Synthesis and copolymerization of a ruthenium(II) complex with the deprotonated form of 2-(acetoacetoxy)ethylmetacrylate

Article abstract of DOI:10.1016/S0020-1693(02)00832-0

The new polymerizable complex Ru(PPh₃)₂(AAEMA)₂ was obtained by reaction of RuCl₂(PPh₃)₃ with the anion of 2-(acetoacetoxy)ethylmethacrylate (AAEMA^-). The complex was characterized by NMR, IR, UV-Vis, mass spectrometry and cyclic voltammetry techniques. In order to obtain a supported metal complex suitable for catalytic applications, Ru(PPh₃)₂(AAEMA)₂ was copolymerized with N,N-dimethylacrylamide as comonomer and N,N′-methylenebisacrylamide as cross-linker. The obtained insoluble resin [Ru-pol] was characterized by elemental analyses, IR, UV-Vis and CP/MAS ³¹P{¹H} NMR techniques.

Full text of DOI:10.1016/S0020-1693(02)00832-0

Inorganica Chimica Acta 335 (2002) 107ꢁ112
/
www.elsevier.com/locate/ica
Synthesis and copolymerization of a ruthenium(II) complex with the
deprotonated form of 2-(acetoacetoxy)ethylmetacrylate
Piero Mastrorilli a, Cosimo Francesco Nobile a,*, Gian Paolo Suranna a,
Maria Rosaria Taurino a, Mario Latronico b
a Dipartimento di Ingegneria Civile ed Ambientale (D.I.C.A.) del Politecnico di Bari-Sezione Chimica, via Orabona 4, I-70125 Bari, Italy and Centro
C.N.R. ICCOM, Italy
b Dipartimento di Ingegneria e Fisica dell’Ambiente, Universita` della Basilicata, C.da Macchia Romana, 80100 Potenza, Italy
Received 21 November 2001; accepted 17 January 2002
Abstract
The new polymerizable complex Ru(PPh3)2(AAEMA)2 was obtained by reaction of RuCl2(PPh3)3 with the anion of 2-
(acetoacetoxy)ethylmethacrylate (AAEMAꢀ). The complex was characterized by NMR, IR, UVꢁ
Vis, mass spectrometry and cyclic
voltammetry techniques. In order to obtain a supported metal complex suitable for catalytic applications, Ru(PPh3)2(AAEMA)2
/
was copolymerized with N,N-dimethylacrylamide as comonomer and N,N?-methylenebisacrylamide as cross-linker. The obtained
insoluble resin [Ru-pol] was characterized by elemental analyses, IR, UVꢁ
/
Vis and CP/MAS 31P{1H} NMR techniques. # 2002
Elsevier Science B.V. All rights reserved.
Keywords: Ruthenium; Supported complexes; Polymerizable complexes; Hydrogenation
1. Introduction
[5] and optically active BINOLꢁ/BINAP supported
complexes [6].
We have recently studied the synthesis [7] and use in
catalysis [8] of several hybrid catalysts based on Group
The ease of separation and potential recyclability of a
supported metal complex are among the most important
reasons for the widespread interest devoted to this topic
by the scientific community [1]. The materials for
catalytic applications obtained by supporting a soluble
metal complex onto an organic polymer are often
referred to as ‘hybrid’ due to the fact that they preserve
the features of the homogeneous catalyst in terms of
activity and selectivity and gain the advantages of
heterogeneous systems, namely their robustness and
recyclability. Very recent works on the topic of ruthe-
nium supported metal complexes include the use of
ruthenium(II) cationic complexes bearing a sulphonated
pendant chain supported by hydrogen bonding on silica
[2], RuCl2(PPh3)3 supported on Merrifield resin [3],
polymer-anchored complexes of Ru(III) with Schiff’s
VIIIꢁX metal complexes with the anion of 2-(acetoace-
/
toxy)ethyl methacrylate (AAEMAꢀ). This paper deals
with the synthesis of the new polymerizable ruthenium
complex Ru(PPh3)2(AAEMA)2, which was copolymer-
ized with a suitable comonomer [N,N-dimethylacryla-
mide
(DMAA)]
and
cross-linker
[N,N?-
methylenebisacrylamide (MBAA)] to obtain a sup-
ported ruthenium(II) complex.
