Electroactive poly zinc, cadmium, manganese ferrocenylphenylphosphinates

Article abstract of DOI:10.1016/j.jorganchem.2004.09.047

The synthesis of ferrocenylphenylphosphinic acid in high yield is reported. The electrochemical behaviour of ethyl ferrocenylphenylphosphinate, ferrocenylphenylphosphinic acid and its sodium salt are compared. The preparation and characterization of zinc,

Full text of DOI:10.1016/j.jorganchem.2004.09.047

Journal of Organometallic Chemistry 690 (2005) 363–370
www.elsevier.com/locate/jorganchem
Electroactive poly zinc, cadmium, manganese
ferrocenylphenylphosphinates
*
´
Olivier Oms, Jean Le Bideau, Andre Vioux, Dominique Leclercq
´ ´
Laboratoire de Chimie Moleculaire et Organisation du Solide, (CNRS UMR 5637), Universite Montpellier 2,
`
Place Eugene Bataillon, Case courrier 007, 34095 Montpellier cedex 05, France
Received 26 July 2004; accepted 20 September 2004
Abstract
The synthesis of ferrocenylphenylphosphinic acid in high yield is reported. The electrochemical behaviour of ethyl ferro-
cenylphenylphosphinate, ferrocenylphenylphosphinic acid and its sodium salt are compared. The preparation and characterization
of zinc, cadmium and manganese ferrocenylphenylphosphinates are reported. They are anhydrous and show a high thermal stabil-
ity. The iso-structurality of these compounds is settled, and a structure involving double bridging phosphinate groups is proposed.
Their half wave potentials, determined by cyclic voltammetry using a cavity micro electrode are similar to each other, and are close
to that of the sodium salt of ferrocenylphenylphosphinic acid, and even to those of the related metal ferrocenylphosphonates
M(II)(HO3PFc)2 Æ xH2O.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Ferrocenylphenylphosphinic acid; Poly metalphosphinate; Electrochemistry
1. Introduction
[13] or by coordination of solvent molecules [11,14].
The mode of coordination of the phosphinate groups in-
volves always the coordination of one oxygen to one me-
tal, even if the linkage of one oxygen to two metals,
currently observed for metal phosphonates [15], has
been postulated in some cases to explain the six-fold
coordination of the metal [13,16].
Metal phosphinates are usually resistant to oxidation
and hydrolysis, the phosphinate groups acting as solid
bridging ligands. Their properties result from both the
nature of the metal atom and the nature of the organic
substituents on the phosphorus atom.
Moreover, ferrocene derivatives are of interest in
many fields such as homogeneous catalysis, medicine
due to their antitumour activity, materials due to their
conducting, magnetic or non-linear optical properties,
electrochemical sensors, luminescent devices, and poly-
mers [17–28]. This is related to the specific geometries
that the ferrocenyl moiety can enforce and its electronic
(redox) properties. Their covalent attachment into
Polymeric metal phosphinates, [MO2PRR0]n, among
which the most studied are divalent metal phosphinates,
form a unique class of inorganic polymers with fully
inorganic one-dimensional framework [1].
The linear chain of structurally characterized poly-
meric metal(II) phosphinates consists of metal atoms
linked either by alternating single and triple bridging
phosphinate groups [2–4], or by double bridging phos-
phinate groups [5–8]. The two modes of bridging have
also been found in related poly Zinc(II) (dialkyl)phos-
phates [9–12] (see Scheme 1).
The coordination number of the metal is usually four;
however, it can reach six in the presence of coordinating
substituents in the organic chain of the phosphonates
*
Corresponding author. Tel.: 33 4 67 14 45 28; fax: 33 4 67 14 38
52.
E-mail address: dleclercq@univ-montp2.fr (D. Leclercq).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.09.047

364
O. Oms et al. / Journal of Organometallic Chemistry 690 (2005) 363–370
R
R'
R
R'
R'
R
P
P
P
O
O
O
O
P
O
O
O
O
M
M
P
M
M
O
O
M
O
O
O
O
R'
or
O
O
R R'
P
P
R
n
R
R'
R
n
P
R'
R'
R
Scheme 1. Modes of coordination of the bridging phosphinates.
