Facile synthesis of new fullerene-Ru(bpy)3 dyads bearing phosphonate groups for hybrid organic-inorganic materials

Article abstract of DOI:10.1016/j.tetlet.2007.03.100

Fullerene reacted with mono- and diphosphonate-bearing bipyridines by way of Bingel-type reactions to give adducts which were easily transformed in the corresponding dyads by forming Ru(bpy)₃ complexes. Electrochemical measurements and the observation of heavy quenching of the Ru(bpy)₃ luminescence manifested strong interactions between the active moieties. Attempts to include the dyads into inorganic matrices derived from zirconium phosphate are reported.

Full text of DOI:10.1016/j.tetlet.2007.03.100

Tetrahedron Letters 48 (2007) 3739–3743
Facile synthesis of new fullerene–Ru(bpy) dyads bearing
3
phosphonate groups for hybrid organic–inorganic materials
a,
a
a
b
*
Ernesto Brunet, Marina Alonso, M Carmen Quintana,
a
a
Olga Juanes and Juan-Carlos Rodr ´ı guez-Ubis
a
Departamento de Qu ı´ mica Org a´ nica, C-I, Facultad de Ciencias, Universidad Aut o´ noma de Madrid, 28049 Madrid, Spain
Departamento de Qu ı´ mica Anal ı´ tica, C-XIII, Facultad de Ciencias, Universidad Aut o´ noma de Madrid, 28049 Madrid, Spain
b
Received 15 February 2007; revised 10 March 2007; accepted 16 March 2007
Available online 21 March 2007
Abstract—Fullerene reacted with mono- and diphosphonate-bearing bipyridines by way of Bingel-type reactions to give adducts
which were easily transformed in the corresponding dyads by forming Ru(bpy) complexes. Electrochemical measurements and
the observation of heavy quenching of the Ru(bpy) luminescence manifested strong interactions between the active moieties.
Attempts to include the dyads into inorganic matrices derived from zirconium phosphate are reported.
2007 Elsevier Ltd. All rights reserved.
3
3
ꢀ
The conversion of solar light into useful chemical energy
is a goal that in principle may artificially be achieved by
the rational design of the appropriate arrangement of
components in the solid state. Nevertheless, even though
the preparation of solid structures is more and more in
the side of designing and predictive principles conceptu-
N
N
N
2+N
Ru
N
N
O
O
N
N
N
2+N
Ru
O
O
O
N
N
O
O
1
ally similar to those used in solution chemistry, we are
-
-
2-
HO3P
PO3H
PO3
still far from this accomplishment. However, the use of
layered inorganic salts in which organic structures (i.e.,
electron-donor and acceptor systems) can be orderly
deposited either by weak interactions or covalent bonds,
a widespread technique to prepare tailored solids with
1
2
Figure 1. Dyads goal of this work.
2
coveted properties, may be applied to approaching this
end. Our recent work in the chemistry of metal phos-
3
phonates thus prompted us to prepare, and hereby de-
0
0
Bromination of 5,5 -dimethyl-2,2 -bipyridine with NBS
under usual conditions rendered the corresponding dibr-
omide whose halogen atoms were easily replaced by eth-
yleneglycol to give diol 6. The hydroxyl groups reacted
with chlorocarbonylmethyl diethyl phosphonate, gener-
ated in situ from its carboxymethyl homologue and
4
scribe, dyad systems 1 and 2 (Fig. 1), with the aim that
their PO groups could be appropriate anchoring points
3
to the suitable inorganic matrix. In this way the charge-
transfer process would probably benefit of a polar, solid
and rigid environment, conditions that seem to be para-
mount in the achievement of long-lived charge-sepa-
rated states.
SOCl , yielding diphosphonate 5 ready for the double
Bingel-type reaction with C . As expected, it rendered
2
5
6
0
a complex mixture as shown by NMR spectra. However,
the MALDI-TOF spectrum of the reaction crude dis-
played an intense peak at m/z = 1377 amu, correspond-
Scheme 1 depicts the straightforward synthetic route
used to prepare dyad 1.
