Synthesis and catalytic properties of di- and trinuclear palladium complexes with PCP-pincer ligands

Article abstract of DOI:10.1023/B:RUJO.0000010214.72250.5a

Linear and branched conjugated pincer ligands having Ph₂P groups were synthesized: 3,3′,5,5′-tetrakis(diphenylphosphinomethyl) diphenylacetylene, 3,3′,5,5′-tetrakis(diphenylphosphinomethyl) diphenyldiacetylene, 1,3,5-tris[3,5-bis(diphenylphosph

Full text of DOI:10.1023/B:RUJO.0000010214.72250.5a

Russian Journal of Organic Chemistry, Vol. 39, No. 9, 2003, pp. 1268 1281. Translated from Zhurnal Organicheskoi Khimii, Vol. 39, No. 9, 2003,
pp. 1342 1354.
Original Russian Text Copyright
2003 by Beletskaya, Chuchuryukin, van Koten, Dijkstra, van Klink, Kashin, Nefedov, Eremenko.
Synthesis and Catalytic Properties of Di- and Trinuclear
Palladium Complexes with PCP-Pincer Ligands
I. P. Beletskaya1, A. V. Chuchuryukin1, G. van Koten2, H. P. Dijkstra2,
G. P. M. van Klink2, A. N. Kashin1, S. E. Nefedov3, and I. L. Eremenko3
1
Faculty of Chemistry, Moscow State University, Vorob’evy gory, Moscow, 119992 Russia
e-mail: beletska@org.chem.msu.ru
2
Debye Institute, Deparment of Metal-Mediated Synthesis, Utrecht University, Padualaan 8,
CH-3584 Utrecht, The Netherlands
3
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, Russia
Received February 20, 2003
Abstract Linear and branched conjugated pincer ligands having Ph2P groups were synthesized: 3,3 ,5,5 -
tetrakis(diphenylphosphinomethyl)diphenylacetylene, 3,3 ,5,5 -tetrakis(diphenylphosphinomethyl)diphenyldi-
acetylene, 1,3,5-tris[3,5-bis(diphenylphosphinomethyl)phenylethynyl]benzene, and hexakis[3,5-bis(diphenyl-
phosphinomethyl)phenylethynyl]benzene. Palladation of these ligands by heating with Pd(BF4)2(MeCN)4 in
boiling acetonitrile gave the corresponding di- and trinuclear ionic pincer palladium complexes. No individual
complex was obtained from hexakis[3,5-bis(diphenylphosphinomethyl)phenylethynyl]benzene. The ionic com-
plexes were converted into the corresponding chloride complexes by treatment with sodium chloride in
a mixture of water with methylene chloride. The structure of the ionic palladium complex with 3,3 ,5,5 -tetra-
kis(diphenylphosphinomethyl)diphenylacetylene was established by X-ray analysis. The obtained palladium
complexes exhibited a considerable catalytic activity in the Heck reaction of iodobenzene with ethyl acrylate
and in the Michael addition of ethyl cyanoacetate with methyl vinyl ketone. The catalytic activity per
palladium atom decreases as the number of palladium atoms in the complex increases.
In the recent years much attention is given to the
synthesis and study of properties of various poly-
nuclear transition metal complexes. A number of such
systems show interesting properties as catalysts,
sensors, and molecular devices [1 5]. Dendrimer
systems containing metallacycles with tridentate
P,C,P -coordinating (pincer) ligands are extensively
studied [6]. We have developed procedures for the
preparation of dinuclear linear pincer palladium com-
plexes bridged through one or two acetylene frag-
ments [7], as well as of related trinuclear complexes
having a 1,3,5-triethynylbenzene moiety as a base unit
[8]. When used as catalysts, such metal dendrimer
systems can be regenerated by separation from the
reaction products via nanomembrane filtration [9 11].
activity in the Heck reaction and Michael addition
at an activated double bond.
The starting material in the synthesis of ligands
Ia IVa was 3,5-bis(bromomethyl)iodobenzene [12]
which was converted (via a sequence of Arbuzov and
Sonogashira reactions) into phosphine oxide Ib as
precursor of Ia; Likewise, phosphine oxide VI was
obtained (Scheme 2). Phosphine oxide Ib was also
prepared by the Sonogashira coupling of aryl iodide V
with ethylnyl derivative VI. Dimerization of phos-
phine oxide VI gave diacetylene derivative IIb.
Finally, tris- and hexakis-substituted benzenes IIIb
and IVb were synthesized by reaction of phosphine
oxide VI with 1,3,5-tribromobenzene and hexabromo-
benzene, respectively (Scheme 3).
In the present work we have synthesized conjugated
pincer ligands Ia IVa with both linear and branched
structure, having Ph2P groups as coordinating frag-
ments (Scheme 1), and the corresponding polynuclear
palladium complexes and examined their catalytic
The resulting polyphosphine oxides Ib IVb were
quantitatively reduced to the corresponding phos-
phines Ia IVa by heating with trichlorosilane in
o-dichlorobenzene at 110 C [13]. Ionic palladium
comlexes Ic IIIc with pincer ligands Ia IIIa were
1070-4280/03/3909-1268$25.00 2003 MAIK Nauka/Interperiodica

SYNTHESIS AND CATALYTIC PROPERTIES
1269
Scheme 1.
Scheme 2.
synthesized by direct electrophilic palladation of the
ligands via treatment with [Pd(MeCN)4](BF4)2 in
boiling acetonitrile (reaction time 1 h). The reaction
resulted in exhaustive palladation of ligands Ia IIIa
(Scheme 4). From ligand IVa we obtained a mixture
of palladium complexes. The yields of complexes Ic,
IIc, and IIIc were 51, 21, and 90%, respectively.
Presumably, the low yield of IIc is explained by the
fact that conjugation with already present palladium
atom hinders secondary palladation.
Ionic palladium complexes Ic IIIc were quantita-
tively converted into the corresponding neutral
chloride complexes Id IIId by treatment with NaCl
in CH2Cl2 H2O (18 C, 3 h; Scheme 4).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

1270
BELETSKAYA et al.
Scheme 3.
All newly synthesized compounds were charac-
palladium atoms in the dication have a nearly square
planar configuration. Each Pd atom is linked to two P
atoms [Pd P 2.330(2) and 2.422(2) ] arranged
trans with respect to each other, one carbon atom
[ -bonded, Pd C 2.019(6) ], and nitrogen atom
of the acetonitrile ligand [Pd N 2.091(7) ]. Specific
geometric parameters of the tridendate pincer ligand
are reflected in some deviations of the palladium
1
terized by H, 13C, and 31P NMR and UV spectra,
MALDI-TOF-MS data, and elemental analyses.
X-Ray diffraction study of complex Ic. X-Ray
structure analysis of complex Ic showed (Fig. 1,
Table 1) that the palladium dication is located at the
crystallographic inversion center and that two BF4
anions reside in the outer coordination sphere. The
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

SYNTHESIS AND CATALYTIC PROPERTIES
1271
Scheme 4.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

