.9;
H, 4.7; N, 5.0; P, 13.0%. 1H NMR (CD3Cl): 7.3–6.9 (m)
6.4 (PC6H5) 4.32 (s, C5H5), 1.54(m CH3), 1.25 (CH2).
13C NMR (CDCl3): 156.7, 129.95, 125.3 121.3
(P(OC6H5)), 133.13, 131.62, 130.95, 129.6, 127.97
(P(C5H5)), 120.18 (CN) 79.3 (C5H5), 24.2 (CH2). UV/
Vis(CH2Cl2): k ¼ 233, 467 and 623 nm.
3.2.2.11. Synthesis of [N3P3(N(CH3)(CH2)2CN)6 ꢀ
(Ru(Cp)(PPh3)2)6][PF6]6 (11).
A
solution of
CpRu(PPh3)2Cl 0.1569 g (0.27 mmol) in CH3OH (30 ml)
was stirred with [N3P3(O–C6H4–CH2–CN)6 0.02182 g
(0.034 mmol) in the presence of NH4PF6 0.6741 g (0.41
mmol) at room temperature for 1 h. The solvent was
removed under reduced pressure and the yellow–orange
residue extracted with CH2Cl2 (15 ml) and filtered
through celite. Then reduced in volume and n-hexane/
dithylether 4:1 mixture was added. The yellow solid
precipitate was twice washed with the same mixture and
dried.
Yield: 0.41g, 97%. Anal. Calc. for C270H252F36N15P18
Ru6: C, 59.34; H, 4.34; N, 4.46; P, 11.53. Found: C,
1
58.79; H, 4.48; N, 2.31; P, 11.9%. H NMR (CD3Cl):
7.8–7.0 (m PC6H5), 4.5 (s, C5H5), 1.6 (CH3) 1.3, 0.8
(CH2). 13C NMR (CDCl3): 134.14, 133.57, 132.38,
132.25, 129.13, 128.96, 128.80( P(C5H5)), 127.85 (CN),
3.2.2.9. Synthesis of [N3P3(O–C6H5)5(N(CH3)
(CH2)2CN) ꢀ Ru(Cp)(PPh3)2]PF6 (9). A solution of

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C. Dıaz et al. / Polyhedron 23 (2004) 1027–1035
1035
€
[8] (a) R. Schneider, C. Kollner, I. Welbey, A. Togni, J. Chem. Soc.
Chem. Commu. 2415 (1999);
81.8 (C5H5), 24.2 (CH2). UV/Vis(CH2Cl2): k ¼ 235 and
349 nm.
(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. of, Inorg. Organomet. Polym. 6 (1999) 145;
Acknowledgements
(c) K.R.J. Thomas, V. Parthasarathy Pal, S.R. Scott, R.
Haldford, A.W. Cordes, Inorg. Chem. 32 (1993) 606;
(d) G.A. Carriedo, F.J. Garcia Alonso, P.A. Gonzalez, P. Gomez-
Elipe, Polyhedron 18 (1999) 2853.
Financial support from FONDECYT, project
1030515, and beca DID,PG-85/2002 (M.B.) U. de Chile,
is gratefully acknowledged.
ꢀ
[9] (a) C. Dıaz, M.L. Valenzuela, Polyhedron 21 (2002) 909;
ꢀ
(b) C. Dıaz, M.L. Valenzuela, Bol. Soc. Quim 45 (2002) 527.
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[10] (a) C. Dıaz, I. Izquierdo, F. Mendizabal, N. Yutronic, Inorg.
Chim. Acta 294 (1999) 207;
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