+
ing to M + 1 of the mixture of the various regioisomers
of 4, together with five much less intense peaks at
m/z = 1961, 2097, 2617, 2754 and 3474 amu. This peak
occurrence may be explained as in Figure 2. It may be
seen that the structures that can be assigned to the
Keywords: Dyads; Fullerene; Ruthenium complexes; Charge transfer.
*
Corresponding author. Tel.: +34 914973926; fax: +34 914973966;
e-mail: ernesto.brunet@uam.es
0040-4039/$ - see front matter ꢀ 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tetlet.2007.03.100

3740
E. Brunet et al. / Tetrahedron Letters 48 (2007) 3739–3743
Br
O
O
O
OH
O
PO3Et2
PO3Et2
O
N
N
N
N
N
N
N
i
ii
iii
N
O
OH
O
Br
O
7
6
5
iv
N
N
N
N
-
N
2+
N
N
2+
N
2PF6
Figure 3. Calculated structures (see text) for the indicated compounds.
Ru
Ru
N
N
N
N
N
N
O
O
O
O
O
O
O
O
O
O
O
vi
v
1
O
O
O
O
O
O
O
peaks above m/z = 1377. The H NMR spectrum regret-
-
-
tably showed a very complex set of signals in the range
of 7.5–8.7 ppm thus suggesting that the reaction was
poorly regioselective, in contrast to what has been re-
ported in similar situations where a tethering approach
has been used to multi-functionalize fullerenes in a quite
HO3P
PO3H
Et2O3P
PO3Et2 Et2O3P
PO3Et2
4
(major) +
1
3
compds. of Figure 2
Scheme 1. Reagents and conditions: (i) NBS/CCl
4
/benzoyl peroxide,
6
regioselective fashion. Despite this outcome, we carried
8
0 ꢁC, 2 h (33%); (ii) Na/ethyleneglycol, rt 12 h (38%); (iii) carboxy-
methyl diethyl phosphonate/Cl SO/Py/CH Cl , 0–25 ꢁC, 12 h (96%);
iv) C60/toluene/DBU/I , rt 2 h (14%); (v) Ru(bpy) Cl /EtOH–H O/
NH PF , reflux, 3 h (20%); (vi) HCl/H O, reflux (61%). Compound 1
was obtained as a mixture of regioisomers (see text).
on because we thought a fixed regiochemistry was not
essential to fulfil the goal of including the dyad into
the inorganic matrix. Figure 3 contains the resulting
molecular model of an idealized arrangement of trans-
2
2
2
(
2
2
2
2
4
6
2
4
isomer of compound 1 (Scheme 1) with the Ru(bpy)3
complex on top of C .
6
0
N
N
N
N
Dyad 1 was obtained by treatment of the mixture of iso-
mers 4 with Ru(bpy) Cl to give tetraethyl diphospho-
O
O
O
O
2
2
7
nate 3 which was finally hydrolyzed in acidic media.
The MALDI-TOF spectrum of 3 showed three impor-
O
O
O
O
O
O
O
O
C60
C60
C60
2+
(
C2H5)2O3P
2 5 2
PO (C H )
(C2H5)2O3P
H
tant peaks at m/z = 895 (doubly charged M ), 1790
3
+
+
1
376.19
1960.16
(M ) and 1935 (M + PF ), while that of 1 displayed
6
N
N
the expected one at m/z = 1679.
4
O
O
Dyad 2 was prepared according to Scheme 2. We started
by Negishi coupling of 2-bromopyridine with ethyl 6-
chloronicotinate to render ester 12 whose condensation
O
O
N
N
O
O
8
O
O
O
(
C2H5)2O3P
PO3(C2H5)2
H
C60
C60
(
C2H5)2O3P
O
with the anion of diethyl methylphosphonate yielded
O
O
O
9
ketophosphonate 11. Its Bingel-type reaction with C
C60
C60
O
O
60
O
O
(
C2H5)2O3P
3 2 5 2
PO (C H )
led to a complex mixture from which monoadduct 9
dominated (m/z = 1053) as shown by the MALDI-
TOF spectrum. Flash-chromatography allowed the iso-
2
096.19
O
N
N
N
1
0
2616.35
lation of 9 and its dephosphorylated counterpart
1
1
1
0
in 53% and 8% yield, respectively. Compound 9
N
N
N
1
2
was easily transformed into the Ru complex 8 and
the phosphonate hydrolyzed to give dyad 2 following
similar procedures as those described above.
