Palladium(II) complexes with o-aryl substituted 1,1′-bis(phosphino) ferrocenes [Fe(η5-C5H4PR2) 2Pd(NCMe)n](OTf)2 (R = o-MeOC6H 4, o-MeC6H4, o-PriC 6H4, C6F5)

Article abstract of DOI:10.1016/j.jorganchem.2005.10.049

The cationic palladium(II) complexes with 1,1′-bis(phosphino) ferrocenes [Fe(η⁵-C₅H₄PR₂) ₂Pd(NCMe)_n](OTf)₂ (n = 0-2) (OTf = CF ₃SO₃; 5, R = o-MeOC₆H₄, n = 0; 6, R = o-MeC₆H₄, n = 1; 7, R = o-PrⁱC ₆H₄, n = 1; 8, R = C₆F₅, n = 1) have been prepared by treatment of the corresponding dichlorides [Fe(η⁵-C₅H₄PR₂) ₂PdCl₂] (1-4) with silver triflate in the presence of acetonitrile. The structures of 5 and 7 have been determined crystallographically. The oxygen of one of the methoxy groups in 5 has been found to coordinate the palladium resulting in decrease of the bite angle P-Pd-P to 94.74(5)°. In contrast, the bulky ortho-isopropylphenyl groups at the phosphorus atoms in 7 increase the P-Pd-P angle to 99.98(6)°and cause also a significant distortion of the square-planar coordination around the palladium atom. A preliminary study on methoxycarbonylation of ethylene catalyzed by 5-8 has been carried out and revealed great effect of the ortho-aryl substituent on both catalyst's activity and selectivity. The anisyl complex 5 was moderately active for production of alternating polyketone, while the o-tolyl derivative 6 gave selectively methyl propanoate. The cationic palladium(II) complexes with highly sterically congested isopropylphenyl ligand and strongly electron withdrawing pentafluorophenyl substituted phosphine, 7 and 8, respectively, under the reaction conditions undergo facile reduction to Pd⁰/Pd ^I species and are therefore inactive in the process.

Full text of DOI:10.1016/j.jorganchem.2005.10.049

Journal of Organometallic Chemistry 691 (2006) 921–927
www.elsevier.com/locate/jorganchem
Palladium(II) complexes with o-aryl substituted
1,10-bis(phosphino)ferrocenes [Fe(g5-C5H4PR2)2Pd(NCMe)n]
(OTf)2 (R = o-MeOC6H4, o-MeC6H4, o-PriC6H4, C6F5):
Synthesis, structure and catalytic properties in
methoxycarbonylation of ethylene
Alexander M. Kalsin, Nikolai V. Vologdin, Tatꢀyana A. Peganova, Pavel V. Petrovskii,
*
Konstantin A. Lyssenko, Fedor M. Dolgushin, Oleg V. Gusev
A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, Vavilov St. 28, 119991 Moscow, Russian Federation
Received 29 September 2005; received in revised form 24 October 2005; accepted 25 October 2005
Available online 19 December 2005
Abstract
The cationic palladium(II) complexes with 1,10-bis(phosphino)ferrocenes [Fe(g5-C5H4PR2)2Pd(NCMe)n](OTf)2 (n = 0–2) (OTf =
CF3SO3; 5, R = o-MeOC6H4, n = 0; 6, R = o-MeC6H4, n = 1; 7, R = o-PriC6H4, n = 1; 8, R = C6F5, n = 1) have been prepared by treat-
ment of the corresponding dichlorides [Fe(g5-C5H4PR2)2PdCl2] (1–4) with silver triflate in the presence of acetonitrile. The structures of 5
and 7 have been determined crystallographically. The oxygen of one of the methoxy groups in 5 has been found to coordinate the pal-
ladium resulting in decrease of the bite angle P–Pd–P to 94.74(5)ꢀ. In contrast, the bulky ortho-isopropylphenyl groups at the phosphorus
atoms in 7 increase the P–Pd–P angle to 99.98(6)ꢀ and cause also a significant distortion of the square-planar coordination around the
palladium atom. A preliminary study on methoxycarbonylation of ethylene catalyzed by 5–8 has been carried out and revealed great
effect of the ortho-aryl substituent on both catalystꢀs activity and selectivity. The anisyl complex 5 was moderately active for production
of alternating polyketone, while the o-tolyl derivative 6 gave selectively methyl propanoate. The cationic palladium(II) complexes with
highly sterically congested isopropylphenyl ligand and strongly electron withdrawing pentafluorophenyl substituted phosphine, 7 and 8,
respectively, under the reaction conditions undergo facile reduction to Pd0/PdI species and are therefore inactive in the process.