2. Results and discussion
Our first attempt to synthesise a polymerizable
ruthenium species was aimed at the preparation of the
homoleptic complex Ru(AAEMA)3. The reaction of
RuCl3 with KAAEMA in ethanol, a procedure success-
fully used for the synthesis of Fe(AAEMA)3 [7b], did
not afford the expected Ru(AAEMA)3. Neutralization
by KOH or NaHCO3 of a Ru(III) acidic solution and
subsequent reaction at room temperature with
bases [4], solꢁgel entrapped ruthenium chiral catalysts
/
* Corresponding author. Tel.: ꢂ
5963-611.
E-mail address: c.f.nobile@poliba.it (C.F. Nobile).
/
39-080-5963-604; fax: ꢂ39-080-
/
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 0 8 3 2 - 0

108
P. Mastrorilli et al. / Inorganica Chimica Acta 335 (2002) 107ꢁ112
/
lines (JXX? comparable with JAX). In the case of
Ru(PPh3)2(AAEMA)2, the signal attributable to the
ipso-carbons of the phenyl rings consists of six lines
and can in no way be interpreted in terms of an AXX’
spin system. However, by admitting a chemical inequi-
valency between the two phosphorus atoms that would
Scheme 1. Synthesis of Ru(PPh3)2(AAEMA)2.
HAAEMA was then tried, adapting the known synth-
esis of Ru(acac)3 [9,10] to our aim. Unfortunately these
tests resulted in the obtainment of complex mixtures of
oily products, from which the isolation of well-defined
compounds was hampered.
The synthesis of a polymerizable ruthenium complex
was achieved by reacting RuCl2(PPh3)3 with AAEMAꢀ
in ethanol, leading to Ru(PPh3)2(AAEMA)2 as a yellow
powder in a 68% yield (Scheme 1).
This compound is air-stable in the solid state but
rapidly decomposes in non-deoxygenated solvents.
Ru(PPh3)2(AAEMA)2 is fairly soluble in THF, di-
methylformamide and acetonitrile, slightly soluble in
methanol, ethanol, diethylether and light petroleum
ether and insoluble in water. It decomposes in acetone,
aromatic and chlorinated solvents, giving deep green
solutions.
result in the occurence of an AXY spin system (A:
13
C
; X, Yꢃ31
P), six lines are predictable for the A
/
ipso
part of the spectrum. A good agreement between
simulated and experimental spectrum (Fig. 1(a)) was
obtained using the following parameters: d(PX) 53.616,
d(PY) 53.584, JAX
ꢃ
/
39.8 Hz, JAY
ꢃ/1.3 Hz, JXY
ꢃ41.0
/
Hz. Due to the very small difference in chemical shift
necessary to fit the Cipso signal, both simulated and
experimental 31P{1H} NMR spectrum of Ru(P-
Ph3)2(AAEMA)2 consists of a singlet at d 53.6 (Fig.
1(b)).
The obtained JXY (41.0 Hz) allows to assign a cis-
geometry for the two coordinated phosphines and rules
out structures d and e among the five possible isomers of
Ru(PPh3)2(AAEMA)2 shown in Fig. 2.
Moreover, the inequivalency between the two P atoms
seems to indicate structure b as the most probable.
Its UV-Vis spectrum exhibits absorptions at lmax
219 nm [oꢃ 18400 l
52940 l molꢀ1 cmꢀ1], 260 nm [oꢃ
molꢀ1 cmꢀ1], 310 nm [oꢃ7900 l molꢀ1 cmꢀ1] and is
ꢃ
/
/
/
The
electrochemical
behaviour
of
Ru(P-
/
Ph3)2(AAEMA)2 was submitted to investigation by
cyclic voltammetry in CH3CN under inert gas (nitrogen)
atmosphere (Fig. 3).