O
P
Li
tBuLi/tBuOK
PhP(O)OEtCl
OEt
Fe
Fe
Fe
Ph
THF, -80ºC
-80ºC
Scheme 2. Synthesis of ethyl ferrocenylphenylphosphinate.
hybrid organic–inorganic materials, such as polym-
etalphosphinates is an important step in the develop-
ment of molecular-level devices. We report here a
simple and convenient method for the preparation of
ferrocenylphenylphosphinic acid in high yield, and the
characterization of the metal phosphinates obtained by
its reaction with zinc, cadmium and manganese salts.
The mode of coordination of the phosphinate group
and the coordination number of the metal are discussed
on the basis of the spectroscopic data.
as a consequence of the chiral nature of the phosphorus
centre (Fig. 1) [31,32]. The diastereotopy introduced by
a chiral substituent into the cyclopentadienyl ring is usu-
ally observed by 13C NMR, but rarely by 1H NMR. [33–
35] The presence of a phosphorus centre seems to favour
the distinction between the four protons of the cyclopen-
tadienyl ring [35,36].
The assignment of the NMR chemical shifts of the
substituted Cp ring (Table 1) was made considering that:
(i) the P(V) is a withdrawing substituent, leading to a
downfield shift for the 2 and 5 positions [37,38], (ii)
the non-equivalence of the carbon atoms of the substi-
tuted Cp is a direct result of the asymmetric substituent,
the greater separation of the 13C resonance having to be
2. Results and discussion
2
2.1. Synthesis and characterization of ferrocenylphenyl-
phosphinic acid
attributed to the C2/C5 atoms [31], (iii) JCP < 3JCP [39].
It has not yet been possible to ascertain the assignment
of C2 and C5 and of C3 and C4 atoms.
Ethyl ferrocenylphenylphosphinate was prepared by
reaction of monolithioferrocene with chloroethyl phe-
nylphosphonate (Scheme 2), which was obtained by chl-
oration of ethyl phenylphosphinate PhP(O)(OEt)H
prepared by ethanolysis of PhPCl2 [29].The high yield,
after purification by chromatography, (88%) results
Ferrocenylphenylphosphinic acid was prepared in
92% yield by conversion of the ester under mild condi-
tions using Me3 SiBr followed by hydrolysis [40].
The ferrocenyl compounds were characterized by cyc-
lic voltammetry using a Voltalab 10 in a three-electrode
cell. A 0.20-cm diameter platinum disc working elec-
trode, a platinum wire auxiliary electrode and a satu-
rated calomel reference electrode were used to record
voltammograms; the electrolyte was nBu4NPF6 (0.1 M
in methanol). The concentration of the electro-active
species was 0.001 M (see Table 2).
As referred to the ferrocene, the electron-withdraw-
ing effect of the phosphinate substituents leads to an in-
crease of the half wave potential of the ferrocene/
ferrocenium couple. The transformation of the ester into
the acid leads to a 65 mV decrease of the half wave
potential. It is noteworthy that a greater effect has been
observed for ferrocenylphosphonates [30], whereas it
does not exist for carboxylate derivatives [41]. The neu-
tralisation of the acid leads to a decrease of 162 mV of
the half wave potential. Again, this effect is more pro-
nounced in the case of ferrocenylphosphonic acid [30].
t
from the use of a ‘‘super base’’ BuLi/tBuOK at ꢀ80
ꢁC as we have reported for the preparation of ferroce-
nylphosphonic acid [30].
The 1H and 13C NMR spectra of FcPhP(O)(OEt)
showed the non-equivalence of the pairs of protons
and carbons in the substituted cyclopentadienyl ring,
Fig. 1. 1H NMR spectrum of the protons of the substituted Cp ring.