ꢁ 2005 Elsevier B.V. All rights reserved.
Keywords: Palladium complexes with 1,10-bis(phosphino)ferrocenes; Methoxycarbonylation of ethylene; Alternating copolymerization of ethylene and CO
1. Introduction
alternating C2H4/CO copolymerization or to formation
of methyl propanoate [2]. In particular, the complexes with
1,10-bis(diphenylphosphino)metallocene ligands, which are
able to form M–Pd bonded species during catalysis, have
been found to catalyze selective production of methyl
propanoate [3]. Recently, palladium complexes with
1,10-bis(dimethylphosphino)ferrocene and 1,10-bis(diethyl-
phosphino)ferrocene have been shown to be effective
catalysts for alternating copolymerization of ethylene
and CO, while palladium complexes with 1,10-bis(diiso-
propylphosphino)ferrocene catalyzes formation of diethy-
lketone and of methyl propanoate [3]. However the
Cationic palladium(II) complexes with chelating diphos-
phines have been found to be efficient catalysts for meth-
oxycarbonylation of a-olefins with the catalytic properties
strongly dependent on the nature of the diphosphine ligand
[1]. The steric and electronic properties of the diphosphineꢀs
backbone has been partially studied earlier and found to
influence the direction of the process either towards the
*
Corresponding author. Tel.: +7 095 1359337; fax: +7 095 1355085.
E-mail address: gusev@ineos.ac.ru (O.V. Gusev).
0022-328X/$ - see front matter ꢁ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.10.049

922
A.M. Kalsin et al. / Journal of Organometallic Chemistry 691 (2006) 921–927
influence of the substituents at the phosphorus, other than
the backbone bridge, has been poorly investigated, with the
only indication that the ortho-substitution in the phenyl
rings in bis(diphenylphosphino)methane ligand affects dra-
matically on the activity of palladium complexes in the
alternating C2H4/CO copolymerization, coming from the
recent paper [4].
are equivalent according to the 19F{1H} NMR spectrum.
In the 13C{1H} NMR spectrum of 5 one singlet at d
58.21 arises from the methoxy group, the Cp-carbons
appear at d 72.01, 75.28 and 79.30, and the six aryl carbons
are in the region d 110–160. These spectral data for 5 and 8
imply facile rotation of the aryl rings around the P–C
bonds.
Here we report on the synthesis of new palladium(II)
complexes with 1,10-bis(phosphino)ferrocenes, bearing var-
ious substituents at the phosphorus, as well as preliminary
study on their catalytic activity in the methoxycarbonyla-
tion of a-olefins, which confirms the relevant effect of the
phosphorus substituents on both catalyst activity and
selectivity.
Increasing the size of the substituents in the ortho posi-
tions of [Fe(g5-C5H4P{o-C6H4Pri}2)2Pd(NCMe)(OTf)]-
(OTf) (7) reduces the symmetry of the cation, most likely
due to hindered rotation of the aryl groups, resulting in
nonequivalence of the two phosphorus atoms, which are
observed in the 31P{1H} NMR spectrum as two doublets
at d 48.9 and 61.1. The asymmetry of the cation of 7 is fur-
thermore confirmed by the presence of eight signals of the
Cp protons, and four fully nonequivalent i-Pr groups with
eight different methyls and four different CH groups.
Interestingly, the NMR spectra of the o-tolyl derivative
[Fe(g5-C5H4P{o-C6H4Me}2)2Pd(NCMe)(OTf)](OTf)(6)ex-
2. Results and discussion
The cationic palladium complexes 5–8 were prepared by
treatment of the dichloride complexes 1–4 [5], with silver
triflate in the presence of acetonitrile (Scheme 1).
1
hibit an intermediate situation. Both the H and 31P{1H}
NMR spectra of this compound are featured by very broad
signals at room temperature (Fig. 1(a)). Upon lowering the
temperature to ꢀ80 ꢀC (Fig. 1(b)), the 31P{1H} NMR sin-
glet splits into two doublets at d 52.1 and 49.0, which cor-
respond to the unsymmetrical complex B (Fig. 1(b), inset).
Besides these doublets the singlet at d 51.2 appears, which
The complexes obtained were characterized by elemen-
tal analysis and by multinuclear NMR spectroscopy.
According to these data the complexes 5–8 have a
square-planar coordination around palladium and a cis-
chelating diphosphine. In complexes with bulky substitu-
ents 6–8 only one molecule of acetonitrile is coordinated
to palladium, the second coordination site at palladium
in the solid state can be occupied by triflate counter-ion.
