Indian Journal of Chemistry
Vol. 52A, November 2013, pp. 1400-1403
Notes
Palladium(II) complex of phosphinic
amide, [Pd(Ph2P(O)CH2NPh)2], and its
catalytic investigation towards
Suzuki-Miyaura cross-coupling reactions
Sk Md Ibrahim, Chelladurai Ganesamoorthy &
Maravanji S Balakrishna*
Phosphorus Laboratory, Department of Chemistry, Indian Institute
of Technology Bombay, Powai, Mumbai 400 076, India
Email: krishna@chem.iitb.ac.in
Received 18 June 2013; revised and accepted 28 September 2013
The reaction between aniline and chlorodiphenylphosphine in
2:1 molar ratio afforded the aminophosphine C6H5NHPPh2 (1)
which on subsequent treatment with paraformaldehyde produced
the methylene inserted product, Ph2P(O)CH2NHPh (2). Treatment
of (2) with Pd(OAc)2 in 2:1 molar ratio produced the complex
[Pd(Ph2P(O)CH2NPh)2] (3), which has been characterized by
various spectroscopic and microanalysis data. The catalytic
activity of complex (3) has been investigated in Suzuki-Miyaura
cross-coupling reactions. The reactions of various aryl halides
with phenylboronic acid using (3) as a catalyst gave moderate
(35–55%) to high yields (100%) of coupled products.
Keywords: Aminophosphines, Aryl halides, Phosphinic amide,
Palladium, Cross-coupling reactions, Suzuki-Miyaura
cross-coupling reactions, Catalytic activity
Hybrid ligands having both soft- and hard-donor
atoms are found to be efficient ligands in coordination
and organometallic chemistry.1-4 They offer unusual
structural features to the late transition metals and
induce interesting reactivity for greater catalytic
activity in organic transformations.2,5,6 In this context,
several groups have focused their attention in making
hybrid ligands having P,O-, P,N-, or P,S-donor sites.7-11
We have a long standing interest in designing
phosphorus based ligands appended with additional
hetero-donor atoms to explore their transition metal
chemistry and catalytic applications.1-3,12-16 Insertion
of carbon fragments into the P—N bonds17,18 led to
the isolation of a new family of heterodifunctional
ligands of the type N,-P(=O) with acidic hydrogen
on nitrogen atoms. Treatment of these ligands
with transition metals under appropriate reaction
conditions can lead to the formation of coordination
complexes having both covalent and coordinate-
covalent bonds through anionic nitrogen and –P(=O)
donors, respectively. As a part of our interest in
syntheses and transition metal chemistry of
aminophosphine ligands19-23 and their catalytic
applications,24-28 we describe herein the palladium(II)
complex [Pd(Ph2P(O)CH2NPh)2] (3) and its utility
in Suzuki-Miyaura cross-coupling reaction.
Experimental
All experimental manipulations were performed
under rigorously anaerobic conditions using
Schlenk techniques. All the solvents were purified by
conventional procedures and distilled prior to use.39
[Pd(OAc)2] was purchased from Aldrich Chemicals
and used as such without further purification.
The phosphinic amide Ph2P(O)CH2NHPh (2) was
prepared from the aminophosphine C6H5NHPPh2 (1)
according to the published procedure.17,18 The 1H and
31
P{1H} NMR ( in ppm) spectra were recorded using
VXR 400 spectrometer operating at the appropriate
frequencies using TMS and 85% H3PO4 as internal
and external references, respectively. The NMR
samples were prepared in a drybox, without exposing
the compound to atmosphere. The spectra were
recorded in CDCl3 solutions with CDCl3 as an internal
lock; positive shifts lie downfield of the standard
in all of the cases. The melting points were observed
in capillary tubes and are uncorrected.
The palladium(II) complex [Pd(Ph2P(O)CH2NPh)2]
(3) was prepared as follows: A solution of palladium
acetate (0.156 g, 0.69 mmol) in dichloromethane
(5 mL) was added dropwise to a solution of (2)
(0.426 g, 1.38 mmol) also in dichloromethane
(10 mL). The mixture was stirred at room temperature
for 4 h, when the color of the solution changed from
orange to brown. The solution was filtered and the
solvent was removed under vacuum to get a brown
solid (3). Yield: 89% (0.442 g). M. pt.: 127-130 ºC
(dec). Anal. (%): Calcd for C38H34N2O2P2Pd: C,
63.47; H, 4.77; N, 3.90. Found: C, 63.55; H, 4.90; N,
3.82. 1H NMR (400 MHz, CDCl3):  7.81-6.65
(m, phenyl, 15H), 3.95 (d, CH2, 2H). 31P {1H} NMR
(162 MHz, CDCl3):  28.7 (s).
The Suzuki-Miyaura cross-coupling reaction was
carried out as follows: In a two-necked round bottom
flask under an atmosphere of nitrogen, were placed the
