Catalytic activity of new PdII-complexes of bidentate PIII - N - PIII-ligands in Suzuki - Miyaura reaction

Article abstract of DOI:10.1007/s11172-015-0954-y

A reaction of readily available bis(diphenylphosphino)amines with (PhCN)₂PdCl₂ was used to synthesize Pd^II-complexes [Pd{Ph₂PN(R)PPh₂}Cl₂] (R = Pr ⁱ, cyclo-C₆H_11<

Full text of DOI:10.1007/s11172-015-0954-y

Russian Chemical Bulletin, International Edition, Vol. 64, No. 4, pp. 909—913, April, 2015
909
Catalytic activity of new PdIIꢀcomplexes
of bidentate PIII—N—PIIIꢀligands in Suzuki—Miyaura reaction
I. M. Aladzheva,a O. V. Bykhovskaya,a A. A. Vasil´ev,b Yu. V. Nelyubina,a and Z. S. Klemenkovaa
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Eꢀmail: shipov@ineos.ac.ru
bN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation
A reaction of readily available bis(diphenylphosphino)amines with (PhCN)2PdCl2 was
used to synthesize PdIIꢀcomplexes [Pd{Ph2PN(R)PPh2}Cl2] (R = Pri, cycloꢀC6H11, Ph), which
exhibited a high activity in the crossꢀcoupling of aryl bromides with phenylboronic acid.
Key words: bis(diphenylphosphino)amines, palladium complexes, Suzuki—Miyaura crossꢀ
coupling.
Complexes of bidentate PIII—N—PIIIꢀligands with
transition metals are a subject of intensive studies of orgaꢀ
nometal chemistry. These ligands can be used for a fine
tuning of activity and selectivity of the catalysts, which is
especially important for the reactions of industrial interꢀ
est, for example, polymerization1 and oligomerization of
ethylene,2 copolymerization of ethylene with carbon oxide
with the formation of polyketones,3 as well as for allylaꢀ
tion,4 hydroformylation,5 etc. It is known that PdIIꢀcomꢀ
plexes of PIII—N—PIIIꢀligands are efficient catalysts for
Heck and Suzuki—Miyaura6 reactions.
The present work describes the synthesis of new
PdIIꢀcomplexes of bis(diphenylphosphino)amines
[Pd{Ph2PN(R)PPh2}Cl2] (1a—c) and results of studies of
their catalytic activity in Suzuki—Miyaura crossꢀcoupling.
Complexes 1a—c were obtained based on readily available
PIII—N—PIIIꢀligands 2a—c (Scheme 1).
with the corresponding amines according to the proceꢀ
dures described earlier.2b,e,7,8 The characteristics of obꢀ
tained compounds 2a—c agree with the literature data.
The reactions of ligands 2a—c with (PhCN)2PdCl2 in the
ratio of 1 : 1 in CH2Cl2 were used to synthesize PdIIꢀcomꢀ
plexes 1a—c.* Compounds 1a—c are crystalline subꢀ
stances, which decompose when heated to determine meltꢀ
ing points. Their solubility in organic solvents dependents
on the nature of substituent at the nitrogen atom: comꢀ
plexes 1a and 1b are soluble in CH2Cl2 and CHCl3, while
efforts were required to make complex 1c to dissolve even
in CH2Cl2.
The structure and composition of complexes 1a—c
were confirmed by elemental analysis, IR spectroscopy,
1
31P and H NMR spectra. The IR spectra of complexes
1a—c, together with other absorption bands, exhibit two
bands of medium strength in the 50—400 cm–1 region
characteristic of Pd—Cl vibrations, which are absent in
the spectra of the starting ligands 2a—c. In the 31P NMR
spectra, the formation of complexes 1a—c is accompanied
by the upfield shift of the signals for the starting ligands
2a—c by more than 20 ppm, and with the broad singlets of
ligands 2a and 2b becoming sharp upon complexation.
The structure of the complexes was also confirmed by
singleꢀcrystal Xꢀray diffraction of compound 1a (Fig. 1)
and a 1 : 1 crystal solvate of 1b with dichloromethane
(1b•CH2Cl2) (Fig. 2). A replacement of the Pri group in
1a with the cycloꢀC6H11 one in 1b•CH2Cl2 leads to the
insignificant changes in their geometrical parameters,
which lie within the ranges characteristic of similar comꢀ
Scheme 1
R = Pri (a), cycloꢀC6H11 (b), Ph (c)
Reagents and conditions: i. Et3N, 0 C; ii. (PhCN)2PdCl2, 20 C,
CH2Cl2.
* Complex 1a was only characterized9 by chemical shift in the
31P NMR spectrum.
The starting bis(diphenylphosphino)amines 2a—c were
synthesized by the aminolysis of chlorodiphenylphosphine
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 0909—0913, April, 2015.
1066ꢀ5285/15/6404ꢀ0909 © 2015 Springer Science+Business Media, Inc.