The anisyl complex 5 does not contain any solvent mole-
cule that is likely due to coordination of the oxygen of
the methoxy group to palladium.
probably corresponds to the symmetrical form
A
(Fig. 1(b), inset)). The 1H NMR signals remain unresolved
even at ꢀ80 ꢀC, hence their unambiguous assignment can-
not be accomplished. Analogous temperature behavior has
been observed for the corresponding dichloride complex
[Fe(g5-C5H4P{o-C6H4Me}2)2PdCl2] (2) [5].
The phosphorus atoms are equivalent in [Fe(g5-C5H4-
P{o-C6H4OMe}2)2Pd(OTf)](OTf) (5) and [Fe(g5-C5H4P-
{C6F5}2)2Pd(NCMe)(OTf)](OTf) (8) and exhibit singlets
at d 51.1, 17.2, respectively, in the 31P{1H} NMR spectra,
which is consistent with complex cations being in fast
exchange with solvent and triflate. The a- and b-cyclopen-
tadienyl protons in the complexes with relatively small
ortho-anisyl (5) and pentafluorophenyl (8) aryl substituents
appear as non-resolved multiplets at d 4.74, 5.04 for 5 and
at d 4.81, 5.35 for 8. The aryl protons in 5 arise as multi-
plets in the region d 6.96–7.56, and the methoxyl groups
– as a singlet at d 3.98. The pentafluorophenyl rings in 8
The crystal structure of the anisyl substituted compound
[Fe(g5-C5H4P{o-C6H4OMe}2)2Pd(OTf)](OTf) (5) shows
the palladium atom coordinated to two cis phosphorus
atoms from the 1,10-bis(di-o-methoxyphenylphosphino)fer-
rocene and to two oxygen atoms, one from a triflate ion,
the other from a methoxy substituent at phosphorus
(Fig. 2).
The intramolecular coordination of the methoxy group
generates a five-membered ring, which decreases the P–
Pd–P bite angle to 94.74(5)ꢀ as compared to the corre-
sponding dichloride complex 1 (100.14ꢀ) [5]. Also the palla-
dium atom in 5 deviates from the plane defined by the
Scheme 1.

A.M. Kalsin et al. / Journal of Organometallic Chemistry 691 (2006) 921–927
923
The crystal structure of the complex [Fe(g5-C5H4-
P{o-C6H4Pri}2)2Pd(NCMe)(OTf)](OTf) (7) shows the
palladium centre to be four coordinated by a cis 1,10-
bis(di-o-isopropylphenylphosphino)ferrocene one acetoni-
trile molecule and one triflate anion (Fig. 3), however the
square-planar configuration at palladium is significantly
distorted (the dihedral angle between the planes P(1)–
Pd(1)–P(2) and N(1N)–Pd(1)–O(1) is 13.2ꢀ). The complex
7 is highly sterically congested most likely due to steric
repulsions between the PAr2 groups so that both aryls at
the same phosphorus cannot be located at one side of the
Cp-plane, resulting in increase of the bite angle P–Pd–P
to 99.98(6)ꢀ and of the dihedral angle P(1)–Fe(1)–P(2)/
P(1)–Pd(1)–P(2) to 41.4ꢀ. The conformation of the Cp-
rings is staggered, the torsion angle C(1)–Cp(1)–Cp(2)–
C(6) is 36.0ꢀ. The Pd–P distances are slightly different,
˚
˚
Pd(1)–P(1): 2.308(2) A and Pd(1)–P(2): 2.292(2) A. The iso-
propyl groups apparently block the molecule in a fixed con-
Fig. 1. The VT 31P{1H} NMR spectra of complex 6 in CD2Cl2: (a) at
+20 ꢀC; (b) at ꢀ80 ꢀC, two isomers, symmetrical A and unsymmetrical B,
are shown.
formation that persists even in solution (31P{1H} and H
1
NMR spectroscopy).