O. Oms et al. / Journal of Organometallic Chemistry 690 (2005) 363–370
365
Table 1
1H and 13C NMR chemical shift of ethyl ferrocenylphenylphosphinate
d (ppm)
1H NMR
13C NMR (JCP Hz)
H–C (2/5)
4.69/4.44
4.40/4.35
4.21
72.27 (11.6)/71.52 (11.1)
71.71 (21.6)/71.99(16.9)
70.15
O
2
7
1
5
H–C (3/4)
H–C (6)
H–C (7)
H–C (8)
H–C (10, 14)
H–C (11, 13)
H–C (12)
C (1)
3
(S)P
9
8
O
3.98
1.36
61.16 (5.5)
16.98 (6.5)
131.84 (9.8)
4
10
Fe
7.89
7.53
6
11
14
128.77 (12.6)
132.28 (2.4)
71.46(178)
7.53
13
12
C (9)
133 (131)
Table 2
Electrochemical data of diethyl ferrocenylphenylphosphinate, ferrocenylphenylphosphinic acid, and its sodium salt in methanol (scan rate: 100
mV sꢀ1
)
Compounds
E oxidation (mV)/SCE
E reduction (mV)/SCE
DE (mV)
E1/2 (mV)/SCE
DE1/2 (mV)/FcH
FcH
390
644
577
406
316
565
499
347
74
79
78
59
353
604
538
377
0
251
186
24
FcPhPO2 Et
FcPhPO2H
FcPhPOꢀ2 Naþ
2.2. Metal ferrocenylphenylphosphinates
to water are present. The CH vibrations appear at
3100, 3080, 3050 cmꢀ1 and the two mains bands at
1164 and 1074 cmꢀ1, 1159 and 1066 cmꢀ1, 1157 and
1070 cmꢀ1 are related to the symmetric and anti sym-
metric PO2 absorption of Zn, Cd and Mn compounds,
respectively. The presence of only two bands indicates
that the phosphinates are of symmetric coordination
mode, i.e., the oxygen atoms are linked to the same
number of metal atoms [16].
2.2.1. Syntheses of metal ferrocenylphenylphosphinates
Due to the low solubility of ferrocenylphenylphosphi-
nic acid in acidic water, the reactions were made at
pH > 8. Metal ferrocenylphenylphosphinates were ob-
tained by addition of metal nitrates to phosphinic acid
in water. The compositions of the powders obtained cor-
responded to M(O2PPhFc)2.
2.2.2. IR spectroscopy of metal ferrocenylphenylphosph-
inates
2.2.3. MAS NMR spectroscopy of metal ferro-
cenylphenylphosphinates
The 31P MAS NMR spectra of the diamagnetic
compounds (M@Zn, spinning rate, s.r., 10 kHz, scan
number, s.n., 360; M@Cd, s.r. 10 kHz, n.s. 480) show
The IR spectra of the three metalferrocenylphenyl-
phosphonates are similar. The IR spectrum of
Mn(O2PPhFc)2 is reported in Fig. 2. No bands related
ν(PO )
2
ν(CH)
ν(CC)
4000
3500
3000
2500
2000
1500
1000
500
Wavenumber (cm-1)
Fig. 2. IR spectrum of Mn(O2PPhFc)2.

366
O. Oms et al. / Journal of Organometallic Chemistry 690 (2005) 363–370
200
0
-100
100
50
δ (ppm)
(b)
0
-50
-100
300
100
100
50
0
-50
-100
δ (ppm)
δ (ppm)
(a)
(c)
Fig. 3. 31P MAS NMR of: (a) Zn(O2PPhFc)2; (b) Cd(O2PPhFc)2; (c) 113Cd MAS NMR of Cd(O2PPhFc)2 (chemical shift vs. Cd(ClO4)2 1 M).
one peak (Fig. 3(a) and (b)). 31P chemical shifts have
been correlated with P–O bond lengths and P–O–P
bond angles [42,43]. The presence of only one 31P
chemical shift for our compounds indicates that the
backbone structure involving mono and triple bridging
phosphinates can be ruled out. Indeed, for Zinc but-
ylphenylphosphinate, dibutylphosphinate and related
di ter-butylphosphates, in which the chain consists of
single and triple bridging phosphinates, the P–O bond
lengths and P–O–P bond angles differ for the mono
and triple bridging phosphinates. Therefore, a mini-
mum of two peaks can be expected for a such
structure.
2.2.4. X-ray powder patterns of metal phosphinates
No single crystals for structural characterization were
obtained. Fig. 4 shows the X-ray powder diffractograms
of the compounds.
The positions of the peaks are quite similar for the
three compounds. The distance and relative intensity
are reported in Table 3.