910
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
Aladzheva et al.
Cl(1)
Pd(1)
Cl(2)
C(20)
crossꢀcoupling of aryl bromides 3a,b with phenylboronic
acid (Scheme 2).
C(22)
C(21)
C(4)
C(6)
C(3)
C(2)
C(5)
C(23)
Scheme 2
C(24)
C(19)
C(1)
P(2)
N(1)
P(1)
C(7)
C(12)
C(13)
C(26)
C(25)
C(8)
C(14)
C(15)
C(16)
C(18)
C(17)
C(9)
R = C(O)Me (3a, 4a), OMe (3b, 4b)
C(11)
C(10)
C(27)
Conditions: K3PO4, DMF, 90—110 C, 5 h.
The reaction was carried out with the 0.1 mol.%
concentration of the catalyst under study within the
90—110 C temperature range for 5 h. According to the
data obtained, the crossꢀcoupling proceeds with high yields
of the final products 4a,b (Table 1).
In the case of more active bromoacetophenone 3a, the
yield of 4a was 96—100%, for less active bromoanisole 3b
the yield of 4b under the same conditions was 70—96%.
From the results obtained, it follows that the studied
PdIIꢀcomplexes 1a—c show a high catalytic activity and
the yields of the final products 4a,b depend little on the
nature of the starting PIII—N—PIIIꢀligand.
The analysis of the reaction mixtures by 31P NMR
showed that complexes 1a—c undergo decomposition in
the course of the process. This suggests the involvement in
the reaction of finely dispersed palladium Pd0 (see Ref. 12),
the precursor of which are compounds 1a—c (cf. Refs 11a
and 13). In particular, it was shown that in such processes
the complicated catalytic systems with distinctly different
kinds of active sites are formed, on each of which the
process can follow a different mechanism.12e The subtle
variations in the structure of the ligands, including those
which eliminate, can strongly influence the structure of
Fig. 1. General view of complex 1a in representation of atoms by
ellipsoids of thermal vibrations (p = 50%).
Cl(1)
C(2)
Cl(2)
C(20)
C(4)
C(3)
C(6)
C(22)
C(21)
Pd(1)
N(1)
C(23)
C(5)
C(24)
C(19)
P(2)
C(1)
P(1)
C(12)
C(7)
C(13)
C(26)
C(14)
C(8)
C(9)
C(18)
C(17)
C(25)
C(30)
C(29)
C(11)
C(15)
C(16)
C(27)
C(28)
C(10)
Fig. 2. General view of complex 1b in crystal solvate 1b•CH2Cl2
in representation of atoms by ellipsoids of thermal vibrations
(p = 50%).
pounds. Thus, the P—N bond lengths remain constant
within the error limits (1.709(2) and 1.7080(15) Å in 1a as
compared to 1.702(2) and 1.7003(16) Å in 1b•CH2Cl2),
whereas the Pd—P and Pd—Cl bonds lengthen by less
than 0.01 Å (Pd—P 2.2081(8) and 2.2206(8) Å as comꢀ
pared to 2.2106(5) and 2.2221(5) Å; Pd—Cl 2.3589(8) and
2.3720(7) Å as compared to 2.3716(5) and 2.3776(5) Å,
respectively). The PdCl2P2 fragment in 1b•CH2Cl2 is
planar within 0.01 Å, whereas in 1a it is considerably
distorted, and the angle between the P—Pd—P and
the Cl—Pd—Cl planes is 8.1(1)° (for comparison: in
1b•CH2Cl2 it is 3.2(1)). The bent angle along the P...P
line in the PdP2N fragment in complex 1a is also much
larger than in complex 1b•CH2Cl2: 9.2(1) and 4.9(1),
respectively.
Table 1. Crossꢀcoupling of aryl bromides 3a,b catalyzed
by complexes 1a—c (0.1 mol.%) at different temꢀ
peraturesa
3
1
Conversionb of 3a,b (%)
90
100
110
C
3a
3a
3a
3b
3b
3b
1a
1b
1c
1a
1b
1c
96
98
96
80
83
70
96
99
96
85
88
80
198
100
100
196
193
192
a The reaction time was 5 h.
b Assumed being equal to the yields of biaryls 4a,b.
The catalytic activity of complexes 1a—c was deterꢀ
mined in a model Suzuki—Miyaura reaction,10,11 the