The complexes 5–8 have been tested as catalyst precur-
sors for the carbonylation of ethylene in MeOH under
standard experimental conditions [3] and the results
Fig. 2. The general view of cation 5 with the representation of atoms by
˚
the thermal ellipsoids at 50% probability level. Selected bond lengths (A):
Pd(1)–P(1) 2.211(1), Pd(1)–P(2) 2.261(1), Pd(1)–O(1) 2.211(3), Pd(1)–
˚
O(1S) 2.140(3), Fe(1)–C(Cp) 2.010(5)–2.073(5), Fe(1)–Cpcent 1.645A, P–
C(Cp) 1.766(5)–1.808(5), P–C(Ph) 1.805(5)–1.826(5); selected bond angles
(ꢀ): O(1S)–Pd(1)–O(1) 91.0(1), P(1)–Pd(1)–P(2) 94.74(5).
atoms P(1)–Fe(1)–P(2), the dihedral angle between the
planes P(1)–Pd(1)–P(2) and P(1)–Fe(1)–P(2) is 42.5ꢀ, while
it is only 0.5ꢀ for 1. The conformation of the Cp-rings is
staggered, with the torsion angle C(1)–Cp(1)–Cp(2)–C(6)
Fig. 3. The general view of cation 7 with the representation of atoms by
the thermal ellipsoids at 50% probability level. The disorder is omitted for
˚
clarity. Selected bond lengths (A): Pd(1)–P(1) 2.308(2), Pd(1)–P(2)
˚
of 30.9ꢀ. The two Pd–P (2.211(1) and 2.261(1) A) distances
2.292(2), Pd(1)–O(1) 2.145(4), Pd(1)-N(1N) 2.045(5), Fe(1)–C(Cp)
are significantly different, showing different trans influence
of the oxygen atoms as well as the fact that P(1) takes part
in a five-membered cycle.
˚
2.012(8)–2.084(8), Fe(1)–Cpcent 1.655 A, P–C(Cp) 1.801(7)–1.807(6);
selected bond angles (ꢀ): O(1S)–Pd(1)–O(1) 87.5(2), P(1)–Pd(1)–P(2)
99.98(6).

924
A.M. Kalsin et al. / Journal of Organometallic Chemistry 691 (2006) 921–927
Table 1
Methoxycarbonylation of ethylene catalyzed by Pd(II) complexes stabilized with Fe(g5-C5H4PR2)2
a
Entry
R
Polyketone (TON)
A (TON)
B (TON)
C (TON)
D (TON)
1
2
3
4
5
a
9, Ph
1070
340
0
1380
0
550
10
0
1780
30
0
0
0
20
1890
5, o-MeOC6H4
6, o-MeC6H4
7, o-PriC6H4
8, C6F5
0
0
0
0
0
0
0
0
0
0
Catalyst (0.01 mmol); 1:1 CO/C2H4 (600 psi); p-BQ (80 equiv.); p-TsOH (20 equiv.); MeOH (100 mL); 85 ꢀC; 1 h; 1400 rpm. TON as mol ethene
incorporated (mol cat)ꢀ1
.
obtained have been compared to those reported for the
prototypical dppf complex [Fe(g5-C5H4PPh2)2Pd(H2O)2]-
(OTs)2 (9) [6]. Selected data are given in Table 1.
ably the sterically hindered ortho-isopropylphenyl and the
electron-withdrawing pentafluorophenyl substituents at
the phosphorus destabilize the cationic palladium(II) com-
plexes and facilitates the reduction of catalytically active
Pd2+ to inactive Pd1+/Pd0 species. Indeed, the cyclic
voltammetry study showed that 7 and 8 exhibit lower
reduction potentials of ꢀ0.24 and ꢀ0.31 V, respectively,
in comparison with the dppf [(dppf)Pd(H2O)2](OTf)2
(ꢀ0.77 V) and the anisyl 7 (ꢀ0.78 V) analogs [8].
The dppf complex has been found to produce a variety
of compounds, spanning from high molecular weight
copolymer to short chain oxygenates (Scheme 2) [6].
The presence of methoxy group in the ortho-position of
the aryl ring, [Fe(g5-C5H4P{o-C6H4OMe}2)2Pd(OTf)]-
(OTf) (5), results in decrease of the activity as compared
to the dppf catalyst 9 and gives the polyketone as the only
product (Table 1, entry 2). Possibly the coordination of the
labile methoxy groups to the palladium centre can compete
with the coordination of ethylene thus slowing down the
catalytic reaction.
In conclusion, new palladium(II) complexes with 1,10-
bis(phosphino)ferrocenes bearing various substituents at
the phosphorus atoms have been synthesized. The ortho-
anisyl and the ortho-tolyl substituted complexes have been
found to be selective catalysts of moderate activity for
methoxycarbonylation of ethylene.