consistent with a Ru(II) involved in an octahedral
coordination [11]. Comparison between the IR spectrum
of Ru(PPh3)2(AAEMA)2 and that of RuCl2(PPh3)3
The proximity of the anodic peak (ꢂ
respect to Ag/AgNO3) to the cathodic peak (ꢀ
/
60 mV with
85 mV
shows the disappearence of the RuꢁCl stretching at
/
/
319 cmꢀ1, and the appearance of the strong combina-
tion bands of the b-ketoesterate ring at 1609 and 1504
cmꢀ1; the b-ketoesterate ring out of plane bending
appears at 772 cmꢀ1. The presence of a strong absorp-
tion at 1717 cmꢀ1 is ascribable to the uncoordinated
methacrylate carbonyl stretching while bands for the
coordinated phosphine appear at 740, 695 and 523
cmꢀ1. The 1H NMR spectrum recorded in CD3OD
shows the methacrylate olefinic protons of the
AAEMAꢀ at d 5.60 and d 6.05. The methynic proton
appears at d 4.58 and the methyl protons of the b-
ketoesterate and of the methacrylate moieties fall at d
1.72 and d 1.90 respectively.
with respect to Ag/AgNO3) potential and the compar-
able anodic and cathodic area indicate the quasi-
reversibility of the first electrochemical process:
[Ru(II)(PPh3)2(AAEMA)2]0
[Ru(III)(PPh3)2(AAEMA)2]ꢂ ꢂeꢀ
At an anodic potential of 845 mV, a peak attributable
to the following process was observed:
[Ru(III)(PPh3)2(AAEMA)2]ꢂ0
[Ru(IV)(PPh3)2(AAEMA)2]2ꢂ ꢂeꢀ
The corresponding reduction peak was observed at 726
mV. Also this process appears to be quasi-reversible.
The complex Ru(PPh3)2(AAEMA)2 was submitted to
MS analysis by MALDI TOF and LC-MS. MALDI
TOF analysis did not return the expected molecular
weight of the complex: choosing 9-nitroantracene as
matrix and C60/C70 as reference, the highest mass peak
The coupling constant between the phosphorus atoms
provides information on the geometry of the phosphine
2
ligands around the metal, being the values of JPP for
trans-phosphines sensibly higher than those for cis-
2
phosphines. The value of JPP can be accessed by
studying the resonance of the ipso-carbons of the phenyl
rings in the 13C NMR spectrum [12].
observed was at m/zꢃ
the calculated (1052 Da). Noteworthy, a peak attribu-
table to the loss of PPh3 at m/zꢃ794 was observed
[expected value of [Mꢀ
262]ꢂ: 790 Da].
/1059, seven m/z units higher than
In the hypothesis of two chemically equivalent co-
ordinated phosphines the appearance of such resonances
has been studied by Nelson et al. [13] who simulated
/
/
13
different AXX? spin systems (A:
varying the JXX? coupling constant. Depending on the
C
; X, X?ꢃ31
P),
/
LC MS analysis performed by direct injection of a
methanol solution of the complex gave the expected
ipso
[Mꢂ
/
Hꢂ] peak at m/zꢃ
1053.2 (Fig. 4) and a satisfac-
tory match with the calculated isotope pattern.
/
relative value of JXX’ and JAX the spectrum was
demonstrated to contain three (JXX?ꢃ20 JAX) or five
/

P. Mastrorilli et al. / Inorganica Chimica Acta 335 (2002) 107ꢁ
/112
109
Fig. 1. (a) Experimental (top trace) and simulated (bottom trace) spectrum for the 13Cipso in Ru(PPh3)2(AAEMA)2. (b) Experimental (top trace) and
simulated (bottom trace) spectrum for the 31P signal in Ru(PPh3)2(AAEMA)2.
Complex Ru(PPh3)2(AAEMA)2 was submitted to
copolymerization with DMAA and MBAA (Fig. 5), at
60 8C in dimethylformamide (DMF) in the presence of
2,2-azobisisobutyronitrile (AIBN) as radical initiator,
tion preserves the ruthenium(II) chemical environment.
In particular, the appearance of the two combination
bands in the IR of Ru-pol at 1610 and 1505 cmꢀ1
proves that the Ru(II) centre is present in the polymer as
a b-ketoesterate. Moreover, peaks attributable to the
coordinated triphenylphosphine appear at 745, 697 and
523 cmꢀ1 appear in the IR of Ru-pol.