The similarities in compositions, in X-ray patterns, in
IR spectra, as well as in 31P NMR spectra allow us to
assume the iso-structurality of the three phosphinates.
The iso-structurality implies the same coordination
number for the metals and the same coordination mode
for the bridging phosphinate groups. The coordination
number of the metals has been determined by 113Cd
NMR to be four. Such coordination is also reported
for zinc phosphinates and is in agreement with the sym-
metry of the PO2 groups determined by IR spectroscopy
[2,3,7,52–56]. The unique peak observed by 31P MAS
NMR agrees with the two crystallographically equiva-
lent phosphinate bridges, as already reported for
[Pb(O2PPh2)2]n [6], [Zn(O2PHC6H5)2]n [7], [Zn(O2P(O-
The solid state 113Cd MAS NMR spectrum of
Cd(O2PPhFc)2 (s.r. 4.5 kHz, n.s. 27448) shows the pres-
ence of one resonance at 100.8 ppm (Fig. 3(c)).
The 113Cd chemical shift is very sensitive to the nat-
ure of the substituents around the Cd centre and also
on its coordination mode, although the isotropic shifts
of the oxo-Cd compounds are not sufficiently discrim-
inating to allow structure-chemical shift correlation
since the coordination polyhedra around the Cd atom
can be very irregular [44]. Nevertheless, a general pat-
tern between 113Cd chemical shifts and coordination
number for oxo-Cd compounds is 50 to 0 ppm for 6-
coordinate Cd, 30 to ꢀ50 for 7-coordinate Cd
[45,46]. A chemical shift of 5-coordinated Cd has been
reported at 90.6 ppm (220.2 ppm/(CdNO3)2) for cad-
mium phosphonocarboxylate Cd2(OH)(O3PC2H4CO2)
[47]. Chemical shifts from 114 to 108 ppm have been
found for 4-coordinated Cd in heterotermetallic iso-
propoxides Cd(OiPr)3 Ba(M2 (OiPr)9)2 (M@Ti, Zr,
Hf) [48,49]. The peak observed at 100.8 ppm corre-
sponds to a CdO4 site, the same coordination number
of cadmium has been found in related cadmium dial-
kyldithiophosphates Cd(S2P(OR)2)2 for both polynu-
clear and binuclear cadmium compounds [50,51]. A
5-coordinate Cd can be ruled out because it implies
the coordination of one oxygen to two Cd atoms,
which would give three bands for the stretching of
the non-symmetric PO2 groups.
(a)
(b)
(c)
5
10
15
2θ (˚)
20
25
Fig. 4. X-ray diffraction of M(O2PPhFc)2: (a) M@Mn; (b) M@Cd; (c)
M@Zn.

O. Oms et al. / Journal of Organometallic Chemistry 690 (2005) 363–370
367
Table 3
X-ray powder patterns of M(O2PR2)2
0
c)
b)
a)
Mn(O2PPhFc)2
Zn(O2PPhFc)2
Cd(O2PPhFc)2
-20
-40
-60
-80
˚
d A (I%)
˚
d A (I%)
d (I%)
12.15 (100)
8.62 (4.3)
12.24 (100)
8.65 (4.0)
6.13 (14.4)
5.49 (16.8)
4.75 (7.9)
4.10 (12.3)
12.08 (100)
8.55 (11.6)
6.10 (29.8)
5.41 (16.6)
4.85 (4.1)
4.22 (39)
6.08 (36.5)
5.45 (16.6)
4.78 (10.6)
4.18 (20.8)
3.84 (17.3)
0
200
400
600
800
1000
T(˚C)
Me)2)2]n [10], [Zn(O2P(OEt)2)2]n [9], and [Zn(O2PF-
cOH)2.2H2O]n [57].
Fig. 5. TGA of M(O2PPhFc)2 under Argon, 5 ꢁC minꢀ1: (a) M@Mn;
(b) Cd; (c) M@Zn.