Further increase of steric bulk of the ortho-aryl substit-
uents changed the catalytic behavior dramatically. The
complex [Fe(g5-C5H4P{o-C6H4Me}2)2Pd(NCMe)(OTf)]-
(OTf) (6) catalyzes selective production of methyl propan-
oate (Table 1, entry 3). A similar behavior has been
previously observed for palladium(II) complexes with
1,10-bis(diphenylphosphino)osmocene and 1,10-bis(diph-
enylphosphino)octamethylferrocene and was rationalized
in terms of the formation of acyl or ester transient species
3. Experimental
3.1. General procedures
All experiments were performed under argon in solvents
1
purified by standard methods. H, 31P{1H}, 19F{1H} and
13C{1H} NMR spectra were recorded on Bruker AMX
400, Bruker WP 200SY and Varian VXR 400 spectrome-
ters. Chemical shifts are reported in ppm (d) with reference
to TMS as an internal standard (1H and 13C{1H} NMR
spectra), and CF3COOH for 19F{1H} NMR or 85%
H3PO4 for 31P{1H} NMR spectra as an external standard.
GC analyses were performed on a Shimadzu GC-14A gas
chromatograph equipped with a flame ionization detector
and a 30-m (0.25 mm i.d., 0.25-lm film thickness) SPB-1
Supelco fused silica capillary column. The product compo-
sition was determined by using dimethoxyethane as exter-
nal standard. The GC/MS analyses were performed on a
Shimadzu QP 5000 apparatus equipped with a column
with
a
tridentate j3-P,P,M 1,10-bis(diphenylphosph-
ino)metallocene ligand [3]. Since it has been demonstrated
that the formation of dative M–Pd bonds (M = Fe, Os) is
favored also by bulky substituents on the phosphorus
atoms [7], it may be suggested that the o-tolyl groups in 6
similarly promote the formation of Fe–Pd interactions dur-
ing the catalysis.
Palladium complexes with the ortho-isopropylphenyl
[Fe(g5-C5H4P{o-C6H4Pri}2)2Pd(NCMe)(OTf)](OTf)
(7)
and the pentafluorophenyl [Fe(g5-C5H4P{C6F5}2)2Pd-
(NCMe)(OTf)](OTf) (8) substituted ligands, have been
found to be almost inactive (Table 1, entries 4 and 5). Prob-
Scheme 2.

A.M. Kalsin et al. / Journal of Organometallic Chemistry 691 (2006) 921–927
925
identical with that used for GC analysis. Carbonylation
reactions were performed at constant pressure with a
250-mL stainless steel autoclave, constructed at the
ICCOM-CNR (Firenze, Italy), equipped with a magnetic
drive stirrer and a Parr 4842 temperature and pressure con-
troller. Microanalyses were performed at the A.N. Nes-
meyanov Institute of Organoelement Compounds. The
compounds 1–4 were synthesized according to published
procedures [5].
3.4. Synthesis of [Fe(g5-C5H4P{o-C6H4Pri}2)2Pd(NCMe)-
(OTf)](OTf) (7)
Silver triflate (0.21 g, 0.82 mmol) was added with stir-
ring to a solution of 3 (0.36 g, 0.40 mmol) in CH2Cl2
(20 mL)/MeCN (1 mL) at ꢀ78 ꢀC. The mixture was slowly
warmed to room temperature and stirred overnight. The
solvent was removed in vacuum and the residue was dis-
solved in CH2Cl2 (30 mL). The solution was filtered
through celite, the filtrate was concentrated to 3–5 mL fol-
lowed by the addition of Et2O (30 mL). The solution was
kept in a fridge overnight to give green crystalline product.
It was filtered off, washed with Et2O and dried in vacuum.