Novel PdII complexes in Suzuki crossꢀcoupling
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
911
2999, 2929, 2854, 1432, 1091, 1063, 914, 857, 841, 743, 696,
507. 1H NMR (CDCl3), : 0.98—1.18, 1.38—1.75, 1.82—2.02
(all m, 10 H, 5 CH2, cуcloꢀC6H11); 3.20—3.35 (m, 1 H, CHN,
cycloꢀC6H11); 7.26—7.48 (m, 20 H, 4 C6H5). 13C NMR (CDCl3),
: 25.37 (s, C(4)); 26.02 (s, C(3), C(5)); 34.92 (t, C(2), C(6),
active species in the course of their formation. The earlier
described palladium complexes with PIII—N—PIII ligands
of more complicated structure exhibited similar catalytic
activity in Suzuki—Miyaura crossꢀcoupling.6
3JP,C = 6.3 Hz); (5 CH2, cycloꢀC6H11); 60.24 (t, C(1), cycloꢀC6H11
,
3
2JP,C = 8.0 Hz); 127.83 (d, Cm, C6H5, JP,C = 6.2 Hz); 128.38
Experimental
2
(s, Cp, C6H5); 132.66 (d, Co, C6H5, JP,C = 21.5 Hz); 139.96
(d, Cipso, C6H5, 1JP,C = 16.8 Hz). 31P NMR (CDCl3), : 50.3 (br.s)
(cf. Ref. 2b: 50.7 (br.s)).
Reactions were carried out in anhydrous solvents under dry
argon. Commercial reactants Ph2PCl (Aldrich) and PriNH2
(Acros) were used in the synthesis. NMR spectra of compounds
obtained were recorded on a Bruker AMXꢀ400 spectrometer,
using signals of the deuterated solvent (CDCl3) as an internal
standard (1H and 13C) and 85% H3PO4 as an external standard
Complexes [Pd{Ph2PN(R)PPh2}Cl2] (1a—c) (general proceꢀ
dure). A solution of the corresponding ligand 2a—c (0.153 mmol)
in CH2Cl2 (5 mL) was added slowly to
a solution of
(PhCN)2PdCl2 (0.153 mmol) in the same solvent (5 mL) at 20 C
under argon. The formation of a small amount of amorphous
precipitate was observed. After 30 min, the reaction mixture was
filtered through a paper filter and was allowed to stand at 20 C
for 24 h. A yellow precipitate formed was filtered, washed with
diethyl ether several times, and dried in vacuo.
Dichloro[N,Nꢀbis(diphenylphosphino)ꢀNꢀisopropylamine]ꢀ
palladium(II) (1a). The yield was 56%, decomp.p. >210 C.
Found (%): C, 54.03; H, 4.70; N, 2.28. C27H27Cl2NP2Pd. Calꢀ
culated (%): C, 53.62; H, 4.50; N, 2.31. IR (KBr), /cm–1: 3053,
2979, 2929, 1436, 1134, 1108, 1101, 1040, 874, 863, 752, 693,
527, 510; (Nujol), /cm–1: 306 and 283 (Pd—Cl). 1H NMR
(CDCl3), : 0.78 (d, 6 H, 2 CH3, Pri, 3JH,H = 6.8 Hz); 3.62—3.82
(m, 1 H, CH, iꢀPr); 7.10—7.40, 7.45—7.80, 8.00—8.15 (all m,
20 H, 4 C6H5). 31P NMR (CH2Cl2), : 28.2 (s) (cf. Ref. 9: 28.9 (s)).
Dichloro[NꢀcyclohexylamineꢀN,Nꢀbis(diphenylphosphino)]ꢀ
palladium(II) (1b). The yield was 69%, decomp.p. >264 C.
(
31P). IR spectra were recorded on a Bruker Tensor 37 Fourierꢀ
transform spectrometer with the 2 cm–1 resolution for the samꢀ
ples in KBr pellets (400—4000 cm–1 range) and a suspension in
Nujol (50—400 cm–1 range).
N,NꢀBis(diphenylphosphino)ꢀNꢀcyclohexylamine (2b). A soluꢀ
tion of cyclohexylamine (0.66 g, 6.13 mmol) in CH2Cl2 (10 mL)
was added dropwise to a solution of Ph2PCl (3.09 g, 14 mmol)
and Et3N (2.02 g, 20 mmol) in CH2Cl2 (20 mL) at 0 °C and with
vigorous stirring over 35 min. The reaction mixture was stirred
for 6 h at 20 C. Then, the solvent was evaporated in vacuo, the
residue was treated with benzene, a precipitate of Et3N•HCl
was filtered off, benzene was evaporated in vacuo. The residue
was recrystallized from ethanol to isolate a white crystalline prodꢀ
uct (0.95 g, 31%) with m.p. 126—128 C. Found (%): C, 77.03;
H, 6.91; N, 2.89; P, 13.36. C30H31NP2. Calculated (%): C, 77.07;
H, 6.69; N, 2.99; P, 13.25. IR (KBr), /cm–1: 3068, 3052,
Table 2. Basic crystallographic data and structure refinement statistics for 1a and 1b•CH2Cl2
Parameter
1a
1b•CH2Cl2
Molecular formula
Molecular weight
C27H27Cl2NP2Pd
604.74
C31H33Cl4NP2Pd
729.72
T/K
120
120
Crystal system
Space group
Orthorhombic
Pbca
Monoclinic
P21/n
Z
8
4
a/Å
b/Å
c/Å
/deg
16.6404(9)
14.8877(8)
20.3035(11)
90.00
5029.9(5)
1.597
13.1715(5 )
13.6150(5)
17.8565(7)
96.5550(10)
3181.3(2)
1.524
3
V/Å
dcalc/g cm–3
/cm–1
10.95
10.42
F(000)
2448
1480
2max/deg
58
58
Number of reflections
measured
37968
6686
5705
25907
8454
7368
independent
with I > 2(I)
Number of refined parameters
R1
wR2
GOOF
300
362
0.0457
0.0973
1.154
0.0277
0.0702
1.036
Residual electron density,
–3
(dmax/dmin)/e Å
0.450/–1.421
1.023/–0.930