1272
BELETSKAYA et al.
Fig. 1. Structure of dicationic complex Ic according to the X-ray diffraction data.
configuration from the classical square planar struc-
ture. For example, the PPdP angle equal to 159.93(7)
considerably differs from 180 C. In addition, the
palladium atoms deviate from the ligand PCP plane
to a distance of 0.111(2) , which, however, does
not affect the geometry of the central carbon fragment
[the CCC angle is 178.6(10) ]. Here, some leveling
of C C distances in the almost linear central chain
benzene rings, which is responsible for the long-wave
absorption.
The spectral parameters of complexes Ic, IIc, IId,
and IIIc and phosphine oxides Ib, IIIb, and
IVb are collected in Table 2. These data show that the
long-wave absorption bands of phosphine oxides Ib,
IIIb, and IVb shift to the red region with increase
of conjugation in their -electron systems (Table 2,
compounds Ib, IIIb, and IVb). All complexes absorb
below 370 nm, and their long-wave absorption
maxima are located at longer wavelengths than the
maxima of the corresponding phosphine oxides. The
C9 C11 C11A C9A is observed [C9 C11 1.394(8)
,
C11 C11A 1.306(12) ]. Probably, this is the result
of electron density redistribution in the above frag-
ment, which gives rise to some contribution (at least,
in crystal) of a delocalized C
C
C
C structure.
largest difference (
plex Ic (cf. the data for Ib and Ic in Table 2), and
the smallest value is characteristic of complex IIIc
40 nm) is observed for com-
Study of complexes Ic IIIc and IId by UV
spectroscopy. By studying the UV spectra of the
palladium complexes synthesized in this work and
comparing them with those of the corresponding
phosphine oxides we were able to estimate mutual
influence of the palladium-containing ring and the
conjugated -electron system of the carbon skeleton.
The UV spectra of phosphine oxides in the region
260 420 nm are almost similar to those of the
corresponding hydrocarbons having no diphenylphos-
phinomethyl substituents. For example, the UV
spectra of Ib and IIb are identical to the reported
spectra of diphenylacetylene and 1,4-diphenylbutadi-
yne, and the spectra of IIIb and IVb are identical to
those of 1,3,5-tris(phenylethynyl)benzene and hexa-
kis(phenylethynyl)benzene. The observed similarity
may be interpreted in terms of a weak effect of the
meta-Ph2P(O)CH2 substituents on the conjugated
-electron system formed by the ethynyl group and
which has the most extended -electron system.
Differences in the position of the other (short-wave)
absorption bands are much smaller, and no fine struc-
ture is observed.
The above long-wave shift is likely to result from
charge transfer between the metal and pincer ligand.
The charge transfer is not influenced by the counter-
ion, so that complexes IIc and IId are characterized
by almost similar positions of the long-wave absorp-
tion maxima (Table 2).
Catalytic activity of complexes Ic IIIc. The
catalytic properties of complexes Ic IIIc were studied
in the Heck and Michael reactions. The Heck reaction
is known to be catalyzed by palladium(0) complexes,
whereas Michael addition requires palladium(II) com-
pounds which act as Lewis acids. All the examined
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

SYNTHESIS AND CATALYTIC PROPERTIES
1273
complexes turned out to efficiently catalyze both
Heck and Michael reactions.
Table 1. Bond lengths d and bond angles in dinuclear
palladium complex Ic
The Heck reaction is frequently used as a model
process to estimate catalytic activities of metal com-
plexes [14]. The complexes under study were tested
in the reaction of iodobenzene with ethyl acrylate in
the presence of Bu3N. The reactions were carried out
in dimethylacetamide (DMA) at 140 C. The progress
of the reactions was monitored following the amount
of released iodide ion by potentiometric titration.
The other products were quantitated by GLC analysis
using an internal standard. The reaction was found to
occur in a selective fashion with quantitative forma-
tion of ethyl cinnamate (Scheme 5).
Bond
d,
Bond
d,
Pd1 P1
Pd1 N1
P1 C3
2.330(2)
2.091(7)
1.828(7)
1.809(8)
1.796(8)
1.121(9)
1.505(10)
1.394(8)
Pd1 P2
Pd1 C5
P1 C12
P2 C7
2.422(2)
2.019(6)
1.823(8)
1.803(7)
1.822(7)
1.458(12)
1.529(9)
1.306(12)
P1 C18
P2 C24
N1 C1
C3 C4
C9 C11
P2 C30
C1 C2
C6 C7
C11 C11A
Angle
, deg
Angle
, deg
Scheme 5.
P1Pd1P2
P2Pd1N1
P2Pd1C5
Pd1P1C3
Pd1P1C18
Pd1P2C24
Pd1N1C1
P1C3C4
159.93(7)
97.7(2)
80.6(2)
P1Pd1N1
P1Pd1C5
N1Pd1C5
Pd1P1C12
Pd1P2C7
Pd1P2C30
N1C1C2
Pd1C5C4
P2C7C6
102.0(2)
79.8(2)
177.6(3)
124.9(3)
97.7(2)
124.8(3)
179.5(13)
120.2(6)
106.6(5)
120.3(7)
99.5(3)
110.5(3)
113.5(3)
177.4(9)
104.6(5)
121.1(5)
120.3(7)
178.6(10)
Table 3 contains the conversions of iodobenzene in
11 h after the reaction started, TON values (turnover
number, i.e., the amount of product obtained with
1 mol of catalyst, which characterizes the efficiency
of the latter), and TON/Pd values (specific activity of
catalyst or catalytic activity per palladium atom).
For comparison, given are the data obtained under
similar conditions with mononuclear palladium com-
plex VII derived from 2,6-bis(diphenylphosphino-
methyl)benzene.
Pd1C5C6
C8C9C11
C9C11C11A
C10C9C11
Table 2. UV spectra of complexes Ic, IIc, IId, and IIIc
and phosphine oxides Ib, IIIb, IVb in MeCN
Compound
max, nm ( max, l mol 1 cm )
1
no.
Ic
Ib
240 (10.1), 324 (8.7), 344 (6.9)
238 (10.5), 272 (5.9), 290 (8.3), 298 (6.1),
308 (7.1)
IIc
242 (12.5), 294 (9.6), 314 (9.2), 340 (9.2),
366 (8.2)
IId
IIIc
IIIb
240 (12.4), 316 (8.9), 340 (8.1), 368 (7.1)
240 (18.6), 314 (21.6), 330 (19.2)
238 (18.1), 272 (13.0), 292 (22.5), 300
(19.5), 310 (23.5)
It is seen that the efficiency of the complexes at
a concentration of 0.1 mol % changes in the series
VII > Ic > IIc > IIIc and that the TON value does
not exceed 1000. Usually, the TON value in the Heck
reaction increases as the catalyst concentration
decreases [14, 15]. This is the case of complex Ic
(Table 3, run nos. 2 and 3). However, complexes IIc
and IIIc show the reverse relation: the conversion
sharply decreases, and TON considerably falls down.
IVb
238 (88.2), 258 (60.1), 356 (114.0), 380
(65.0)
(Table 3; run nos. 1, 2, 4, 6 and 3, 5, 7). It follows
that the catalytic activity of mononuclear complex VII
is greater by a factor of 4 than the activity of complex
IIIc having the most branched structure. Presumably,
this is the result of a considerable contribution of
The above differences in the behavior of complexes
VII, Ic, IIc, and IIIc (Table 3; run nos. 1, 2, 4, and 6)
become even stronger in going to TON/Pd values
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