Yield of 7: 0.27 g (58%). Anal. Calc. for C50H55F6Fe-
NO6P2PdS2: C, 51.40; H, 4.75, N, 1.20. Found: C, 51.19;
H, 4.87; N, 1.23%. 1H NMR (CDCl3): d 0.01 (s, 3H,
Me); 0.24 (s, 3H, Me); 0.71 (s, 3H, Me); 0.95 (s,
3H, Me); 1.29 (s, 3H, Me); 1.45 (s, 3H, Me); 1.81 (s, 3H,
MeCN); 1.82 (s, 3H, Me); 2.02 (s, 3H, Me); 2.00 (s, 1H,
CHMe2); 2.71 (s, 1H, CHMe2); 3.64 (s, 1H, CHMe2);
4.35 (s, 1H, C5H4); 4.42 (s, 1H, C5H4); 4.51 (s, 1H,
C5H4); 4.58 (s, 1H, C5H4); 4.72 (s, 1H, C5H4); 4.79 (s,
1H, C5H4); 5.53 (s, 1H, C5H4); 5.67 (s, 2H, 1H C5H4 +
1H CHMe2); 6.6–8.0 (br. m, 14H, C6H4); 8.62 (br. m,
1H, o-H(Ar)); 9.17 (br. m, 1H, o-H(Ar)). 31P{1H} NMR
3.2. Synthesis of [Fe(g5-C5H4P{o-C6H4OMe}2)2-
Pd(OTf)](OTf) (5)
Silver triflate (0.57 g, 2.22 mmol) was added with stirring
to a solution of 1 (0.91 g, 1.07 mmol) in CH2Cl2 (40 mL)/
MeCN (0.2 mL) at ꢀ78 ꢀC. This mixture was allowed to
warm to room temperature and stirred overnight. The sol-
vent was evaporated to dryness and the residue was dis-
solved in CH2Cl2 (30 mL). The solution was filtered
through celite, the filtrate was concentrated to 10 mL and
then 5–10 mL of Et2O were added to induce slow precipita-
tion of dark-green crystals. They were filtered off, washed
with Et2O and dried in vacuum. Yield of 5 · CH2Cl2:
0.80 g (64%). Anal. Calc. for C41H38Cl2F6FeO10P2PdS2:
1
C, 42.31; H, 3.29. Found: C, 42.54; H, 3.34%. H NMR
2
(CDCl3): d 48.9 (br. d, 1P, JPP = 42 Hz); 61.1 (br. d, 1P,
(CDCl3): d 3.98 (s, 12H, OMe), 4.74 (s, 4H, C5H4), 5.04
(s, 4H, C5H4), 6.96 (br. m, 4H, o-C6H4OMe), 7.09 (br. m,
4H, o-C6H4OMe), 7.56 (br. m, 8H, o-C6H4OMe). 31P{1H}
NMR (CDCl3): d 51.1 (s). 13C{1H} NMR (CDCl3):
2JPP = 42 Hz).
3.5. Synthesis of [Fe(g5-C5H4P{C6F5}2)2Pd(NCMe)-
(OTf)](OTf) (8)
1
d 58.21 (s, OMe); 72.0 (d, JPC = 77.1 Hz, ipso-Cp);
3
2
75.28 (t, JPC = 4.6 Hz, b-Cp); 79.30 (t, JPC = 6.6 Hz, a-
2
1
Cp); 112.91 (t, JPC = 2.6 Hz, Ar); 115.96 (d, JPC
=
Silver triflate (0.25 g, 0.97 mmol) was added with stir-
ring to a solution of 4 (0.50 g, 0.46 mmol) in CH2Cl2
(30 mL) MeCN (0.2 mL) at ꢀ78 ꢀC. The mixture was
slowly warmed to room temperature and stirred for 3 h.
The precipitate of AgCl was filtered off and the solvent
was removed in vacuum. The residue was then washed with
CH2Cl2 (2 · 10 mL) to afford green crystalline poorly solu-
ble in CH2Cl2. It was washed with Et2O and dried in vac-
uum. Yield of 8: 0.27 g (42%). Anal. Calc. for
C38H11F26FeNO6P2PdS2: C, 33.57; H, 0.82; N, 1.03.
63.4 Hz, ipso-C(Ar)); 120.23 (q, 1JCF = 320.0 Hz, CF3SO3);
3
3
122.27 (t, JPC = 5.6 Hz, Ar); 134.17 (t, JPC = 4.0 Hz,
Ar); 135.90 (s, p-Ar); 160.23 (t, JPC = 2.0 Hz, ipso-
2
C(OMe)).
3.3. Synthesis of [Fe(g5-C5H4P{o-C6H4Me}2)2-
Pd(NCMe)(OTf)](OTf) (6)
Silver triflate (0.26 g, 1.02 mmol) was added with stir-
ring to a solution of 2 (0.40 g, 0.51 mmol) in CH2Cl2
(40 mL)/MeCN (0.2 mL) at ꢀ78 ꢀC. This mixture was
allowed to warm to room temperature and stirred over-
night. The precipitate was filtered off and the filtrate was
concentrated to 5 mL and then treated with Et2O
(40 mL). The light green crystals were filtered off, washed
with Et2O and dried in vacuum. Yield of 6: 0.46 g (91%).
Anal. Calc. for C42H39F6FeNO6P2PdS2: C, 47.77; H,
3.72; N, 1.33. Found: C, 47.74; H, 3.92; N, 1.75%.
1
Found: C, 34.17; H, 1.03; N, 1.22%. H NMR (CD3CN):
d 4.81 (s, 4H, C5H4), 5.35 (s, 4H, C5H4). 31P{1H} NMR
(CD3CN): d 17.2 (br. s). 19F{1H} NMR (CD3CN): d
3
ꢀ82.1 (t, JFF = 19.3 Hz, 8F, m-F(C6F5)); ꢀ66.5 (t,
3JPP = 19.3 Hz, 4F, p-F(C6F5)); ꢀ50.1 (br. t, 8F, o-
F(C6F5)); ꢀ1.3 (s, CF3SOꢀ).