A structure with tetracoordinated metals and double
bridged phosphinate groups can be proposed for the me-
tal ferrocenylphenylphosphinates (Scheme 3). The pro-
posed structure is similar to the structure of
Zn(HO3PFc)2 Æ 2H2O [57]
initial formation of benzene taking place without rup-
ture of the polymer backbone [55]. For the metal ferro-
cenylphenylphosphinates, the escape of one equivalent
of benzene would lead to weight losses of 10.9%,
10.2% and 11.1% for Zn(O2PPhFc)2, Cd(O2PPhFc)2
and Mn(O2PPhFc)2, respectively. However, the first
weight losses are in agreement with the escape of one
equivalent of ferrocene 25.1% (calc. 25.9%) for
Zn(O2PPhFc)2, 18.6% (calc. 24.4%) for Cd(O2PPhFc)2,
and 24.4% (calc. 26.3%) for Mn(O2PPhFc)2. The second
weight losses, which are of the same order of magnitude,
would result from the escape of the second equivalent of
ferrocene.
The thermal stability of metal phosphinates depends
on the substituents on the phosphorus atom: a sharp
weight loss occurs at 134 ꢁC for Zn(O2P(tBuO)2)2 [12],
550 ꢁC for Zn(O2PPh2)2, 460 ꢁC for Zn(O2PMe2)2, 420
ꢁC for Zn(O2PMePh)2 [54], whereas, for Zn(O2PFcPh)2
a three steps process begins at 400 ꢁC. The thermal sta-
bility depends also on the nature of the metal, the order
of stability found for metal ferrocenylphenylphosphi-
nates being: Mn > Zn > Cd.
2.2.5. Thermal stability of metalphosphinates
of
The
thermal
stability
metal
ferro-
cenylphenylphosphinates has been determined by TGA
(Fig. 5). As expected no weight loss corresponding to
the loss of water can be observed. Furthermore, the
products are stable until 355 ꢁC for cadmium phosphi-
nate, 400 ꢁC for zinc phosphinate, and 445 ꢁC for man-
ganese phosphinate. The weight losses occur in three
steps, the second one starting between 450 and 500 ꢁC.
This behaviour is in contrast with the ones reported
for Zn(O2PPh2)2, Zn(O2PMePh)2, Zn(O2PMe2)2 and
Zn(O2P(OtBu)2)2 for which a substantial weight loss oc-
curs in only one step [12,54,55]. The proposed mode of
decomposition of Zn(O2PPh2)2 at 500ꢁC involves the
Fe
Fe
2.2.6. Electrochemistry of poly metalphosphinates
Cyclic voltammetry experiments were performed in a
three electrode cell, in which the working electrode was a
P
P
´
cavity microelectrode furnished by the ‘‘reseau micro
O
O
O
O
`
´
electrode a cavite du CNRS’’ (France), the counter elec-
trode was a platinum wire, and the reference electrode
was a saturated calomel electrode (SCE). The electrolyte
was KCl 1 M in water. The cavity microelectrode has
been developed to study the electrochemical properties
of powdered materials [58]. The low reaction volume
(10ꢀ8 cm3) minimizes the distortions due to the large oh-
mic drop and capacitive current encountered with the
composite electrode device [59–62].
O
M
M
M
O
O
O
P
P
n
Fe
Fe
Fig. 6 shows the cyclic voltammograms of the three
compounds. Their half wave potentials are very close
to each other: 261, 255 and 265 mV for Zn(O2PPhFc)2,
Scheme 3. Proposed structure of Zinc, Cadmium and Manganese
ferrocenylphenylphosphinates.

368
O. Oms et al. / Journal of Organometallic Chemistry 690 (2005) 363–370
4. Experimental
200
100
0
4.1. Solvents and reagents
t
Ferrocene (Aldrich) was sublimed before use. BuLi
(Acro˜s) 1.5 M solution in pentane was titrated prior to
use. THF was distilled first over CaH2 and then over
Na/benzophenone. CH2Cl2 was dried over P2O5. tBuOK
(Avocado), dichlorophenylphosphine (Avocado) were
used as received.
Zn
Mn
Cd
-100
-200
4.2. Syntheses
-0.4
-0.2
0.0
0.2
0.4
0.6
0.8
Potentiel (V)
4.2.1. Ethyl chlorophenylphosphonate
In a two necked flask was added drop-wise 20 mL
(0.147 mol) of dichlorophenylphosphine to 45 mL
(0.76 mol) of ethanol at 0 ꢁC under stirring which was
maintained over night. The solvent was eliminated in
vacuum and the product was distilled
Fig. 6. Cyclic voltammograms of M(O2PPhFc)2, M@Zn, Cd, Mn.