1274
BELETSKAYA et al.
Table 3. Reaction of ethyl acrylate with iodobenzene in
the presence of complexes Ic IIIc and VIIa
data, addition products Xa and Xb are formed with
participation of one or two molecules of ketone IX,
repsectively (Scheme 6).
Run Com-
no. plex
Pd,
Conversion
TONc TON/Pdd
mol % of PhI,b %
Scheme 6.
1
2
3
4
5
6
7
VII
Ic
Ic
IIc
IIc
IIIc
IIIc
0.1
0.1
0.05
0.1
0.05
0.1
90
90
92
79
28
64
15
900
900
1840
790
560
640
440
900
450
920
400
280
210
147
0.034
a
The reactions were carried out in DMA (1 ml) at 140 C (reac-
tion time 11 h); amounts of the reactants: iodobenzene,
0.049 mmol; ethyl acrylate, 0.061 mmol; tributylamine,
0.05 mmol.
b
c
d
Determined by titration of the librated iodide ion and con-
firmed by the GLC data.
The number of moles of the product obtained with 1 mol
of catalyst.
TON/Pd = TON/n, where n is the number of palladium atoms
in the complex.
The data given in Table 4 include the conversion
of ester VIII and overall yield of products Xa and
Xb, depending on the reaction time, in the catalytic
and noncatalytic processes. The plots of the conver-
sion of VIII and the yields of Xa and Xb versus time
in the reaction catalyzed by complex VII are shown
in Fig. 2. It is seen that the yield of monoadduct Xa
initially increases and then decreases due to the secon-
dary process leading to bis-adduct Xb. The yield of
Xb changes correspondingly. As follows from the
data in Table 4, complexes Ic and VII accelerate the
Michael reaction approximately twofold with almost
equal efficiencies. Acceleration of the process also
affects the ratio of products Xa and Xb. By the end
of the reaction (after 24 h), when the conversion of
initial ester VIII is complete, the ratio Xb:Xa is
equal to 20, while in the noncatalytic reaction it is
equal to 3. An analogous effect on the product ratio
was observed in the reaction catalyzed by trifluoro-
methanesulfonate platinum complexes with an NCN
pincer ligand [17].
steric factor due to large size of the dendrimer-like
molecule.
The catalytic activities of ionic complexes Ic and
VII in the Michael addition were compared using the
reaction of of ethyl cyanoacetate (VIII) with methyl
vinyl ketone (IX) as model. This reaction is often
used [16 18] (together with the aldol condensation of
benzaldehyde with ethyl isocyanoacetate [19 22])
while studying the activity of platinum metal com-
plexes as Lewis acids. The reactions were carried out
in methylene chloride at room temperature in the
presence of 10 mol % of ethyl(diisopropyl)amine and
1 mol % of the complex. According to the GC MS
Comparison of the specific catalytic activity of
complexes Ic and VII (per palladium atom) shows
that the latter is twice as active as dinuclear complex
Ic. The lower catalytic activity of Ic may be explained
by steric factor or conjugation between the two palla-
dium atoms. Thus, in the Michael addition, as well as
in the Heck reaction, the specific activity of pincer
palladium complexes decreases as the number of
metal atoms in the catalyst molecule rises. An ana-
logous pattern was observed in the same reaction for
another three-nuclear NCN -pincer system based on
1,3,5-triphenylbenzene [18]. However, in some reac-
tions catalyzed by dendrimeric cyclopalladated
Fig. 2. Conversion of ethyl cyanoacetate VIII and yields
of products Xa and Xb (%) in the reaction with methyl
vinyl ketone in the presence of complex VII.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

SYNTHESIS AND CATALYTIC PROPERTIES
1275
Table 4. Reaction of ethyl cyanoacetate (VIII) with methyl vinyl ketone (IX), catalyzed by complexes Ic and VIIa
Noncatalytic reaction
Catalyzed by complex VII
Catalyzed by complex Ic
Reaction
time,
conversion
yield of
ratio
conversion
yield of
ratio
conversion
yield of
ratio
min
of VIII, % Xa+ Xb,b % Xb: Xa of VIII, % Xa+ Xb,b % Xb: Xa of VIII, % Xa+ Xb,b % Xb: Xa
35
70
9
8
0.14
42
54
39
51
0.56
1.7
38
41
35
40
0.3
0.54
95
31
41
55
30
40
54
0.25
0.3
0.69
150
230
340
1460
63
90
92
98
60
86
87
93
1.7
6.1
8.7
66
78
90
98
64
78
87
95
2.8
5.0
9.9
75
73
3.1
18
22
a
The reactions were carried out in methylene chloride (1 ml) at 18 C in the presence of 10 mol % of (i-Pr)2NEt and 1 mol % of
complex Ic or VII; amounts of the reactants: ethyl cyanoacetate, 0.6 mmol; methyl vinyl ketone, 1.43 mmol.
Determined by GLC using dodecane as internal standard.
b
carbosilane-based CN-systems, the catalytic activity
was reported to increase with rise in the number of
catalytic centers [23].
structure was solved by the direct method and was
refined in the full-matrix anisotropic approximation
for all non-hydrogen atoms. The positions of hydro-
gen atoms were refined according to the rider
model. The calculations were performed using
SHELX97 software package [24, 25]. The principal
bond lengths and bond angles are given in Table 1,
and the crystallographic data, in Table 5.
Heck reaction procedure. A specified amount of
palladium complex was dissolved in 1 ml of dimethyl-
acetamide. The solution was utilized within 24 h; it
was purged with argon prior to use. An ampule was
charged with a mixture of 10.0 mg (0.049 mmol) of
iodobenzene, 6.11 mg (0.061 mmol) of ethyl acrylate,
9.27 mg (0.05 mmol) of tributylamine, a solution of
1,4-di-tert-butylbenzene (internal standard) in di-
methylacetamide, about 10 l of the catalyst solution,
and 1 ml of dimethylacetamide. The solution was
degassed under high vacuum (two freezing evacuation
cycles), and the ampule was sealed off and heated
for 11 h at 140 C on an oil bath. A 20 50- l sample
of the reaction mixture was withdrawn for titration
(it was preliminarily mixed with 1.5 ml of 0.1 M
HNO3). For GLC analysis, a sample of the mixture
was diluted with 5% hydrochloric acid and extracted
with diethyl ether (3 2 ml), and the organic phase
was dried over MgSO4.
EXPERIMENTAL
1
The H, 13C, and 31P NMR spectra were recorded
on Varian VXR-400 and Bruker AC-200 spectrom-
eters using TMS (1H and 13C) and 85% phosphoric
acid (31P) as external reference. The MALDI-TOF
mass spectra were obtained on a Voyager-DE Bio-
Spectrometry Workstation (PerSeptive Biosystems
Inc., Flamingham, MA), equipped with a nitrogen
laser ( 337 nm). The UV spectra were measured on
an M-40 spectrophotometer (Carl Zeiss, Jena).
GLC analysis was performed on a Hewlett Packard
5890 Series II Plus chromatograph equipped with
a flame-ionization detector. The Heck reaction prod-
ucts were analyzed using an HP-1701 capillary
column (15 m 0.32 mm 0.25 m); oven tempera-
ture programming from 35 to 280 C at 7 deg/min.
The Michael reaction products were analyzed using
an HP-1 capillary column (25 m 0.32 mm
0.25 m); oven temperature programming from 80 to
280 C at 10 deg/min. Iodide ion determination was
performed with a Radiometer Titrator TTT1c com-
plex, Titrigraph SBR2c, equipped with an ABU1
0.25-ml autoburette and Selectrode F1212S electrode;
the titrant was a 0.03 M AgNO3/0.1 M HNO3 solu-
tion; titration accuracy 2%. The product yields deter-
mined by GLC and by titration coincided within 7%.
Michael reaction procedure. The reaction was
carried out at 25 C under argon pressure. Ethyl cyano-
acetate, 0.204 g (1.80 mmol), methyl vinyl ketone,
0.301 g (4.29 mmol), ethyl(diisopropyl)amine, 31
l
X-Ray diffraction study of a single crystal of
complex Ic was performed on a Syntex P21 automatic
diffractometer (graphite monochromator, 293 K). The
(10 mol %), and dodecane, 29.3 mg (standard),
were dissolved in 3 ml of methylene chloride, and
1 ml of this solution was added to 6 mmol (1 mol %)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