Solid state CP/MAS 31P{1H} NMR spectra of the
obtained resin showed a broad signal at d 53.0, in
accordance with the signal observed for Ru(P-
Ph3)2(AAEMA)2 in CD3OD [d 31P{1H} 53.6 ppm]. It
can be thus assumed that the coordination mode of
obtaining a yellowꢁ
/
orange powder referred to in the
following as Ru-pol.
The copolymer is insoluble in all common organic
solvents, swells in halogenated and polar solvents and
shrinks in hexane or diethyl ether. Elemental analysis
showed a ruthenium content of 1.85%. The comparison
of IR and UVꢁ/Vis spectra of the copolymer with those
of the precursor complex indicates that the polymeriza-
Fig. 2. Possible isomers for the complex Ru(PPh3)2(AAEMA)2.

110
P. Mastrorilli et al. / Inorganica Chimica Acta 335 (2002) 107ꢁ112
/
recorded on a Bruker AM 500 or on a Bruker Avance
DRX500 spectrometer; frequencies are referenced to
Me4Si (1H and 13C) and 85% H3PO4 (31P). The high
resolution 31P solid state NMR spectra were performed
on a JEOL GSE 270 (6.34 T) operating at 109.4 MHz
under conditions of 1H0
/
31P cross-polarization, high
power proton decoupling and magic angle spinning. The
908 pulse was 6.0 ms and the contact pulse was 5 ms. The
spectra of the complexes were collected after 1000
transients and a relaxation delay of 10 s. The line
broadening was set to 100 Hz. H3PO4 85% was used as a
reference (dꢃ0). Cylindrical 6 mm o.d. zirconia rotors
/
with sample volume of 120 ml were employed with
spinning speed of 6.5 KHz. The magic angle was
adjusted from the 79Br MAS spectrum of KBr by
minimizing the linewidth of the spinning side band
satellite transitions.
GC-MS analyses were acquired on a HP 5973
instrument. Conversions and yields were calculated by
GLC analysis using the internal standard method.
MALDI-TOF mass spectrometry was performed on a
Voyager-DE Biospectrometry Workstation (PerSpective
Biosystems Inc., Framingham, MA) mass spectrometer
equipped with a nitrogen laser emitting at 337 nm. The
instrument was set to linear mode at an accelerating
Fig. 3. Cyclic voltammogram for a 0.01 M Ru(PPh3)2(AAEMA)2 in
acetonitrile containing 0.1 M TEAP.
triphenylphosphine is unchanged in the monomeric
complex and in its heterogeneous analogue.
In order to check for catalytic activity of Ru(P-
Ph3)2(AAEMA)2 and of its heterogeneous analogue, 1-
heptene was submitted to hydrogenation at 65 8C in
methanol at P(H2)ꢃ20 bar. The first results show that
/
both Ru(PPh3)2(AAEMA)2 and Ru-pol act as moder-
ately active hydrogenation catalyst with TOF of 8 and
16 hꢀ1, respectively. Work is in progress in order to
confirm the higher activity of Ru-pol respect to Ru(P-
Ph3)2(AAEMA)2 and to verify if the catalyst can be
recycled and used in the hydrogenation of other organic
substrates.
voltage in the range 23 000ꢁ25 000 V. External calibra-
/
tion was performed using C60/C70. The detecting system
was composed of a linear detector and a digitising
oscilloscope (frequency: 500 MHz). The sample was
prepared with an approximate concentration of 30 mg
mlꢀ1 in THF. The chosen matrix was 9-nitroantracene
in THF. A 0.2-ml sample of the solution and 0.2 ml of the
matrix solution were mixed, placed on a golden target
and then analysed after solvent evaporation. LC-MS
analyses were performed on a Agilent HPLC system
equipped with DAD and MS systems (Agilent 1100 LC
MS). The LC-MS system was controlled by Agilent
Chemstation software, which allowed full instrument
3. Experimental
All reactions were carried out under nitrogen using
standard Schlenk techniques.