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
C60
C60
(
C2H5)2O3P
PO3(C2H5)2
(C2H5)2O3P
(C2H5)2O3P
2 5 2
PO (C H )
3
C60
C60
C60
The electrochemical profiles of dyads 1 and 2 in solution
were quite complex as expected because one might antic-
ipate a reduction pattern involving up to twelve negative
potentials, half of them belonging to fullerene and the
other half to Ru complex. Figure 4a and b display the
reduction patterns of dyads 1 and 2, respectively, to-
gether with the corresponding model compounds 4
and 9 for the C60 moiety and the complexes Ru(5)(bpy)2
(
C2H5)2O3P
O
PO3(C2H5)2
O
PO3(C2H5)2
O
O
O
O
O
O
O
N
N
N
N
2
752.38
3472.38
Figure 2. Proposed structure and molecular weights of the main
products of the Bingel-type reaction between 5 and C60 (Scheme 1).
and Ru(11)(bpy) prepared ad hoc by us for this study.
2
The reduction profile of dyad 1 resembles that of 4, its
C60 parent, since the expected Ru complex potentials
were not clearly discerned. In contrast, Ru complex of
dyad 2 was reduced in an almost identical profile as that
of its Ru(11)(bpy) counterpart. Reduction of C of
observed m/z values correspond to the reaction of two
or three C60 units, unfavourable on entropy grounds.
2
60
Fortunately, flash chromatography over silica-gel
allowed separation in 14% yield of a fraction whose
MALDI-TOF spectrum only contained traces of the
dyad 2 occurred at much less negative potentials
(ꢀ0.58 and ꢀ0.96 V) as compared to its C precursor
6
0
9 (ꢀ0.80 and ꢀ1.26 V), indicating that the C reduction
6
0

E. Brunet et al. / Tetrahedron Letters 48 (2007) 3739–3743
3741
PO3Et2
O
CO2Et
O
N
N
Br
N
N
N
N
N
i
ii
iii
R
9
(R = PO3Et2; major) +
1
0 (R = H) +
12
11
polyadducts
iv
N
N
N
N
N
N
2+N
2+N
Ru
Ru
O
N
N
O
N
N
v
PO3H2
PO3Et2
2
8
Scheme 2. Reagents and conditions: (i) ethyl 6-chloronicotinate/t-BuLi/THF, ꢀ78 ꢁC/ZnCl
CH PO Et , rt 2 h (53%); (iv) Ru(bpy)
O, reflux (83%).
2
, rt/Pd(dba)
3
ÆCHCl
3
/t-BuP/THF, reflux (50%); (ii)
3
3
2
/BuLi/THF, ꢀ78 ꢁC, 12 h (86%); (iii) C60/toluene/DBU/I
2
2
Cl /EtOH–H O/NH PF , reflux, 3 h (72%); (vi)
2
2 4 6
HCl/H
2
Observation of Figure 5 shows that the UV–vis spectra
of dyads 1 and 2 were the simple addition of those of
their individual components within experimental error.