1276
BELETSKAYA et al.
Table 5. Crystallographic parameters of complex Ic
H 4.73; P 8.71. Pure bis(diphenylphosphinoylmethyl)-
iodobenzene was isolated as an amorphous substance
by decomposition of the solvate at 91 C under
reduced pressure. 1H NMR spectrum (200 MHz,
CDCl3), , ppm: 3.43 d [4H, CH2P(O), J = 13.8 Hz],
Parameter
Formula
Ic
C70H64B2F8N2P4Pd2
1443.53
Molecular weight
6.95 t (1H, Harom, J = 1.8 Hz), 7.15 d (2H, Harom,
Space group
P-1
J = 1.8 Hz), 7.3 7.7 m [20H, P(O)Ph2]. 13C NMR
spectrum (50.3 MHz, CDCl3), C, ppm: 37.8 d (J =
65.9 Hz), 94.1, 128.8 d (J = 12 Hz), 131.3 d (J =
9.7 Hz), 131.7 t (J = 5.0 Hz), 132.2, 133.1, 133.6 d
(J = 10.6 Hz), 137.5 t (J = 3.7 Hz). 31P NMR spec-
a,
9.834(3)
b,
c,
, deg
, deg
, deg
12.925(3)
14.659(3)
65.449(15)
75.912(19)
77.431(18)
1629.5(6)
1
trum (80.96 MHz, CDCl3):
30.2 ppm. Found, %:
P
C 60.63; H 4.45; P 9.66. C32H27O2P2I. Calculated, %:
C 60.77; H 4.30; P 9.79.
3
V,
Z
3,5-Bis(diphenylphosphinoylmethyl)trimethyl-
silylethynylbenzene. 3,5-Bis(diphenylphosphinoyl-
methyl)iodobenzene benzene solvate, 11.2 g
(15.8 mmol), trimethylsilylacetylene, 1.8 g (19 mmol),
dichlorobis(triphenylphosphine)palladium, 0.1 g
(0.14 mmol), and copper(I) iodide, 30 mg
(0.16 mmol), were dissolved in succession in 65 ml of
piperidine, and the mixture was stirred for 3 h at
80 C. The solvent (piperidine) was removed under
reduced pressure, the residue was dissolved in 200 ml
of methylene chloride, and the solution was washed
with water (5 200 ml), dried over MgSO4, and
evaporated. The solid residue was recrystallized from
benzene. Yield 9 g (95%), colorless solid, mp 205 C.
1H NMR spectrum (200 MHz, CDCl3), , ppm: 0.12 s
(9H, Me3Si), 3.48 d [4H, CH2P(O), J = 13.2 Hz],
calc, g/cm3
, mm
1.471
0.716
1
Radiation
Mo-K ( = 0.71073
1.55 26.05
6352
)
2
scan range, deg
Number of independent
reflections
Number of reflections with
5954
I
2 (I)
R1
wR2
0.0602
0.1353
of solid catalyst. Samples of the colorless transparent
solution were withdrawn for GLC analysis. For
calibration, compounds Xa and Xb were isolated by
HPLC (colorless oily liquids). Mass spectrum, m/z
(Irel, %): Xa: 183 (100), 168 (35), 140 (97), 127 (7),
113 (15); Xb: 183 (100), 182 (39), 180 (43), 164
(27), 138 (26), 137 (49), 124 (35), 122 (24), 110 (42),
109 (26).
The ligands and palladium complexes were syn-
thesized from commercial reagents using commercial
solvents which were purified by standard procedures;
their parameters coincided with published data.
6.94 t (1H, Harom, J = 1.4 Hz), 7.04 d (2H, Harom
,
J = 1.4 Hz), 7.3 7.7 m [20H, P(O)Ph2]. 13C NMR
spectrum (50.3 MHz, CDCl3), C, ppm: 0.14, 37.8 d
(J = 66 Hz), 94.5, 104.7, 123.5, 128.8 d (J = 12 Hz),
131.1 d (J = 9.6 Hz), 131.8 d (J = 10.1 Hz), 132.0,
132. 2 132.6 m, 133.3. 31P NMR spectrum
(80.96 MHz, CDCl3):
30.2 ppm. Found, %:
C 73.64; H 6.13; P 10.34.PC37H36O2P2Si. Calculated,
%: C 73.73; H 6.02; P 10.28.
3,5-Bis(diphenylphosphinoylmethyl)iodobenzene
(V). A mixture of 14 g (35.9 mmol) of 3,5-bis(bromo-
methyl)iodobenzene and 16.6 g (72 mmol) of ethyl
diphenylphosphinite in 20 ml of m-xylene was heated
to 130 C and was stirred for 1 h at that temperature. It
was then cooled to room temperature and concentrated
under reduced pressure. Benzene, 70 ml, was added
to the residue, and the mixture was heated, filtered
while hot, and left to stand for crystallization. The
precipitate, crystalline 3,5-bis(diphenylphosphinoyl-
methyl)iodobenzene benzene solvate (1:1), was fil-
tered off and washed with benzene on a filter. Yield
25 g (98%), mp 91 C. Found, %: C 64.14; H 4.75;
P 8.80. C32H27O2P2I C6H6. Calculated, %: C 64.21;
3,5-Bis(diphenylphosphinoylmethyl)ethynylben-
zene (VI). To a solution of 9.0 g (15 mmol) of
3,5-bis(diphenylphosphinoylmethyl)trimethylsilyl-
ethynylbenzene in 100 ml of methanol we added
3.5 ml of a 5 M aqueous solution of NaOH. The mix-
ture was stirred for 2 h at room temperature, and
100 ml of water and 100 ml of methylene chloride
were added. The organic phase was separated, washed
with water (2 100 ml), dried over MgSO4, and
evaporated under reduced pressure, and the residue
was recrystallized from benzene to isolate 8.9 g
(97%) of 1 : 1 3,5-bis(diphenylphosphinoylmethyl)-
ethynylbenzene benzene solvate as colorless crystals
with mp 110 C. Found, %: C 78.85; H 5.75; P 10.16.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