appropriate amounts of the catalyst and solvent (5 mL).
 NOTES
The correct amount of catalyst was added as a THF
solution made up of multiple volumetric dilutions
of stock solution. After stirring for 5 minutes, aryl
halide (0.5 mmol), phenyl boronic acid (0.75 mmol)
and K2CO3 (0.138 g, 1 mmol) were introduced into
the reaction flask. The mixture was stirred at room
temperature or at the required temperature under an
atmosphere of nitrogen (the course of reaction was
monitored by GC analysis). Then, the solvent was
removed under reduced pressure. The resultant
residual mixture was diluted with H2O (10 mL) and
Et2O (10 mL), followed by repeated extraction
(2×6 mL) with Et2O. The combined organic fraction
was dried (MgSO4), stripped of the solvent under
vacuum and the residue was dissolved in 5 mL of
dichloromethane. An aliquot was taken with a
syringe and subjected to GC analysis. Yields were
calculated versus aryl halides or dodecane as an
internal standard.
Results and discussion
The reaction of aniline with chloro diphenyl-
phosphine in 2:1 molar ratio at room temperature
afforded the aminophosphine, C6H5NHPPh2 (1) which
on subsequent treatment with paraformaldehyde
produced methylene inserted product
Ph2P(O)CH2NHPh (2) in good yield (Scheme 1).17,18
Compounds (1) and (2) are white crystalline
solids and are highly soluble in most of the organic
solvents. The compound (2) is stable towards
air and moisture; however, compound (1) decomposes
slowly on exposure to air to form aniline and
phosphinic acid.
The reaction of (2) with Pd(OAc)2 in 2:1 molar ratio
afforded the chelate complex [Pd(Ph2P(O)CH2NPh)2]
(3) in good yield. The 31P{1H} NMR spectra of
compounds (2) and (3) show sharp singlets at 27.9 and
28.7 ppm, respectively. The 1H NMR spectrum of (3)
shows a doublet centered at 3.95 ppm corresponding to
the methylene protons (2JPH = 8.8 Hz), whereas the
aromatic protons appear as multiplet at 6.66-7.81 ppm.
On exposure to air, the complex (3) readily
decomposes to give palladium black, both in solution
1401
and in solid state. The reaction of (3) with
[Pd(COD)Cl2] did not proceed irrespective of the
reaction conditions and stoichiometry of reactants.
The palladium-catalyzed Suzuki-Miyaura cross-
coupling reaction is one of the efficient methods for
forming symmetric and nonsymmetric biaryl
compounds in organic synthesis.29-38 The unstable
nature of (3) in solid and solution state seldom
rendered a direct investigation of its catalytic property
in its pure form. However, facile reactivity of (2)
with Pd(OAc)2 prompted us to make the compound
in situ in a catalytic reaction medium under inert
atmosphere. A mixture of Pd(OAc)2 and (2) (1:2 ratio,
respectively) effectively catalyzes Suzuki-Miyaura
cross-coupling reactions of a variety of aryl halides
with phenyl boronic acid affording the desired biaryls
in moderate to good yields (Tables 1 and 2).
The catalytic reactions have been systematically
studied to find the optimum conditions to afford
biaryls in good yield. It is important to achieve
good yields using minimum amounts of catalyst.
We therefore examined the effect of catalyst
loading on a convenient coupling between
4-bromoacetophenone and phenylboronic acid
(Table 1). Complete conversion of the starting
materials into biaryl was achieved with 0.05 mol%
of catalyst in 1 h. High yields are maintained from
normal catalyst loads down to a level of 0.01 mol% and
0.005 mol%. A moderate yield (48%) was achieved
even at catalyst loading as low as 0.001 mol% with
a TON of 48,000.
The coupling reaction with various aryl halides
was investigated. A solution of Pd(OAc)/(2)
(0.2 mol% of Pd) in MeOH containing K2CO3
(2 equiv.) proved to be an active catalyst for
easy-to-couple substrates like 4-bromoacetophenone,
4-bromobenzaldehyde and 4-bromobenzonitrile which
coupled with phenylboronic acid to give quantitative
yields of the corresponding biphenyls at room
temperature in 1 h (Table 2, entries 1-3). However,
the coupling of deactivated and electron rich aryl
bromides produced the coupled products in low
to moderate yields (Table 2, entries 4 and 5).
The coupling of sterically bulky aryl bromides
with boronic acid also gave moderate yields (Table 2,
entries 5 and 6). For example, the coupling of
2-bromo-6-methoxy naphthalene with phenylboronic
acid in the presence of 0.2 mol% of catalyst
at room temperature gave 2-phenyl-6-methoxy
naphthalene in 60% yield. In most cases the catalytic
1402 INDIAN J CHEM, SEC A, NOVEMBER 2013