a 0.0
Luminescence measurements revealed again the intense
interaction between fullerene and Ru complex in the
dyads. It may easily be seen in Table 1 that the quantum
yields of Ru emission were strongly reduced in dyads 1
and 2. Whether this emission quench is: (i) the conse-
quence of the promoted electron being passed to fuller-
ene thus creating a charge-separated state and heavily
reducing the probability of direct, radiative deactivation
of the metal complex; or (ii) the effect of energy transfer
to the low lying triplet excited-state of C60 remains to be
seen until further experiments are performed. The fact
that increasing solvent polarity further decreased /
seems to point to charge separation because this is to
be stabilized in the more polar solvent. In any case,
Ru(5)(bpy)2
4
Dyad 1
-
-
1.0
2.0
-
2.0
-1.5
-1.0
-0.5
0.0
Potential (V) vs. SCE
0
.0
b
-
1.0
2.0
3.0
the interaction between C60 and Ru(bpy) appeared to
3
be: (i) more effective in dyad 1 as suggested by the high-
est diminution of / (ca. 99% regardless of solvent) rela-
tive to its reference compound; (ii) more sensitive to
solvent polarity in dyad 2 because / was further reduced
in CH CN (91%) as compared to the less polar CH Cl
2
Ru(11)(bpy)2
9
Dyad 2
-
-
3
2
(71%). These observations may be the consequence of
-2.0
-1.5
-1.0
-0.5
0.0
the structural differences between the studied dyads, stif-
Potential (V) vs. SCE
fer 1 displaying a better performance.
Figure 4. Current–potential responses obtained from square wave
voltammetry (SWV) of the dyads 1 (a) and 2 (b) and reference
Unfortunately, all attempts of slipping dyads
and 2 within the walls of zirconium phosphate were
1
compounds in dichloromethane with 0.1 M Bu
4 6
NPF as supporting
ꢀ1
electrolyte, scan rate = 0.1 V s
electrode.
and glassy carbon at working
in dyad 2 was greatly facilitated by the neighbouring Ru
complex as it was previously observed.13 These findings
show the strong mutual influence of the acceptor and
donor moieties in dyads 1 and 2. Reversible Ru(II) to
Ru(III) oxidation (not shown in Fig. 4) was relatively
uneventful because it occurred at similar values (1:
1
.29 V; 2: 1.40 V) as those of the reference compounds
Figure 5. UV–vis absorption spectra of dyads 1, 2 and reference
compounds (10 M in dichloromethane).
ꢀ5
(
Ru(5)(bpy) : 1.28 V; Ru(11)(bpy) : 1.43 V).
2
2

3742
E. Brunet et al. / Tetrahedron Letters 48 (2007) 3739–3743
Table 1. Luminescence data of dyads 1, 2 and reference compounds in aerated solutions
a
ꢀ4
)
Compound (solvent)
kexc (nm)
kems (nm)
Emission intensity
/ (10
Ru(5)(bpy)
2
(a)
455
457
447
442
455
457
447
442
606
617
618
619
606
616
601
612
996
283
220
77
8
3
19
10
12.54
4.51
3.62
2.24
0.09
0.03
0.83
0.21
(b)
Ru(11)(bpy)
2
(a)
(b)
Dyad 1 (a)
(
b)
Dyad 2 (a)
b)
(
a
ꢀ5
2 2 3
c = 10 M; a = CH Cl ; b = CH CN.
unsuccessful using the typical exfoliating methods (1:1
solid state (kexc = 455 nm) what suggests that the strong
interaction between the active moieties observed in solu-
tion prevailed in the solid state. Further studies are
under way to include these dyads into crystalline
inorganic matrices.
water/acetone suspension at 80 ꢁC and alkylamine inter-
3
calation) . In the case of dyad 2, we tried an alternative
1
4
method by means of its treatment with Zr(n-BuO) in
4
n-BuOH. In this way we obtained an amorphous solid
(
it gave no discernible powder X-ray pattern), whose ele-
1
5
mental analyses by combustion and ICP-MS were
compatible with the approximate molecular formula
Zr(2)0.2–0.4(n-BuO)3.6–3.8 what suggests that the dyad
was in fact integrated in the inorganic matrix. Solid-
Acknowledgements
Financial support from the Spanish Ministry of
Science and Education (Grants MAT2003-03243 and
3
1
state MAS ‘non-CP’ P NMR spectra (Fig. 6a) showed
the phosphonate signals slightly shielded (12 ppm) rela-
tive to the starting dyad whose multiplet at ꢀ144.7
MAT2006-00570)
and
indirect
funding
from
ERCROS-Farmacia S.A. (Aranjuez, Spain) are grate-
fully acknowledged.