SYNTHESIS AND CATALYTIC PROPERTIES
1277
C40H34O2P2. Calculated, %: C 78.93; H 5.63; P 10.18.
3,5-Bis(diphenylphosphinoylmethyl)ethynylbenzene
was isolated as a colorless amorphous substance by
decomposition of the solvate at 110 C under reduced
[40H, P(O)Ph2]. 13C NMR spectrum (50.3 MHz,
CDCl3), C, ppm: 38.0 d (J = 65 Hz), 89.4, 123.6,
128.8 d (J = 12 Hz), 131.2 d (J = 9.2 Hz), 131.6
132.4 m, 133.3. 31P NMR spectrum (80.96 MHz,
1
pressure. H NMR spectrum (200 MHz, CDCl3), ,
CDCl3):
30.3 ppm. Found, %: C 76.43; H 5.30;
P
ppm: 2.89 s (1H, HC ), 3.48 d [4H, CH2P(O), J =
13.6 Hz], 7.0 s (3H, Harom), 7.3 7.7 m [20H,
P 11.82. C66H54O4P4. Calculated, %: C 76.59; H 5.26;
P 11.97.
P(O)Ph2]. 13C NMR spectrum (50.3 MHz, CDCl3),
,
1,4-Bis[3,5-bis(diphenylphosphinoylmethyl)phe-
nyl]butadiyne (IIb). 3,5-Bis(diphenylphosphinoyl-
methyl)ethynylbenzene benzene solvate, 1.15 g
(1.9 mmol), iodine, 0.3 g (1.2 mmol), dichlorobis(tri-
phenylphosphine)palladium, 0.013 g (0.018 mmol),
and copper(I) iodide, 3 mg (0.016 mmol), were dis-
solved in succession in 12 ml of piperidine. The mix-
ture was stirred for 4 h at 80 C, the solvent was
removed under reduced pressure, the residue was
washed with benzene and dissolved in 20 ml of
methylene chloride, and the solution was washed with
water (3 20 ml), dried over MgSO4, and evaporated.
The crude product was dispersed in 15 ml of benzene,
and the mixture was heated for 30 min under reflux
and cooled. The precipitate was filtered off and dried
at 100 C under reduced pressure. Yield 0.9 g (90%),
ppm: 37.9 d (J = 66 Hz), 77.6, 83.2, 122.4, 128.8 Cd
(J = 12.6 Hz), 131.2 d (J = 10 Hz), 131.9 d (J =
10 Hz), 132.1, 132.4 t (J = 3.7 Hz), 132.8 t (J =
5.0 Hz), 133.2. 31P NMR spectrum (80.96 MHz,
CDCl3):
30.2 ppm. Found, %: C 76.88; H 5.51;
P
P 11.57. C34H28P2O2. Calculated, %: C 76.97; H 5.32;
P 11.68.
3,3 ,5,5 -Tetrakis(diphenylphosphinoylmethyl)-
diphenylacetylene (Ib). a. 3,5-Bis(diphenylphosphi-
noylmethyl)iodobenzene benzene solvate, 1.35 g
(1.9 mmol), 3,5-bis(diphenylphosphinoylmethyl)-
ethynylbenzene benzene solvate, 1.15 g (1.9 mmol),
dichlorobis(triphenylphosphine)palladium, 13 mg
(0.018 mmol), and CuI, 3 mg (0.016 mmol), were dis-
solved in succession in 12 ml of piperidine. The mix-
ture was stirred for 4 h at 80 C, the solvent was
removed under reduced pressure, and the residue was
washed with benzene and dissolved in 40 ml of
methylene chloride. The solution was washed with
water (3 40 ml), dried over MgSO4, and evaporated
under reduced pressure. The crude product was dis-
persed in 30 ml of benzene, and the mixture was
heated for 30 min under reflux and cooled to room
temperature. The precipitate was filtered off and dried
at 100 C under reduced pressure. Yield 1.86 g (95%).
1
mp 287 C. H NMR spectrum (200 MHz, CDCl3), ,
ppm: 3.46 d [8H, CH2P(O), J = 13.6 Hz], 6.97 d (4H,
Harom, J = 1.8 Hz), 7.0 t (2H, Harom, J = 1.8 Hz), 7.3
7.7 m [40H, P(O)Ph2]. 13C NMR spectrum (50.3 MHz,
CDCl3), C, ppm: 37.9 d (J = 66.3 Hz), 74.3, 81.1,
122.0, 128.8 d (J = 12.4 Hz), 131.2 d (J = 9.7 Hz),
132.0, 132.2, 132.6 t (J = 3.7 Hz), 133.1, 133.3 t (J =
5.0 Hz). 31P NMR spectrum (80.96 MHz, CDCl3):
30.3 ppm. Found, %: C 77.22; H 5.02; P 11.43.
P
C68H54O4P4. Calculated, %: C 77.12; H 5.14; P 11.70.
1,3,5-Tris[3,5-bis[(diphenylphosphinoylmethyl)-
phenylethynyl]benzene (IIIb). 1,3,5-Tribromoben-
zene, 1 g (3.17 mmol), 3,5-bis(diphenylphosphinoyl-
methyl)ethynylbenzene benzene solvate, 8 g
(13.16 mmol), dichlorobis(triphenylphosphine)palla-
dium, 0.19 g (0.27 mmol), triphenylphosphine, 35 mg
(0.14 mmol), triethylamine, 3.64 g (5 ml, 36 mmol),
and copper(I) iodide, 20 mg (0.11 mmol), were dis-
solved in succession in 50 ml of THF. The mixture
was heated for 100 h under reflux with stirring, the
solvent was removed under reduced pressure, the
residue was washed with benzene and dissolved in
100 ml of methylene chloride, and the solution was
washed with water (4 100 ml), dried over MgSO4,
and evaporated. The residue was recrystallized from
benzene and dried at 100 C under reduced pressure.
Yield 3.5 g (66%), mp 158 159 C. 1H NMR spectrum
(200 MHz, CDCl3), , ppm: 3.55 d [12H, CH2P(O),
J = 13.6 Hz], 7.10 s (9H, Harom), 7.36 7.76 m [63H,
b. 3,5-Bis(diphenylphosphinoylmethyl)iodoben-
zene benzene solvate, 11.23 g (15.6 mmol), dichloro-
bis(triphenylphosphine)palladium, 0.1 g (0.142 mmol),
and copper iodide, 30 mg (0.18 mmol), were dis-
solved in succession in 60 ml of piperidine. The mix-
ture was heated to 80 C, and acetylene was bubbled
through the mixture over a period of 3 h under
stirring. The solvent was removed under reduced pres-
sure, the solid residue was washed with benzene and
dissolved in 150 ml of methylene chloride, and the
solution was washed with water (3 150 ml), dried
over MgSO4, and evaporated under reduced pressure.
The crude product was dispersed in 150 ml of ben-
zene, and the mixture was heated for 30 min under
reflux and cooled to room temperature. The precipitate
was filtered off and dried at 100 C under reduced
1
pressure. Yield 7.5 g (92%), mp 285 C. H NMR
spectrum (200 MHz, CDCl3), , ppm: 3.47 d [8H,
CH2P(O), J = 13.6 Hz], 7.0 s (6H, Harom), 7.3 7.7 m
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