Cd(O2PPhFc)2 and Mn(O2PPhFc)2, respectively. The
value is also close to the one of the sodium salt of the
ferrocenylphenylphosphinic acid FcPhP(O)OꢀNa+ (251
mV) measured in water.
The half wave potential of the metal ferro-
cenylphenylphosphinates are almost insensitive to the
nature of the metal.
Unexpectedly, the half wave potential of metal ferr-
ocenylphosphonates M(O2PFcOH) Æ xH2O containing
an unreacted OH group on the phosphorus are also
very close: 255 mV for Zn(HO3PFc)2. 2H2O, 238
mV for Cd(HO3PFc)2 Æ 3.5H2O, and 243 mV for
Mn(HO3PFc)2 Æ 3H2O and 246 mV for Na(HO3PFc)
[63]. The substitution of the phenyl group by an OH
group has very little effect on the half wave potential
of the ferrocene/ferrocenium couple. The influence of
the nature of the second substituent on the redox
behaviour of FeII/FeIII couple is currently under
investigation.
(b.p. 110 ꢁC/3 mm Hg) leading to 22.49 g (0.132 mol,
90% yield) of ethyl phenylphosphonate PhP(O)(OEt)H.
1H NMR (CDCl3, d ppm): 7.62 (m, 2H); 7.37 (m, 3H),
1
7.5 (d, 1H, JPH = 573 Hz); 4.07 (m, 2H); 1.37 (t, 3H).
31P NMR (CDCl3, d ppm): 27.42.
22.49 g (0.132 mol) of ethyl phenylphosphonate were
dissolved in 150 mL of CCl4 and frozen to 0 ꢁC. Cl2 gas
was bubbled trough the solution until it became green.
The excess of chlorine was eliminated by bubbling
nitrogen trough the solution. The solvent was evapo-
rated under vacuum and the product distilled (b.p. 90
ꢁC/3 mm Hg) giving 16.06 g (0.0785 mol, 59% yield)
1
of ethyl chlorophenylphosphonate. H NMR (CDCl3,
d ppm): 7.77 (m, 2H), 7.38 (m, 3H); 4.27 (m, 2H);
1.30 (t, 3H).
4.2.2. Ethyl ferrocenylphenylphosphinate
In a Schlenk tube was added drop-wise, at ꢀ78 ꢁC, 14
t
mmol of BuLi in pentane to a solution of 19.6 mmol
t
(3.63 g) of ferrocene and 3.5 mmol (0.39 g) of BuOK
in 80 mL of THF under stirring. After stirring for 30
min, 19.6 mmol (4 g) of ethyl chlorophenylphosphonate
in 10 mL of THF were added drop-wise. The mixture
was left to return to room temperature and 10 mL of
a 1 M NaOH solution were added. The mixture was ex-
tracted with 3 · 30 mL of CH2Cl2. The organic phase
was dried over MgSO4, filtered, and the solvent evapo-
rated in vacuum. The compound was then purified by
silica column chromatography using CH2Cl2 to elimi-
nate the excess of ferrocene, and then CH2Cl2/THF
(70/30). After evaporation of the solvent under vacuum,
12.3 mmol (4.36 g) of ethyl ferrocenylphenylphosphinate
3. Conclusion
Electroactive polymetal phosphinates have been pre-
pared starting from ferrocenylphenylphosphinic acid
synthesized in high yield. The zinc, cadmium and man-
ganese derivatives are iso-structural based on the com-
position, and on IR and NMR spectroscopy, and on
the X-ray powder diffractogramme. The structure pro-
posed involves tetracoordinated metals double bridged
by the phosphinate groups. The metal ferro-
cenylphenylphosphinates possess a great stability in
spite of the presence of the ferrocenyl moiety. The half
wave potential of the ferrocene/ferrocenium couple re-
mains the same whatever the metal. Thus, ferrocenyl-
phenylphosphinic acid cannot be used to detect metal
salts electrochemically.