belonging to the PF counterions is hardly visible in
6
the Zr derivative, indicating that Ru(II) charge compen-
sation is no longer performed by these anions. Solid-
1
3
state CP MAS C NMR spectra (Fig. 6b) revealed
the aliphatic carbons of the butoxide. Thermogravimet-
ric analysis indicated that the solid is stable at tempera-
tures below ca. 300 ꢁC. Above this mark, a heavy 80%
loss was attained in a relatively narrow temperature
range (>200 ꢁC) where all carbon content was lost.
References and notes
1
2
. Desiraju, G. R. In Stimulating Concepts in Chemistry;
Wiley-VCH, 2000; pp 293–306; Dey, A.; Kirchner, M. T.;
Vangala, V. R.; Desiraju, G. R.; Mondal, R.; Howard, J.
A. K. J. Am. Chem. Soc. 2005, 127, 10545.
. Kumar, C. V.; Raju, B. B. Mol. Supramol. Photochem.
2
001, 8, 505; Mitzi, D. B. Chem. Mater. 2001, 13, 3283;
Pergher, S. B. C.; Corma, A.; Fornes, V. Quim. Nova 1999,
2, 693; Byrd, H.; Suponeva, E. P.; Andrew, B.; Bocarsly,
Last but not least, we observed that the organic–inor-
ganic assembly resulted negligible luminescent in the
2
A. B.; Thompson, M. E. Nature 1996, 380, 610.
3
. Brunet, E.; Huelva, M.; V a´ zquez, R.; Juanes, O.; Rodr ´ı -
guez-Ubis, J. C. Chem. Eur. J. 1996, 12, 1578; Brunet, E.;
de la Mata, M. J.; Juanes, O.; Rodriguez-Ubis, J. C.
Chem. Mater. 2004, 16, 1517; Brunet, E.; de la Mata, M.
J.; Juanes, O.; Rodriguez-Ubis, J. C. Angew. Chem., Int.
Ed. 2004, 43, 619–621; Brunet, E. Chirality 2002, 14, 135;
Brunet, E.; Alhendawi, H. M. H.; Cerro, C.; de la Mata,
M. J.; Juanes, O.; Rodr ´ı guez-Ubis, J. C. Angew.
Chem., Int. Ed. 2006, 45, 6918; Brunet, E.; Alonso, M.;
de la Mata, M. J.; Fernandez, S.; Juanes, O.; Chavanes,
O.; Rodriguez-Ubis, J. C. Chem. Mater. 2003, 15,
1
232.
4
. For recent examples of several dyad systems see: Modin,
J.; Johanson, H.; Grennberg, H. Org. Lett. 2005, 7, 3977;
Cardinali, F.; Gallan, J.-L.; Schergna, S.; Maggini, M.;
Nierengarten, J.-F. Tetrahedron Lett. 2005, 46, 2969;
Chaignon, F.; Torroba, J.; Blart, E.; Borgstr o¨ n, M.;
Hammarstr o¨ n, G.; Odobel, F. New J. Chem. 2005, 29,
1
272; Clifford, J. N.; Accorsi, G.; Cardinali, F.; Nieren-
garten, J.-F.; Armaroli, N. C.R. Chimie 2006, 9, 1005;
Zhou, Z.; Sarova, G. H.; Zhang, S.; Ou, Z.; Tat, F. T.;
Kadish, K. M.; Echegoyen, L.; Guldi, D. M.; Schuster, D.
I.; Wilson, S. R. Chem. Eur. J. 2006, 12, 4241.
3
1
1
Figure 6. Solid-state NMR spectra ((a) MAS, ‘non-CP’ P; (b) CP-
5. Spectroscopic data of 5 (mp 46 ꢁC): H NMR (CDCl3,
1
3
MAS C) of dyad 2 and the compound resulting from its reaction with
Zr(On-Bu)
300 MHz) d: 1.18 (t, 12H, J = 6.9 Hz, 4 · CH
); 2.89 (d,
3
4
.