1278
BELETSKAYA et al.
P(O)Ph2, Harom]. 13C NMR spectrum (50.3 MHz,
the organic phase was separated, dried over MgSO4,
and evaporated. The residue was washed with hexane
and dried under reduced pressure. Yield 1.05 g (98%),
CDCl3), , ppm: 38.0 d (J = 65.8 Hz), 88.2, 90.3,
C
123.1, 124.1, 128.8 d (J = 12.0 Hz), 131.3, 132.0,
132.1, 132.6, 133.3, 134.1. 31P NMR spectrum
(80.96 MHz, CDCl3): 30.2 ppm. MALDI-TOF-MS
data (3,5-dihydroxybenzoic acid matrix): m/z 1770.10
[M + Ag]+). C108H84AgO6P6. Calculated: M 1771.65.
1
mp 187 C. H NMR spectrum (200 MHz, CDCl3), ,
ppm: 3.34 s (8H, CH2P), 6.86 t (2H, Harom, J =
1.2 Hz), 7.05 d (4H, Harom, J = 1.2 Hz), 7.3 7.5 m
(40H, PPh2). 13C NMR spectrum (50.3 MHz, CDCl3),
C, ppm: 36.1 d (J = 16.1 Hz), 89.5, 123.4, 128.7 d
(J = 6.4 Hz), 129.0, 130.4 d (J = 6.9 Hz), 130.8 t
(J = 7 Hz), 133.2 d (J = 18.4 Hz), 137.9 d (J =
8.2 Hz), 138.4 d (J = 15.2 Hz). 31P NMR spectrum
Hexakis[3,5-bis(diphenylphosphinoylmethyl)-
phenylethynyl]benzene (IVb). Hexabromobenzene,
1 g (1.81 mmol), 3,5-bis(diphenylphosphinoylmethyl)-
ethynylbenzene benzene solvate, 8 g (13.16 mmol),
dichlorobis(triphenylphosphine)palladium, 190 mg
(0.27 mmol), triphenylphosphine, 35 mg (0.14 mmol),
triethylamine, 3.64 g (5 ml, 36 mmol), and copper(I)
iodide, 20 mg (0.11 mmol), were dissolved in succes-
sion in 50 ml of THF. The mixture was heated for
300 h under reflux with stirring, the solvent was
removed under reduced pressure, the residue was
washed with benzene and dissolved in 100 ml of
methylene chloride, and the solution was washed with
water (4 100 ml), dried over MgSO4, and evaporated.
The residue was dissolved in 5 ml of methanol, the
solution was filtered, the filtrate was evaporated, and
the residue was recrystallized in succession from
benzene and 2-propanol and dried at 100 C under
reduced pressure. Yield 1.5 g (25%), yellow sub-
stance, mp 169 C (a sample for elemental analysis
was preliminarily melted under reduced pressure).
1H NMR spectrum (200 MHz, CDCl3), , ppm: 3.40 d
[24H, CH2P(O), J = 13.6 Hz], 6.91 s (6H, Harom),
7.08 s (12H, Harom), 7.18 7.68 m [120H, P(O)Ph2].
13C NMR spectrum (50.3 MHz, CDCl3), , ppm:
37.6 d (J = 65.9 Hz), 87.4, 99.1, 123.3, 127.5, 128.7 d
(J = 12 Hz), 131.3 d (J = 9.7 Hz), 131.5, 132.0,
(80.96 MHz, CDCl3):
9.0 ppm. Found, %:
C 81.45; H 5.55; P 12.56P. C66H54P4. Calculated, %:
C 81.64; H 5.61; P 12.76.
1,4-Bis[3,5-bis(diphenylphosphinomethyl)phe-
nyl]-1,3-butadiyne (IIa). 1,4-Bis[3,5-bis(diphenyl-
phosphinoylmethyl)phenyl]butadiyne, 5 g (4.7 mmol),
was dispersed in 100 ml of o-dichlorobenzene under
argon, and 9 g (65 mmol) of trichlorosilane was added
through a syringe. The mixture was heated to 100 C,
stirred at that temperature until the initial phosphine
oxide dissolved completely, and cooled, excess tri-
chlorosilane was removed under reduced pressure, and
a degassed solution of 12 g (300 mmol) of sodium
hydroxide in 70 ml of water was added. The mixture
was stirred for 15 min, and the organic phase was
separated, dried over MgSO4, and evaporated. The
residue was washed with hexane and dried under
1
reduced prssure. Yield 4.6 g (98%), mp 195 C. H
NMR spectrum (200 MHz, CDCl3), , ppm: 3.32 s
(8H, CH2P), 6.93 t (2H, Harom, J = 1.5 Hz), 7.03 d
(4H, Harom, J = 1.5 Hz), 7.3 7.5 m (40H, PPh2). 13C
NMR spectrum (50.3 MHz, CDCl3), C, ppm: 36.0 d
(J = 16.6 Hz), 74.0, 81.9, 121.8, 128.7 d (J = 6.5 Hz),
129.1, 131.3 d (J = 6.9 Hz), 131.9 t (J = 7 Hz),
133.1 d (J = 18.9 Hz), 138.1 d (J = 15.2 Hz), 138.1 d
(J = 8.2 Hz). 31P NMR spectrum (80.96 MHz,
132.2 d (J = 10.6 Hz), 133.1, 133.4. 31P NMR spec-
trum (80.96 MHz, CDCl3):
30.1 ppm. MALDI-
TOF-MS data (3,5-dihydroxyPbenzoic acid matrix):
m/z 3355.94 [M + Ag]+. C210H162O12P12. Calculated:
M 3249.27. Found, %: C 77.50; H 5.06; P 11.38.
C210H162O12P12. Calculated, %: C 77.63; H 5.03;
P 11.44.
CDCl3):
8.7 ppm. Found, %: C 81.96; H 5.32;
P
P 12.40. C68H54P4. Calculated, %: C 82.08; H 5.47;
P 12.45.
1,3,5-Tris[3,5-bis(diphenylphosphinomethyl)-
phenylethynyl]benzene (IIIa). 1,3,5-Tris[3,5-bis(di-
phenylphosphinoylmethyl)phenylethynyl]benzene,
1.7 g (1 mmol), was dispersed in 30 ml of benzene
under argon, and 4 g (30 mmol) of trichlorosilane was
added through a syringe. The mixture was heated for
16 h under reflux, excess trichlorosilane was removed
under reduced pressure, and a degassed solution of
3 g (75 mmol) of sodium hydroxide in 15 ml of water
was added. The mixture was stirred for 15 min, and
the organic phase was separated, dried over MgSO4,
and evaporated under reduced pressure. Yield 1.5 g
3,3 ,5,5 -Tetrakis(diphenylphosphinomethyl)di-
phenylacetylene (Ia). 3,3 ,5,5 -Tetrakis(diphenylphos-
phinoylmethyl)diphenylacetylene, 1.14 g (1.1 mmol),
was dispersed in 25 ml of o-dichlorobenzene under
argon, and 1.8 g (13 mmol) of trichlorosilane was
added through a syringe. The mixture was heated to
100 C under stirring until it became homogeneous
and cooled, excess trichlorosilane was removed under
reduced pressure, and a degassed solution of 2.5 g
(62.2 mmol) of sodium hydroxide in 15 ml of water
was added. The mixture was stirred for 15 min, and
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