3
3.6. Catalytic carbonylation of ethene in methanol
1H NMR (CDCl3): d 1.63 (br. s, 6H, Me), 3.39 (br. s,
6H, Me), 4.32 (br. s, 2H, C5H4), 4.34 (br. s, 2H, C5H4),
4.51 (br. s, 2H, C5H4), 4.89 (br. s, 2H, C5H4), 7.2–7.6
(br. m, 16H, o-C6H4Me). 31P{1H} NMR (CDCl3): d 49.1
(br. s); 31P{1H} NMR (CD2Cl2 at ꢀ80 ꢀC): d 49.0 (d,
Typically, MeOH (100 mL) was introduced by suction
into a 250-mL autoclave, previously evacuated by a vac-
uum pump, containing 0.01 mmol of precatalyst along with
0.8 mmol of 1,4-benzoquinone (BQ) and 0.2 mmol of p-tol-
uenesulfonic acid (TsOH). The autoclave was then pressur-
ized with 1:1 CO/C2H4 (600 psi) at room temperature and
2
2JPP = 41.5 Hz); 52.1 (d, JPP = 41.5 Hz); 51.2 (s).

926
A.M. Kalsin et al. / Journal of Organometallic Chemistry 691 (2006) 921–927
heated to 85 ꢀC. As soon as the reaction mixture reached
the desired temperature, stirring (1400 rpm) was applied
for 1 h. A constant pressure was maintained all over the
experiment time, by a constant feeding of the same mixture
of CO/C2H4 from a gas reservoir. The reaction was
stopped by cooling the autoclave to room temperature by
means of an ice-acetone bath. After the unreacted gases
were released, the insoluble copolymer, if any, was filtered
off and washed with cold methanol and dried overnight
under reduced pressure at 70 ꢀC. In any case the filtrate
was analysed by GC using dimethoxyethane as the external
standard.
atoms. Hydrogen atoms in 5 and 7 were placed in geo-
metrically calculated positions and included in final the
refinement using the ‘‘riding’’ model with the Uiso(H)
parameters equal to 1.2 Ueq(Ci) or 1.5 Ueq(Cii), where
U(Ci) and U(Cii) are, respectively, the equivalent thermal
parameters of the aromatic and methylene carbon atoms
to which corresponding H atoms are bonded. The anal-
ysis of the Fourier density synthesis have revealed that
Et2O solvate in 5 and 7 as well as SO3CF3 anion and
one of the o-PriC6H4 substituents in 7 are disordered
by two positions with equal occupancies. Crystal data
and structure refinement parameters for 5 and 7 are
given in Table 2. All calculations were performed using
the SHELXTL software [10].
3.7. X-ray structure determination
Crystals of 5 and 7 suitable for X-ray analysis were
obtained by slow diffusion of diethyl ether into solutions
of the complexes in dichloromethane. X-Ray diffraction
experiments for 5 and 7 were carried out with a Bruker
SMART 1000 CCD area detector, using graphite mono-
4. Supplementary material
The crystallographic data have been deposited with the
Cambridge Crystallographic Data Center, CCDC No.
251344 for 5 and No. 251345 for 7. Copies of this informa-
tion may be obtained free of charge from: The Director,
CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK
(Fax: +44-1223-336033; e-mail: deposit@ccdc.cam.ac.uk
or http://www.ccdc.cam.ac.uk).
˚
chromated Mo Ka radiation (k = 0.71073 A, x-scans
with a 0.3ꢀ step in x and 10 s per frame exposure) at
110 K [9]. Reflection intensities were integrated using SAINT
software [10] and absorption correction was applied
semi-empirically. The structures were solved by direct
method and refined by the full-matrix least-squares
against F2 in anisotropic approximation for no-hydrogen
Acknowledgments
Authors gratefully acknowledge Dr. Claudio Bianchini
and Dr. Werner Oberhauser for the catalytic testing of
the cationic palladium complexes. Thanks are due to a
CNR-RAS bilateral agreement, to the Russian Foundation
for Basic Research (Grant 03-03-32471) and to the Science
Support Foundation of Russian Federation for financial
support.