4H, JH–P = 21.5 Hz, 2 · CH P); 3.63 (t, 4H, J = 4.8 Hz,
2

E. Brunet et al. / Tetrahedron Letters 48 (2007) 3739–3743
3743
2
2
· CH
· CH
ꢀ3
2
); 4.04 (m, 8H, 4 · CH
); 4.51 (s, 4H, 2 · CH
= 2.1 Hz, H ); 8.25 (d, 2H, J
2
); 4.23 (t, 4H, J = 4.8 Hz,
H4
0
Þ; 8.54 (d, 1H, H
0
Þ; 8.66 (d, 1H, J3–4 = 8.5 Hz, H
3
);
); 9.91
(d, 1H, H6). C NMR (CDCl , 75 MHz) d: 16.3 (d,
3
); 7.67 (dd, 2H,
8.74 (dd, 1H, H
0
Þ; 8.96 (dd, 1H, J4ꢀ6 = 2.3 Hz, H
4
2
2
6
1
3
J4 = 8.1 Hz, J
=
4ꢀ6
4
3ꢀ4
3
1
3
8
(
CH
.1 Hz, H
CDCl , 75 MHz) d: 16.1 (CH
P); 62.4 (CH ); 64.1; 67.8; 70.2 (3CH
3
); 8.50 (d, 2H, J6ꢀ4 = 2.1 Hz, H
); 33.4 (d, JC–P = 114.7 Hz,
); 120.4 (C );
6
). C NMR
J
J
C–P = 6.3 Hz, CH
C–P = 8.4 Hz, CH
); 137.1 ðC
3
); 22.1 (d, JC–P = 117.9 Hz, C); 64.6 (d,
); 120.8 ðC Þ; 122.4 (C ); 124.8 ðC Þ;
0
0
5
3
3
2
3
3
130.0; 136.9 (C
142.1; 142.7; 142.9; 143.0; 143.1; 144.0; 144.5; 144.6; 144.7;
144.9; 145.0; 145.2; 145.3; 149.5 (C
5
0
4
Þ; 138.4 (C ); 141.0; 141.9;
2
2
2
3
4
1
33.1 (C ); 136.0 (C ); 148.2 (C ); 155.1 (C ); 165.4 (CO).
5 4 6 2
+ +
MS. (L-SIMS+): 661.2 (M+H , 100); 683.2 (M+Na , 21).
. See, for example, Reuther, U.; Brandm u¨ ller, T.; Dona-
ubauer, W.; Hampel, F.; Hirsch, A. Chem. Eur. J. 2002, 8,
6
); 151.4 ðC6 Þ; 154.8
0
6
7
(C
2
); 160.1 ðC2
0
Þ; 186.9 (CO). MS (MALDI-TOF): 1053.2
+
(M ).
1
2
261.
11. Spectroscopic data of 10: H NMR (CDCl
3
, 300 MHz) d:
1
. Its H NMR (CDCl
3
, 300 MHz) was very complex but the
6.69 (s, 1H, CH); 7.47 (m, 1H); 7.89 (m, 1H); 8.52 (m, 1H);
following groups of signals could be discerned at d: 1.47
8.59 (m, 1H); 8.78 (d, 1H, J = 4.2 Hz); 9.41 (d, 1H,
J = 1.5 Hz). MS (MALDI-TOF): 917.2 (M ).
+
(
4
2
12H, 4 · CH ); 4.01 (4H, 2 · CH ); 4.54 (m, 12H,
3
2
1
· CH
2
, 2 · CH
2
); 4.64 (m, 4H, 2 · CH
2
); 7.67–8.98 (m,
12. Spectroscopic data of 8: H NMR (acetone-d
6
, 300 MHz)
); 4.42 (m, 4H,
); 7.58 (m, 3H); 7.65 (m, 2H); 8.19 (m, 11H);
2H).
d: 1.39 (t, 6H, J = 7.1 Hz, 2 · CH
2 · CH
8.77 (m, 4H); 8.99 (m, 1H); 9.11 (m, 2H). C NMR
(acetone-d , 75 MHz) d: 16.5 (d, JC–P = 6.3 Hz, CH ); 20.0
(d, JC–P = 95.8 Hz, C); 65.8 (d, JC–P = 6.3 Hz, OCH );
3
8
9
. L u¨ tzen, A.; Hapke, M. Eur. J. Org. Chem. 2002, 2292.