HAAEMA was purchased from Polyscience, RuCl3
was purchased from Johnson Matthey UK. Reagents
were used as received. RuCl2(PPh3)3 was prepared by
control, simultaneous mass spectrometry and UVꢁ
/
Vis
Vis
literature methods [14]. UVꢁVis spectra were recorded
on a Uvikon 942 spectrophotometer. IR spectra were
recorded on a Bruker Vector 22. NMR spectra were
/
spectrum data acquisition and data analysis. UVꢁ
/
detection was carried out at a wavelength of 254 nm.
Fig. 4. LC MS spectrum of Ru(PPh3)2(AAEMA)2.

P. Mastrorilli et al. / Inorganica Chimica Acta 335 (2002) 107ꢁ
/112
111
Fig. 5. Synthesis of the heterogeneous analogue of Ru(PPh3)2(AAEMA)2.
APCI conditions were: positive ion mode, solvent
methanol, flow rate 0.5 ml/min, nitrogen as nebulizing
and drying gas, nebulizer pressure 60 psig, drying gas
flow 3 l minꢀ1 at 325 8C, vaporizer temperature
325 8C, capillary voltage 4000 V, corona current 4
mA, fragmentor voltage 150 V. Mass spectrometry data
prepared under nitrogen, in degassed CH3CN contain-
ing 0.1 M tetraethylammonium perchlorate (TEAP) and
0.01 M in Ru(PPh3)2(AAEMA)2. The scan rate was 50
mV sꢀ1
.
were acquired in the scan mode (mass range m/z 50ꢁ
/
3.1. Synthesis of Ru(PPh3)2(AAEMA)2
1500). C and H elemental analyses were carried out on a
Carlo Erba EA 1108. Ruthenium elemental analyses
were carried out on a Perkin Elmer Optima 3000 ICP-
AES instrument equipped with a diode array detector.
The ICP torch uses Argon as feed gas and nitrogen for
the elimination of oxygen traces in the plasma. The
electromagnetic induction power was set to 1300 W. The
RuCl2(PPh3)3 (1g, 1.04 mmol) was dissolved in 150 ml
ethanol. Under vigorous stirring, 0.725 ml (3.75 mmol)
of HAAEMA and 0.524 ml (3.75 mmol) of triethyla-
mine was added dropwise to the metal complex solution,
and reacted, for 32 h at room temperature (r.t.). The
solution colour slowly turned from dark red to dark
yellow. The solvent mixture was evaporated to 15 ml
and a light yellow solid precipitated. The remaining
readings were taken at lꢃ
The cyclic voltammograms were recorded with a
potentiostatꢁgalvanostat PAR 273 EG&G (Princeton
Applied Research) coupled with an HP 1070 XꢁYꢁt
/
240.272 nm.
/
solution was removed and the solid washed with 3ꢄ
/
15
/
/
ml of ethanol, 2ꢄ15 ml of degassed water and
/
recorder and a conventional three electrode system
(counter electrode: Pt plate; reference electrode Ag/
AgNO3, working electrode Pt plate). The solution was
eventually with 15 ml of ethanol. After drying in vacuo,
0.750 g of the pure product was obtained as yellow
powder (yield 68%).

112
P. Mastrorilli et al. / Inorganica Chimica Acta 335 (2002) 107ꢁ112
/
Elemental analysis: Anal. Calc. for C56H56O10P2Ru:
C, 63.93; H, 5.36; P, 5.89 Ru, 9.61. Found: C, 63.37; H,
5.43; P, 6.0; Ru, 9.4%. M.p.: 112ꢁ
120 8C (dec). 1H
NMR (CD3OD, 500 MHz, 293 K): [ppm] dꢃ
3H, C(O)CH3), 1.90 (dd, Jtrans 1.0 Hz, Jcis
3H, methacrylate CH3), 3.46ꢁ
4.01ꢁ4.04 (m, 2H, OꢁCH2), 4.58 (s, 1H, C(O)CHC(O)),
5.59ꢁ5.60 (m, 1H, cis vinyl proton), 6.046ꢁ6.05 (m, 1H,
trans vinyl proton), 7.05ꢁ7.08 (m, 12H, Phortho), 7.22ꢁ
7.25 (m, 18H, Phmeta, Phpara); 13C{1H} NMR (THF-d8,
125 MHz, 293 K): [ppm] dꢃ18.45 (s, methacrylate
CH3), 27.87 (OꢁC(O)CHC(O)CH3), 62.30, (CH2ꢁ
CH2), 63.67 (CH2ꢁCH2), 83.91 (OꢁC(O)CHC(O)CH3),
125.30 (s, OꢁC(O)CꢀC), 127.76 (m, Phmeta), 129.34 (s,
Phpara), 135.36 (m, Phortho), 136.62 (m, Phipso), 137.48 (s,
OꢁC(O)C ꢀC), 166.95 (s, OꢁC(O)CꢀC), 169.62 (s, Oꢁ
C(O)CHC(O)CH3), 188.87 (s, OꢁC(O)CHC(O)CH3).