Table 1—Influence of catalyst loading on the Suzuki-Miyaura cross coupling reaction

Entry Aryl halide Amt of catalyst Time Producta Conv.b TONc

(mol%) (h) (%)

1 MeCO Br 0.05 1 MeCO 100 2000

2 MeCO Br 0.01 2 MeCO 93 9300

3 MeCO Br 0.005 1 MeCO 79 15800

4 MeCO Br 0.001 1 MeCO 48 48000

5 NC Br 0.005 1 NC 80 16000

a
Condition: Aryl halide (0.5 mmol), phenyl boronic acid (0.75 mmol), K2CO3 (1 mmol), MeOH (5 mL).
b
Conversion to coupled product determined by GC, based on aryl halides; average of two runs.
c
In units of mol product/mol catalyst (Pd).

Table 2—Suzuki-Miyaura cross-coupling of aryl halides with phenyl boronic acids catalyzed by Pd(OAc)2 and Ph2P(O)CH2NHPh (2)

Pd(OAc)2/2
Br + B(OH)2
K2CO3, MeOH
R R

Entry Substrate Product Cond.a Conv.b (%)

1 MeCO Br MeCO 0.2 mol % 100

RT, 1 h

2 NC Br NC
0.2 mol % 100
RT, 1 h
3 OHC Br OHC
0.2 mol % 100
RT, 1 h
4 MeO Br MeO 0.2 mol % 28
RT, 1 h
OMe OMe

5 Br Ph 0.2 mol % 60
RT, 1 h
MeO MeO
6 Br Ph 0.1 mol % 58
MeO MeO
RT, 1 h

7 NC Cl NC
2 mol % 20
60 °C, 2 h

8 I 0.2 mol % 100

RT, 1 h
a
Aryl halide (0.5 mmol), phenyl boronic acid (0.75 mmol), K2CO3 (1 mmol), MeOH (5 mL).
b
Conversion to coupled product determined by GC, based on aryl halides; average of two runs.
 NOTES 1403

mixture showed maximum efficiency within 2 h 12 Ganesamoorthy C, Balakrishna M S, George P P & Mague J T,
and further improvement in the yield was not Inorg Chem, 46 (2007) 848.
13 Chandrasekaran P, Mague J T & Balakrishna M S, Inorg
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by prolonging the reaction time. 14 Chandrasekaran P, Mague J T & Balakrishna M S, Inorg
The present study shows that the phosphinic amide Chem, 44 (2005) 7925.
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16 Balakrishna M S, Panda R & Mague J T, Inorg Chem, 40
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