2
1
13
. Spectroscopic data of 11: H NMR (CDCl , 300 MHz) d:
3
1
2
J5
.42 (t, 6H, J = 7.1 Hz, 2 · CH
2.1 Hz, CH
¼ 1:1 Hz, J
3
); 3.82 (d, 2H, JH–P
=
6
3
2
); 4.30 (m, 4H, 2 · CH
2
); 7.51 (ddd, 1 H,
2
0
0
0
0
¼ 9:6 Hz, J
0
0
¼ 5:0 Hz, H
0
Þ; 7.98
124.6; 124.8; 124.9; 125.1; 125.4; 126.8; 128.3; 128.4; 128.5;
128.6; 129.5; 137.1; 137.1; 138.4; 138.7; 138.8; 141.3; 141.4;
141.9; 142.5; 143.0; 143.4; 143.5; 143.6; 144.3; 144.6; 145.0;
145.1; 145.4; 145.6; 145.6; 149.7; 151.6; 151.7; 152.3; 156.1;
157.0; 157.2; 157.4; 161.5; 184.5 (CO). MS (MALDI-
ꢀ3
5 ꢀ4
5 ꢀ6
5
(
ddd, 1H, J
0
0
¼ 7:9 Hz, J
0
0
¼ 2:1 Hz H Þ; 8.52 (m,
0
4
ꢀ3
4 ꢀ6
4
1
J
H); 8.59 (m, 1H); 8.86 (d, 1H, J = 4.2 Hz); 9.41 (d, 1H,
13
6ꢀ5 = 1.5 Hz, H
6
). C-RMN (CDCl
3
, 75 MHz) d: 16.1
(
CH ); 38.7 (d, J
= 128.4 Hz, CH P); 62.5 (OCH );
3
C–P
2
2
2
+
+
+
1
1
1
19.4 ðC3
0
Þ; 122.4 (C
3
); 123.4 ðC
0
Þ; 134.1 (C
5
); 136.8 ðC4
0
Þ;
6
TOF): 734.0 (M ); 1466.0 (M ); 1611.0 [(M+PF ) ].
5
37.0 (C
4
); 148.9 (C
6
); 149.8 ðC
0
Þ; 154.5 (C
2
); 159.4 ðC
0
Þ;
13. Rio, Y.; Enderlin, G.; Bourgogne, C.; Nierengarten, J.-F.;
Gisselbrecht, J.-P.; Gross, M.; Accorsi, G.; Armaroli, N.
Inorg. Chem. 2003, 42, 8783.
14. Ngo, H. L.; Hu, A.; Lin, W. J. Mol. Catal. A: Chem. 2004,
215, 177.
6
2
90.4 (d, JC–P = 6.3 Hz, CO). MS (MALDI-TOF): 335.1
M+H ).
0. Spectroscopic data of 9: H NMR (CDCl
+
(
1
1
3
, 300 MHz) d:
);
¼ 5:0
1
7
.17 (t, 6H, J = 7.1 Hz, 2 · CH
.39 (ddd, 1H, J
3
); 4.40 (m, 4H, 2 · CH
2
0
0
¼ 1:2 Hz, J
0
0
¼ 9:7 Hz, J
0
0
15. Elemental analysis found: 66.2 C, 3.3 H, 3.5 N. ICP-MS:
Zr (100 u.m.a.), Ru (23.7 u.m.a.), P (16.5 u.m.a.).
5
ꢀ3
5 ꢀ4
5 ꢀ6
Hz, H5
0
Þ; 7.87 (ddd, 1H, J
0
0
¼ 7:9 Hz, J
0
0
= 2.1 Hz
4 ꢀ3
4 –6