SYNTHESIS AND CATALYTIC PROPERTIES
1279
1
(98%), mp 74 75 C. H NMR spectrum (200 MHz,
48.03 ppm. Found, %: C 58.31; H 4.01; N 1.81.
P
CDCl3), , ppm: 3.32 s (12H, CH2P), 6.85 s (3H,
Harom), 7.04 s (6H, Harom), 7.3 7.5 m (60H, PPh2),
7.52 d (3H, Harom, J = 0.8 Hz). 13C NMR spectrum
(50.3 MHz, CDCl3), C, ppm: 36.0 d (J = 16.1 Hz),
87.8, 90.9, 122.8, 124.3, 128.7 d (J = 6.9 Hz), 129.1,
130.5 d (J = 4.6 Hz), 131.2 t (J = 6.9 Hz), 133.1 d
(J = 18.4 Hz), 134.1, 137.9 d (J = 6.4 Hz), 138.1 d
(J = 13.4 Hz). 31P NMR spectrum (80.96 MHz,
C70H58B2F8N2P4Pd2. Calculated, %: C 58.48; H 4.07;
N 1.95.
Complex IIc. A solution of 1.15 g (2.59 mmol) of
Pd(CH3CN)4(BF4)2 in 100 ml of acetonitrile was
added to 1.3 g (1.31 mmol) of 1,4-bis[3,5-bis(di-
phenylphosphinomethyl)phenyl]-1,3-butadiyne (IIa).
The mixture was heated for 1 h under reflux and
cooled, and the solvent was removed under reduced
pressure. The residue was recrystallized from aceto-
CDCl3):
9.0 ppm. Found, %: C 82.58; H 5.54;
P
1
P 11.71. C108H84P6. Calculated, %: C 82.74; H 5.40;
P 11.85.
nitrile. Yield 0.4 g (21%), colorless crystals. H NMR
spectrum (400 MHz, CDCl3), , ppm: 4.21 t (8H,
CH2P, J = 4.8 Hz), 7.38 s (4H, Harom), 7.6 7.9 m
(40H, PPh2). 31P NMR spectrum (161.9 MHz,
Hexakis[3,5-bis(diphenylphosphinomethyl)phe-
nylethynyl]benzene (IVa). Hexakis[3,5-bis(diphenyl-
phosphinoylmethyl)phenylethynyl]benzene, 1.2 g
(0.37 mmol), was dispersed in 25 ml of o-dichloro-
benzene under argon, and 1.8 g (13.4 mmol) of tri-
chlorosilane was added through a syringe. The mix-
ture was stirred for 5 h at 110 C and cooled, excess
trichlorosilane was removed under reduced pressure,
and a degassed solution of 2.5 g (62.5 mmol) of
sodium hydroxide in 15 ml of water was added. The
mixture was stirred for 15 min, and the organic phase
was separated, dried over MgSO4, and evaporated
under reduced pressure. The residue was washed with
hexane and dried under reduced pressure. Yield 1.1 g
CD3CN):
46.8 ppm. Found, %: C 59.32; H 4.08;
P
N 1.83. C72H58B2F8N2P4Pd2. Calculated, %: C 59.17;
H 4.00; N 1.92.
Complex IIIc. A 0.39-g (2.2-mmol) portion of
PdCl2 was dissolved in 50 ml of boiling acetonitrile,
and a solution of 0.86 g (4.4 mmol) of AgBF4 in
20 ml of acetonitrile was added. The mixture was
stirred for 5 min, cooled to room temperature, filtered,
degassed, and added under nitrogen to 1.15 g
(0.73 mmol) of 1,3,5-tris[3,5-bis(diphenylphosphino-
methyl)phenylethynyl]benzene. The resulting mixture
was heated for 1 h under reflux, cooled, and evaporat-
ed under reduced pressure. The residue was dissolved
in 50 ml of CH2Cl2, the solution was filtered, and
the filtrate was evaporated under reduced pressure.
The residue was recrystallized from acetonitrile
1
(98%), yellow amorphous powder. H NMR spectrum
(200 MHz, CDCl3), , ppm: 3.14 s (24H, CH2P),
6.67 s (6H, Harom), 7.04 s (12H, Harom), 7.1 7.4 m
(120H, PPh2). 13C NMR spectrum (50.3 MHz,
CDCl3), C, ppm: 36.1 d (J = 16.5 Hz), 87.2, 99.7,
123.2, 127.6, 128.6 d (J = 6.4 Hz), 129.0, 130.7 d
(J = 5.1 Hz), 131.4 t (J = 7.1 Hz), 133.0 d (J =
18.4 Hz), 134.1, 137.8 d (J = 7.8 Hz), 138.2 d (J =
15.6 Hz). 31P NMR spectrum (80.96 MHz, CDCl3):
1
methanol. Yield 1.5 g (90%), colorless crystals. H
NMR spectrum (200 MHz, CDCl3), , ppm: 4.20 t
(12H, CH2P, J = 4.7 Hz), 7.38 s (6H, Harom), 7.6
8.0 m (63H, PPh2, Harom). 13C NMR spectrum
(50.3 MHz, CDCl3), , ppm: 38.7 t (J = 15.2 Hz),
C
9.1 ppm. Found, %: C 82.36; H 5.34; P 12.10.
86.2, 88.7, 119.7, 122.5, 125.2 t (J = 12 Hz), 127.9 t
(J = 5.1 Hz), 128.3 t (J = 22.6 Hz), 130.4, 131.3 t
(J = 6.9 Hz), 132.2, 146.9 t (J = 9.9 Hz), 155.7. 31P
P
C210H162P12. Calculated, %: C 82.50; H 5.34; P 12.16.
Complex Ic. A solution of 1.83 g (4.12 mmol) of
Pd(CH3CN)4(BF4)2 in 150 ml of acetonitrile was
added to 2.0 g (2.06 mmol) of 3,3 ,5,5 -tetrakis(di-
phenylphosphinomethyl)diphenylacetylene (Ia). The
mixture was heated for 2 h under reflux and cooled,
and the solvent was removed under reduced pressure.
The residue was recrystallized from acetonitrile. Yield
NMR spectrum (80.96 MHz, CDCl3):
MALDI-TOF-MS data (9-nitroanthracene matrix):
m/z 1921.73 [M 3CH3CN 2BF3
BF4]+.
46.1 ppm.
P
C108H81F2P6Pd3. Calculated: M 1921.95. Found, %:
C 60.21; H 4.01. C114H90B3F12N3P6Pd3. Calculated,
%: C 60.39; H 4.00.
1
1.5 g (51%), colorless crystals. H NMR spectrum
Complex Id. A suspension of 0.35 g (0.24 mmol)
of complex Ic in 40 ml of methylene chloride was
mixed with 40 ml of a saturated aqueous solution of
sodium chloride, and the mixture was stirred for 12 h.
The organic phase was separated and dried over
MgSO4, and the solvent was distilled off under
(200 MHz, CDCl3), , ppm: 4.21 t [8H, CH2P, J =
4.8 Hz], 7.34 s (4H, Harom), 7.6 8.0 m (40H, PPh2).
13C NMR spectrum (50.3 MHz, CDCl3), C, ppm:
40.5 t (J = 15.2 Hz), 89.4, 122.1, 126.9 t (J =
11.7 Hz), 129.70 t (J = 5.3 Hz), 130.2 t (J = 22.3 Hz),
132.2, 133.2 t (J = 6.9 Hz), 148.70 t (J = 10.4 Hz),
156.9. 31P NMR spectrum (80.96 MHz, CD3CN):
1
reduced pressure. Yield 0.3 g (98%). H NMR spec-
trum (200 MHz, CDCl3), , ppm: 3.92 t (8H, CH2P,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