Table 2
Crystallographic data for complexes 5 and 7
5
7
Formula
C
40H36F6FeO10P2PdS2 C52H54F6FeNO6P2PdS2
Æ 1/2(C4H10O)
120
Triclinic, P1
Æ 1/2(C4H10O) Æ (CH3CN)
120
Orthorhombic, Pbca
T (K)
Crystal system,
space group
ꢀ
References
˚
a (A)
11.1598(9)
11.6408(9)
17.422(1)
100.319(2)
99.789(2)
91.668(2)
2190.2(3)
2(1)
1116.06
9.95
1130
1.692
58.00
21.288(2)
16.084(1)
33.584(6)
˚
b (A)
[1] (a) E. Drent, H.M. Budzelaar, Chem. Rev. 96 (1996) 663;
(b) R.A. Robertson, D. Cole-Hamilton, J. Coord. Chem. Rev. (225)
(2002) 67;
(c) C. Bianchini, A. Meli, Coord. Chem. Rev. 225 (2005) 35.
[2] (a) E. Drent, J.A.M. van Broekhoven, M.J. Doyle, J. Organomet.
Chem. 417 (1991) 235;
(b) W. Clegg, G.R. Eastham, M.R.J. Elsegood, R.P. Tooze, X.L.
Wang, K. Whiston, J. Chem. Soc., Chem. Commun (1999) 1877.
[3] (a) C. Bianchini, A. Meli, W. Oberhauser, P.W.N.M. van Leeuwen,
M.A. Zuideveld, Z. Freixa, P.C.J. Kamer, A.L. Spek, O.V. Gusev,
A.M. Kalsin, Organometallics 22 (2003) 2409;
˚
c (A)
a (ꢀ)
b (ꢀ)
c (ꢀ)
3
˚
V (A )
11,499(2)
8(1)
1245.37
7.62
5120
1.439
Z(Z0)
M
l (cmꢀ1
F(000)
)
qcalcd (g cmꢀ3
2hmax (ꢀ)
)
52.00
62,970 (0.0815)
(b) O.V. Gusev, A.M. Kalsin, P.V. Petrovskii, K.A. Lyssenko, Yu.F.
Oprunenko, C. Bianchini, A. Meli, W. Oberhauser, Organometallics
22 (2003) 913.
No. of reflections
measured (Rint
19,503 (0.0630)
)
No. of independent 11,023
reflections
No. of reflections
with I > 2r(I)
No. of parameters
R1
11,349
7256
[4] S.J. Dossett, A. Gillon, A.G. Orpen, J.S. Fleming, P.G. Pringle,
D.F. Wass, M.D. Jones, J. Chem. Soc., Chem. Commun (2001) 699.
[5] O.V. Gusev, A.M. Kalsin, N.V. Vologdin, K.A. Lyssenko, P.V.
Petrovskii, A.L. Tsvetkov, I.P. Beletskaya, Organometallics, submit-
ted for publication.
[6] O.V. Gusev, A.M. Kalsin, M.G. Peterleitner, P.V. Petrovskii, K.A.
Lyssenko, N.G. Akhmedov, C. Bianchini, A. Meli, W. Oberhauser,
Organometallics 21 (2002) 3637.
6573
579
872
0.0630
0.1422
1.059
0.0757
0.1877
1.069
0.748/ꢀ0.568
wR2
GOF
Maximum/mininum 1.082/ꢀ0.631
[7] (a) M.A. Zuidevelt, B.H.G. Swennenhuis, P.C.J. Kamer, P.W.N.M.
van Leeuwen, J. Organomet. Chem. 637 (2001) 805;
ꢀ3
˚
peak (e A
)

A.M. Kalsin et al. / Journal of Organometallic Chemistry 691 (2006) 921–927
927
(b) M.A. Zuideveld, B.H.G. Swennenhuis, M.D.K. Boele, Y. Guari,
G.P.F. van Strijdonck, J.N.H. Reek, P.C.J. Kamer, K. Goubitz, J.
Fraanje, M.L. Lutz, A.L. Spek, P.W.N.M. van Leeuwen, J. Chem.
Soc., Dalton Trans. (2002) 2308.
(b) O.V. Gusev, M.G. Peterleitner, A.M. Kalsin, N.V. Vologdin,
Russ. J. Electrochem. 39 (2003) 1293.
[9] SMART V5.051 and SAINT V5.00, Area Detector Control and Integra-
tion Software, 1998, Bruker AXS Inc., Madison, WI-53719, USA.
[10] G.M. Sheldrick, SHELXTL-97, Version 5.10, Bruker AXS Inc., Mad-
ison, WI-53719, USA.
[8] (a) O.V. Gusev, M.G. Peterleitner, N.V. Vologdin, A.M. Kalsin,
Electrokhimiya 39 (2003) 1444;