31P{1H} NMR (CD3OD, 202 MHz, 293K) dꢃ
53.6 (s).
IR (nujol, CsI pellets): [cmꢀ1] nꢃ
1717 vs (methacrylate
Cꢃ
assistance. Italian C.N.R. and M.I.U.R. are gratefully
acknowledged for financial support.
/
/
1.72 (s,
ꢃ
/
ꢃ
/
1.5 Hz,
References
/
3.50 (m, 2H, OꢁCH2),
/
[1] (a) D.D. Whitehurst, Chemtech 10 (1980) 44;
(b) F.R. Hartley, Supported Metal Complexes, D. Reidel,
Dordrecht, 1985;
/
/
/
/
/
/
(c) A. Choplin, F. Quignard, Coord. Chem. Rev. 180 (1998) 1679;
(d) D. Brunel, N. Bellocq, P. Sutra, A. Cauvel, M. Lasperas, P.
Moreau, F. Di Renzo, A. Galarneau, F. Fajula, Coord. Chem.
Rev. 180 (1998) 1085;
/
/
/
(e) R. Psaro, S. Recchia, Catal. Today 41 (1998) 139.
[2] C. Bianchini, V. Dal Santo, A. Meli, W. Oberhauser, R. Psaro, F.
Vizza, Organometallics 19 (2000) 2433.
/
/
/
/
[3] N.E. Leadbeater, J. Org. Chem. 66 (2001) 2168.
[4] M.K. Dalal, R.N. Ram, J. Mol. Catal. A 159 (2000) 285.
[5] F. Gelman, D. Avnir, H. Schumann, J. Blum, J. Mol. Catal. A
146 (1999) 123.
/
/
/
/
/
/
/
[6] H.B. Yu, Q.S. Hu, L. Pu, J. Am. Chem. Soc. 122 (2000) 6500.
[7] (a) B. Corain, M. Zecca, P. Mastrorilli, S. Lora, G. Palma,
Makrom. Chem., Rapid Commun. 14 (1993) 799;
(b) P. Mastrorilli, C.F. Nobile, G. Marchese, Inorg. Chim. Acta
233 (1995) 65;
/
/
O), 1609 vs, 1504 vs (b-ketoesterate combination
bands), 1259 vs, 1161 vs, 1087 s, 982 m, 772 m (b-
ketoesterate ring out of plane bending), 740 m, 723 m,
(c) P. Mastrorilli, A. Rizzuti, G.P. Suranna, C.F. Nobile, Inorg.
Chim. Acta 304 (2000) 21.
695 s, 543 m, 523 s, 280 w, 254 w, 226 m; UVꢁ
[ethanol, 6.27ꢄ 52940 l
10ꢀ5 mol lꢀ1]: 219 nm [oꢃ
molꢀ1 cmꢀ1], 260 nm [oꢃ18400 l molꢀ1 cmꢀ1], 310
nm [oꢃ
7900 l molꢀ1 cmꢀ1].
/Vis
/
/
[8] (a) P. Mastrorilli, C.F. Nobile, Tetrahedron Lett. 35 (1994) 4193;
(b) L. Lopez, P. Mastrorilli, G. Mele, C.F. Nobile, Tetrahedron
Lett. 35 (1994) 3633;
/
/
(c) R. Giannandrea, P. Mastrorilli, C.F. Nobile, G.P. Suranna, J.