912
Russ.Chem.Bull., Int.Ed., Vol. 64, No. 4, April, 2015
Aladzheva et al.
Found (%): C, 55.94; H, 4.95; Cl, 10,95; N, 2.10; P, 9.53.
C30H31Cl2NP2Pd. Calculated (%): C, 55.88; H, 4.85; Cl 10.99;
N, 2.17; P, 9.60. IR (KBr), /cm–1: 3051, 2926, 2857, 1436,
1108, 928, 868, 749, 691, 516; (Nujol), /cm–1: 303 and 287
(Pd—Cl). 1H NMR (CDCl3), : 0.60—0.79, 0.83—1.00, 1.29—1.52
(all m, 10 H, 5 CH2, cycloꢀC6H11); 3.15—3.40 (m, 1 H, CHN,
cycloꢀC6H11); 7.55—7.73, 8.02—8.19 (both m, 20 H, 4 C6H5).
31P NMR (CH2Cl2), : 28.4 (s).
A. Neveling, S. Otto, M. J. Overett, A. M. Z. Slawin, P. Wassꢀ
erscheid, S. Kuhlmann, J. Am. Chem. Soc., 2004, 126, 14712;
(c) K. Blann, A. Bollmann, J. T. Dixon, F. M. Hess,
E. Killian, H. Maumela, D. H. Morgan, A. Neveling, S. Otto,
M. J. Overett, J. Chem. Soc., Chem. Commun., 2005, 622;
(d) S. Kuhlmann, K. Blann, A. Bollmann, J. T. Dixon,
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Dichloro[N,Nꢀbis(diphenylphosphino)ꢀNꢀphenylamine]palꢀ
ladium(II) (1c). The yield was 72%, decomp.p. > 210 C. Found (%):
C, 56.24; H, 4.09; N, 2.17; P, 9.65. C30H25Cl2NP2Pd. Calculatꢀ
3. S. J. Dossett, A. Gillon, A. G. Orpen, J. S. Fleming, P. G.
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ed (%): C, 56.39; H, 3.92; N, 2.19; P, 9.71. IR (KBr), /cm–1
:
3062, 3050, 2984, 1492, 1435, 1245, 1106, 1095, 949, 912, 753,
687, 499, 490, 481; (Nujol), /cm–1: 317 and 297 (Pd—Cl).
31P NMR (CH2Cl2), : 34.1 (s).
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2000, 11, 4153; (b) Y. Wang, X. Li, K. L. Ding, Tetrahedron
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Xꢀray diffraction studies of 1a and 1b•CH2Cl2 were carried
out on Bruker SMART APEX II DUO and Bruker APEX II
DUO CCD (MoꢀK radiation, graphite monochromator, ꢀscan
technique), respectively. The structures were solved by direct
method and refined by the least squares method in anisotropic
fullꢀmatrix approximation on F2hkl. Positions of hydrogen atoms
were calculated geometrically and refined in isotropic approxiꢀ
mation using a riding model. Basic crystallographic data and
structure refinement statistics are given in Table 2. All the calcuꢀ
lations were carried out using the SHELXTL PLUS software
package.14 Crystallographic data for 1a and 1b•CH2Cl2 were
deposited with the Cambridge Crystallographic Data Center
(CCDC 1014295 and 1014296, respectively).
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degassed by pumping off the air and filling the tube with argon.
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to the yields of products 4.
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Received September 25, 2014;
in revised form January 20, 2015