1
were obtained as a brown solid (88% yield). H NMR
3
(CDCl3, d ppm): 1.36 (t, 3H, H8, JHH = 7.1 Hz); 3.98
(m, 2H, H7); 4.21 (s, 5H, H6); 4.35 (m, 1H, H3); 4.40
(m, 1H, H4); 4.44 (m, 1H, H5); 4.69 (m, 1H, H2); 7.53

O. Oms et al. / Journal of Organometallic Chemistry 690 (2005) 363–370
369
(m, 3H, H11, H12, H13); 7.89 (m, 2H, H10, H14); 13C
Cd, 14.74. Found: C, 50.22; H, 3.68; Fe, 14.40; P, 8.12;
Cd, 14.46%. 31P MAS NMR: 30.6 ppm. 113Cd MAS
NMR 100.8 ppm vs. Cd(ClO4)2 1 M.
3
NMR (CDCl3, d ppm): 16.98 (d, C8, JCP = 6.5 Hz);
61.16 (d, C7, JCP = 5.5 Hz); 70.15 (s, C6); 71.46 (d,
2
1
C1, JCP = 178.1 Hz); 71.52 (d, C5, JCP = 11.1 Hz);
2
3
71.71 (d, C3, JCP = 21.6 Hz); 71.99 (d, C4, JCP = 16.9
3
4.2.6. Manganese ferrocenylphenylphosphinate, Mn(O2-
PPhFc)2
2
Hz); 72.27 (d, C2, JCP = 11.6 Hz); 128.76 (d, C11, C13,
3
2JCP = 12.6 Hz); 131.84 (d, C10, C14, JCP = 9.9 Hz);
The pH of a solution of 0.1 g (0.31 mmol) of ferroce-
nylphenylphosphinic acid in 30 mL of water was ad-
justed to 9.4 by addition of NaOH (1 M). 0.069 g
(0.28 mmol) of manganese nitrate tetra hydrate was
added and the solution was left for 6 days at room tem-
perature. The yellow solid was filtered, washed with
CH3OH and Et2O and dried under vacuum, yielding
0.088 g (0.13 mmol, 84% yield) of yellow powder. Anal.
Calc. for C32H28Fe2P2MnO4: C, 54.47; H, 3.97; Fe,
15.83; P, 8.79; Mn, 7.79. Found: C, 54.53; H, 3.60; Fe,
15.73; P, 8.31; Mn, 7.72%.
4
1
132.3 (d, C12, JCP = 2.4 Hz); 133 (d, C9, JCP = 131
Hz); 31P (CDCl3, d ppm): 37.7. IR (KBr) m (P@O):
1208 cmꢀ1. Anal. calc. for C18H19 FePO2: C, 61.01; H,
5.37, P, 8.76; Fe, 15.76. Found: C, 61.10; H, 5.61; P,
8.66; Fe, 15.00%.
4.2.3. Ferrocenylphenylphosphinic acid
1.35 g (3.8 mmol) of ethyl ferrocenylphenylphosphi-
nate were dissolved in 10 mL of CH2Cl2 in a Schlenk
tube. 1 mL (7.6 mmol) of Me3SiBr was added drop-wise,
the solution was stirred overnight. and 10 mL of water
were added leading to the precipitate, which is filtered
and washed with CH2Cl2 and Et2O. 1.14 g (3.5 mmol)
of ferrocenylphenylphosphinic acid was obtained (92%
4.3. Physical measurements
The NMR spectra of solutions were performed on a
1
Bruker Avance DPX 200, chemical shifts for H and
1
yield). H NMR (CD3OD, d ppm): 4.28 (m, 4H); 4.51
(s, 5H); 7.54 (m, 3H), 7.83 (m, 2H); 13C NMR (CD3OD,
13C–1H are referenced to SiMe4 and deuterated solvent
and for 31P to H3PO4 (85%) and deuterated solvent.