Mol. Catal. 99 (1994) 27;
(d) P. Mastrorilli, C.F. Nobile, J. Mol. Catal. 99 (1994) 19;
(e) M.M. Dell’Anna, P. Mastrorilli, C.F. Nobile, G.P. Suranna, J.
Mol. Catal. 103 (1995) 17;
3.2. Copolymerization of Ru(PPh3)2(AAEMA)2
solution containing 0.715 of Ru(P-
(f) P. Mastrorilli, C.F. Nobile, G.P. Suranna, J. Mol. Catal. 103
(1995) 23;
A
g
Ph3)2(AAEMA)2 (0.68 mmol), 0.119 g of MBAA (0.78
mmol), 2.21 g of DMAA (22.3 mmol) and 3.0 mg of
AIBN (18 mmol) in 2 ml of DMF was heated under
vigorous stirring at 60 8C. After 5 min the stirring
stopped because of the formation of a gelatinous
polymer and, after cooling at r.t., 20 ml of diethyl ether
was added. The solid was filtered off, washed with
methyl alcohol, diethyl ether and dried under vacuum.
Yield: 3.0 g of yellow solid. Elemental analysis: C,
60.1; H, 8.7; N, 10.4; P, 1.11; Ru, 1.85%. IR (KBr):
(g) P. Mastrorilli, C.F. Nobile, G.P. Suranna, L. Lopez, Tetra-
hedron 51 (1995) 7943;
(h) M.M. Dell’Anna, P. Mastrorilli, C.F. Nobile, J. Mol. Catal.
108 (1996) 57;
(i) M.M. Dell’Anna, P. Mastrorilli, C.F. Nobile, L. Lopez, J. Mol.
Catal. 111 (1996) 33;
(j) P. Mastrorilli, A. Rizzuti, G.P. Suranna, C.F. Nobile, Inorg.
Chim. Acta 304 (2000) 17;
(k) M.M. Dell’Anna, M. Gagliardi, P. Mastrorilli, G.P. Suranna,
C.F. Nobile, J. Mol. Catal. A 158 (2000) 515;
(l) P. Mastrorilli, C.F. Nobile, A. Rizzuti, G.P. Suranna, D.
Acierno, E. Amendola, J. Mol. Catal. A 178 (2002) 35.
[9] A. Endo, M. Watanabe, S. Hayashi, K. Shimizu, G.P. Sato, Bull.
Chem. Soc. Jpn. 51 (1978) 800.
[cmꢀ1] nꢃ
1495 s, 1402 s, 1257 m, 1149 s, 1055 m, 745 w, 697 w, 523
m. UVꢁ
Vis [nujol]: 187, 281, 316 nm. 31P{1H} CP MAS
NMR: dꢃ53.0 ppm.
/3480 vs vb, 1719 s, 1610 w, 1618 vs, 1505 w,
[10] Gmelins Handbuch der anorganischen Chemie, vol 63, 8th ed.
Verlag Chemie-GmbH, Weinheim, 1970, p. 468.
[11] N.C. Pramanik, S. Bhattacharya, Transition Met. Chem. 24
(1999) 95.
/
/
[12] P.S. Pregosin, R.K. Kunz, in: P. Diehl, E. Fluck, R. Kosfeld
(Eds.), 31P and 13C NMR of Transition Metal Phosphine
Complexes, NMR Basic Principle and Progress, vol. 16,
Springer-Verlag, Berlin, 1979.
Acknowledgements
[13] (a)D.A.Redfield,L.W.Cary,J.H.Nelson,Inorg.Chem.14(1975)50;
(b) A.W. Verstuft, J.H. Nelson, L.W. Cary, Inorg. Chem. 15 (1976)
732;
The authors gratefuly acknowledge Professor R.
Gobetto for carrying out solid state NMR experiments,
Professor L. Torsi for cyclic voltammetry experiments,
Dr. A. Arink for MALDI analysis, Dr. G. Ciccarella for
LC-MS analysis and Mr. E. Pannacciulli for technical
(c) A.W. Verstuft, J.H. Nelson, L.W. Cary, Inorg. Chem. 15 (1976)
1128.
[14] P.S. Hallman, T.A. Stephenson, G. Wilkinson, Inorg. Synth. 12
(1970) 237.