1280
BELETSKAYA et al.
J = 4.6 Hz), 7.26 s (4H, Harom), 7.3 8.0 m (40H,
03-06175 and 03-03-89009) and by the Integration
of Higher School and Academy of Sciences program
(project no. AO-115).
PPh2). 13C NMR spectrum (50.3 MHz, CDCl3),
,
ppm: 42.7 t (J = 14.5 Hz), 89.8, 120.8, 126.1 t (J C=
11.2 Hz), 129.1 t (J = 5.3 Hz), 130.9, 131.9 t (J =
21.7 Hz), 133.2 t (J = 6.7 Hz), 148.3 t (J = 10.8 Hz),
REFERENCES
161.6. 31P NMR spectrum (80.96 MHz, CDCl3):
34.3 ppm. Found, %: C 63.10; H 4.05. C66H52Cl2-
PP4Pd2. Calculated, %: C 63.28; H 4.18.
1. Braga, D. and Grepioni, F., Acc. Chem. Res., 2000,
vol. 33, p. 601.
2. Braga, D., J. Chem. Soc., Dalton Trans., 2000,
Complex IId. A suspension of 0.2 g (0.14 mmol)
of complex IIc in 20 ml of methylene chloride was
mixed with 20 ml of a saturated aqueous solution of
sodium chloride, and the mixture was stirred for 12 h.
The organic phase was separated and dried over
MgSO4, and the solvent was removed under reduced
pressure. Yield 0.17 g (97%). 1H NMR spectrum
(400 MHz, CDCl3), , ppm: 3.96 t (8H, CH2P, J =
4.2 Hz), 7.29 s (4H, Harom), 7.3 8.0 m (40H, PPh2).
13C NMR spectrum (100.6 MHz, CDCl3), C, ppm:
42.40 t (J = 14.5 Hz), 73.95, 81.89, 118.94, 126.64 t
(J = 11.4 Hz), 128.8 t (J = 5.4 Hz), 130.71, 131.50 t
(J = 21.4 Hz), 132.91 t (J = 6.8 Hz), 148.17 t (J =
11.2 Hz), 163.05. 31P NMR spectrum (161.6 MHz,
p. 3705.
3. Schwab, P.F.H., Levin, M.D., and Michl, J., Chem.
Rev., 1999, vol. 99, p. 1863.
4. De Cola, L. and Belser, P., Coord. Chem. Rev.,
1998, vol. 177, p. 301.
5. Balzani, V., Juris, A., Venturi, M., Campagna, S.,
and Serroni, S., Chem. Rev., 1996, vol. 96, p. 759.
6. Beletskaya, I.P. and Chuchuryukin, A.V., Usp.
Khim., 2000, vol. 69, p. 699.
7. Beletskaya, I.P., Chuchurjukin, A.V., Dijkstra, H.P,,
van Klink, G.P.M., and van Koten, G., Tetrahedron
Lett., 2000, vol. 41, p. 1075.
8. Beletskaya, I.P., Chuchurjukin, A.V., Dijkstra, H.P.,
van Klink, G.P.M., and van Koten, G., Tetrahedron
Lett., 2000, vol. 41, p. 1081.
CDCl3):
32.8 ppm. Found, %: C 63.78; H 4.01.
P
C66H52Cl2P4Pd2. Calculated, %: C 63.97; H 4.10.
9. Dijkstra, H.P., Kruithof, C.A., Ronde, N., van
de Coevering, R., Ramon, D.J., Vogt, D., van
Klink, G.P.M., and van Koten, G. J. Org. Chem.,
2003, vol. 68, p. 675.
Complex IIId. A suspension of 0.2 g (0.09 mmol)
of complex IIIc in 20 ml of methylene chloride was
mixed with 20 ml of a saturated aqueuos solution of
sodium chloride, and the mixture was stirred for 12 h.
The organic phase was separated and dried over
MgSO4, and the solvent was removed under reduced
10. Brinkmann, N., Giebel, D., Lohmer, G., Reetz, M.T.,
and Kragl, U., J. Catal., 1999, vol. 183, p. 163.
11. De Groot, D., Eggling, E.B., de Wilde, J.C.,
Kooijman, H., van Haaren, R.J., van der Made, A.W.,
Spek A.L., Vogt, D., Reek, J.N.H., Kamer, P.J.C.,
and van Leeuwen, P.W.N.M., J. Chem. Soc., Chem.
Commun., 1999, p. 1623.
1
pressure. Yield 0.172 g (98%). H NMR spectrum
(200 MHz, CDCl3), , ppm: 3.92 t (12H, CH2P,
J = 4.4 Hz), 7.28 s (6H, Harom), 7.30 7.46 m (36H,
PPh2), 7.54 s (3H, Harom), 7.76 7.96 m (24H, PPh2).
13C NMR spectrum (50.3 MHz, CDCl3): C, ppm:
42.7 t (J = 14.7 Hz), 88.1, 91.2, 120.2, 124.4, 126.3 t
(J = 11.5 Hz), 129.1 t (J = 5.1 Hz), 131.0, 131.9 t
(J = 21.9 Hz), 133.2 t (J = 6.7 Hz), 148.4 t (J =
10.8 Hz), 162.3. 31P NMR spectrum (80.96 MHz,
CDCl3): P 34.2 ppm. MALDI-TOF-MS data (9-nitro-
anthracene matrix): m/z 1954.79 [M Cl]+. C108H81-
Cl2P6Pd3. Calculated: m/z 1954.86. Found, %:
C 65.01; H 4.12. C108H81Cl3P6Pd3. Calculated, %:
C 65.18; H 4.10.
12. Duchene, K.H. and Vogtle, F., Synthesis, 1986,
p. 659.
13. Steenwinkel, P., Kolmschot, S., Gossage, R.A.,
Dani, P., Veldman, N., Spek, A.L., and van
Koten, G., Eur. J. Inorg. Chem., 1998, p. 477.
14. Beletskaya, I.P. and Cheprakov, A.V., Chem. Rev.,
2000, vol. 100, p. 3009.
15. Beletskaya, I.P., Kashin, A.N., Karlstedt, N.B.,
Mitin, A.V., Cheprakov, A.V., and Kazankov, G.M.,
J. Organomet. Chem., 2001, vol. 622, p. 89.
16. Stark, M.A., Jones, G., and Richards, C.J., Organo-
metallics, 2000, vol. 19, p. 1282.
The authors are grateful to the X-Ray Research
Center (Institute of Organometallic Compounds,
Russian Academy of Sciences, Moscow, Russia) for
providing the possibility of acquiring experimental
data with the aid of their diffractometer.
17. Fossey, J.S. and Richards, C.J., Organometallics,
2002, vol. 21, p. 5259.
18. Dijkstra, H.P., Meijer, M.D., Patel, J., Kreiter, R.,
van Klink, G.P.M., Lutz, M., Spek, A.L., Canty, A.J.,
and van Koten, G., Organometallics, 2001, vol. 20,
p. 3159.
This study was financially supported by the Rus-
sian Foundation for Basic Research (project nos. 02-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003

SYNTHESIS AND CATALYTIC PROPERTIES
1281
19. Gorla, F., Togni, A., and Venanzi, L.M., Organo-
metallics, 1994, vol. 13, p. 1607.
23. Kleij, A.W., Gebbink, R.J.M.K., van den Nieuwen-
huijzen, P.A.J., Kooijman, H., Lutz, M., Spek, A.L.,
and van Koten, G., Organometallics, 2001, vol. 20,
p. 634.
20. Longmire, J.M., Zhang, X., and Shang, M., Organo-
metallics, 1998, vol. 17, p. 4374.
24. Sheldrick, G.M., SHELX97. Program for the Solu-
tion of Crystal Structures, Gotinngen: University
of Gottingen, 1997.
21. Schlenk, C., Kleij, A.W., Frey, H., and van
Koten, G., Angew. Chem., Int. Ed., 2000, vol. 39,
p. 3445.
22. Albrechet, M., Kocks, B.M., Spek, A.L., and van
Koten, G., J. Organomet. Chem., 2001, vol. 624,
p. 271.
25. Sheldrick G.M., SHELXL97. Program for the Refine-
ment of Crystal Structures, Gottingen: University
of Gottingen, 1997.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 9 2003