3
d ppm): 69.8 (s,C6); 71.53 (d, C3, C4, JCP = 14.6 Hz);
71.65 (d, C2, C5, JCP =11.6 Hz); 128.53 (d, C11, C13,
2
1
31P MAS H decoupled NMR spectra were recorded
3
2JCP = 13.1 Hz); 130.83 (d, C10, C14, JCP = 10.1 Hz);
on a Bruker DPX 300 operating at 121.5 MHz, chemical
shifts are referenced to H3PO4 (85%), the magic angle
spinning rates was 10kHz, and the scan numbers were
between 360 and 600 with a pulse angle of p/2. 113Cd
1
132.00 (d, C12); 134.9 (d, C9, JCP = 138 Hz); 31P
NMR (CD3OD, d ppm): 35.4. IR (KBr) m(P@O): 1224
cmꢀ1. Anal. Calc. for C16H15FePO2: C, 58.89; H, 4.61;
P, 9.51, Fe, 17.11. Found: C, 58.46; H, 4.50; P, 8.96,
Fe, 16.69%.
1
MAS H decoupled spectra were recorded on a Bruker
AM 400 operating at 88.75 MHz, chemical shifts were
referenced to Cd(ClO4)2 1 M, the spinning rate was
4.5 kHz, the scan number was 27448, with a pulse angle
of p/6. Samples (60–80 mg) of the metal ferro-
cenylphenylphosphinates were placed in a zirconium
dioxide rotor 4 mm in diameter. The width of a refer-
ence line for crystalline adamantane was used to check
the uniformity of the magnetic field. Infrared spectra
were taken on a Thermo Nicolet Avatar 320 FT-IR
spectrophotometer as KBr pellets. Cyclic voltammo-
grams were obtained with a Voltalab 10 in a three-elec-
trode cell. A 0.20 cm diameter platinum disc working
electrode, a platinum wire auxiliary electrode and a sat-
urated calomel reference electrode were used to record
voltammograms of soluble compounds. The electrolyte
was nBu4NPF6 (0.1 M in methanol). For the insoluble
metal ferrocenylphenylphosphinates, a cavity microelec-
4.2.4. Zinc ferrocenylphenylphosphinate: Zn(O2PPhFc)2
To 0.1 g (0.31 mmol) of ferrocenylphenylphosphinic
acid dissolved in 35 mL of EtOH was added 0.12 g
(0.41 mmol) of zinc nitrate hexahydrate. After 6 days,
the precipitate was filtered, washed with methanol and
ether and dried under vacuum. 0.073 g (0.11 mmol) of
a fibrous yellow solid was obtained (73% yield based
on the acid). Anal. Calc. for C32H28Fe2P2ZnO4: C,
53.67; H, 3.91; Fe, 15.60; P, 8.67; Zn, 9.14. Found: C,
53.79; H, 4.03; Fe, 15.28; P, 8.61; Zn, 8.91%. 31P MAS
NMR: 26.8 ppm.
4.2.5. Cadmium ferrocenylphenylphosphinate, Cd(O2-
PPhFc)2
0.1 g (0.31 mmol) of ferrocenylphenylphosphinic acid
was dissolved in 27 mL of water. The pH of the solution
was adjusted to 8 by addition of NaOH (1 M). 0.096 g
(0.31 mmol) of cadmium nitrate tetrahydrate was added
and the solution was left for 6 days at room tempera-
ture. The precipitate was filtered washed with methanol
and ether and dried under vacuum. Yellow needles were
obtained (0.55 g, 0.07 mmol, 45% yield). Anal. Calc. for
C32H28Fe2P2CdO4: C, 50.36; H, 3.67; Fe, 14.64; P, 8.13;
´
trode of Pt, furnished by the ’’reseau microelectrode a
cavite du CNRS’’ France, was used as working elec-
´
`
´
trode. The electrolyte was KCl (1 M in water). The scan
rate was 100 mV sꢀ1. TGA were recorded on a Netzch
409 thermobalance. X-ray powder diffraction was per-
formed on an X Pert Philips diffractometer. Elemental
analyses were performed by the CNRS ‘‘Service central
dꢀanalyse’’ in Vernaison France.

370
O. Oms et al. / Journal of Organometallic Chemistry 690 (2005) 363–370
[30] O. Oms, F. Maurel, F. Carre, J. Le Bideau, A. Vioux, D.
Acknowledgement
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Chem. 60 (1973) C53.
Financial support from the Centre National de la
Recherche Scientifique, CNRS, and from the French
Minister of Research is gratefully acknowledged.
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