Synthesis and characterization of new bis(diphenylphosphino)aniline ligands and their complexes: X-ray crystal structure of palladium(II) and platinum(II) complexes, and application of palladium(II) complexes as pre-catalysts in Heck and Suzuki cross-coup

Article abstract of DOI:10.1016/j.poly.2009.04.033

Two new bis(diphenylphosphino)isopropylphenylamines, (PPh₂)₂N-C₆H₄-CH(CH₃)₂, having the isopropyl substituent at the carbon atom 2 (1) or 4 (2), were prepared by the aminolysis of chlorodip

Full text of DOI:10.1016/j.poly.2009.04.033

Polyhedron 28 (2009) 2313–2320
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Synthesis and characterization of new bis(diphenylphosphino)aniline ligands
and their complexes: X-ray crystal structure of palladium(II) and platinum(II)
complexes, and application of palladium(II) complexes as pre-catalysts in Heck
and Suzuki cross-coupling reactions
a
a
b
Murat Aydemir a, Feyyaz Durap a, Akın Baysal a, , Osman Akba , Bahattin Gümgüm , Saim Özkar ,
*
Leyla Tatar Yıldırım c
a Dicle University, Department of Chemistry, TR-21280 Diyarbakır, Turkey
b Middle East Technical University, Department of Chemistry, TR-06531 Ankara, Turkey
c Hacettepe University, Department of Engineering Physics, Beytepe, TR-06800 Ankara, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
Two new bis(diphenylphosphino)isopropylphenylamines, (PPh2)2N-C6H4-CH(CH3)2, having the isopropyl
substituent at the carbon atom 2 (1) or 4 (2), were prepared by the aminolysis of chlorodiphenylphos-
phine with isopropyl substituted aniline at the ortho- or para-position, respectively, under anaerobic con-
ditions. Oxidation of 1 and 2 with either aqueous hydrogen peroxide, elemental sulfur or grey selenium in
thf gave the corresponding oxides, sulfides and selenides (Ph2P@E)2N-C6H4-CH(CH3)2, where E = O, S or
Se, respectively. The palladium and platinum complexes [M{(Ph2P)2N-C6H4-CH(CH3)2}Cl2] (M = Pd, Pt)
and the copper complex [Cu{(Ph2P)2N-C6H4-CH(CH3)2}2]PF6 were isolated from the reaction of the
bis(phosphino)anilines with MCl2(cod) or [Cu(CH3CN)4]PF6, respectively. The new compounds were char-
acterized by NMR, IR spectroscopy and elemental analysis. Furthermore, the solid-state structures of two
representative complexes were determined using single crystal X-ray diffraction analysis. The com-
pounds of palladium (1d) and platinum (1e), both mononuclear complexes, crystallize in the monoclinic
P21/c space group. In both compounds the metal ion has a distorted square–planar coordination geome-
try. The structural properties of complexes 1d and 1e in the solid state are very similar. The palladium
complexes were also tested for their catalytic activities in C–C coupling reactions.
Received 9 March 2009
Accepted 10 April 2009
Available online 4 May 2009
Keywords:
Aminophosphine
Complexes
Crystal structures
Catalysis
Heck reaction
Suzuki coupling
Ó 2009 Elsevier Ltd. All rights reserved.
1. Introduction
chemistry and in homogeneous catalysis as these ligands can be
used for fine tuning the activity and selectivity of the catalyst
Tertiary phosphines have long been used in the design and syn-
thesis of transition metal complexes with catalytic properties [1–
3], especially with late transition metals like nickel, rhodium,
ruthenium, palladium and platinum [4] that can be used as highly
active catalysts in industrially important reactions such as allylic
alkylation [5–8], amination [9–11], the Heck reaction [12–20], Su-
zuki coupling [21–25], hydroformylation [26–29], and hydrogena-
tion of olefins [30–33]. In particular, palladium complexes
containing phosphine ligands serve as highly active catalysts for
the straightforward formation of carbon–carbon bonds [34–37].
Compounds containing phosphorus–nitrogen direct bonds have
been known for many years and their chemistry has been of con-
siderable interest because of their applications in increasingly di-
[40]. A variety of PNP and related diphosphine ligands, specially
in combination with Cr(III) compounds, were reported to be very
active and efficient catalysts for ethylene tri- and tetramerization
[41–44]. Bis(phosphino)amines display their versatility by exhibit-
ing different coordination behavior when the donor–acceptor
properties are altered by incorporating a substituent at the ligand
backbone [45]. Synthesis and coordination chemistry of bis(phos-
phino)anilines have also been studied in some detail [46,47]. It
has been shown that coordination of bis(phosphino)anilines to
transition metal ions occurs mainly via the phosphorus centers
due to the low basicity of the amine nitrogen, attributable to the
P–N
p interaction between the phosphorus d and nitrogen p
p p
orbitals [48].
verse
fields
[38,39].
The
applications
of
chelating
Herein, we report the synthesis of two new bis(diphenylphos-
phino)anilines by the aminolysis of chlorodiphenylphosphine with
isopropyl substituted aniline at the ortho- or para-positions and the
corresponding oxides, sulfides and selenides as well as their com-
plexes with selected transition metal ions (Cu+, Pd2+ and Pt2+). The
bis(phosphino)amine ligands is widespread in organometallic
* Corresponding author. Tel.: +90 412 2488550x3175; fax: +90 412 2488039.
E-mail address: akinb@dicle.edu.tr (A. Baysal).
0277-5387/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2009.04.033

2314
M. Aydemir et al. / Polyhedron 28 (2009) 2313–2320
compounds were isolated from the reaction mixture by crystalliza-
tion and fully characterized using elemental analysis, FT-IR, multi-
nuclear NMR spectroscopy. The solid-state structures of two of the
products were established by single crystal X-ray diffraction anal-
yses. We also report on the catalytic activities of the palladium(II)
complexes as pre-catalysts in the Heck and Suzuki coupling
reactions.
resonance at 62.2 and 68.5 ppm, respectively, in line with the val-
ues previously observed for similar compounds [50,51]. The 13C
NMR spectra of the compounds give four signals for the phenyl car-
bon atoms, two signals for the isopropyl groups, and six or four sig-
nals for the aniline ring in 1 or 2, respectively.
Oxidation of 1 and 2 with aqueous hydrogen peroxide or ele-
mental sulfur or selenium in thf gave the corresponding oxides
(1a, 2a), sulfides (1b, 2b), and selenides (1c, 2c), respectively
(Scheme 1).
2. Results and discussion
Oxidation of both 1 and 2 using aqueous H2O2 was very rapid
even at ambient temperature. However, the reaction with elemen-
tal sulfur or selenium had to be carried out at elevated tempera-
tures, as expected because elemental sulfur and selenium are
weaker oxidizing agents than hydrogen peroxide, especially to-
wards phosphorus atoms with bulky phenyl groups [52–55]. The
31P–{1H} NMR spectra display one singlet for each of 1a and 2a
(23.9 and 24.2 ppm) and 1b and 2b (68.5 and 68.9 ppm), suggest-
ing that the two phosphorus atoms are chemically equivalent in
these compounds. The 31P NMR signals of 1c and 2c are also sing-
lets, but they are accompanied by selenium satellites at 67.8 ppm
(1J(31P–77Se) = 787 Hz) and 67.3 ppm (1J(31P–77Se) = 792 Hz),
respectively.
In the reaction of [M(cod)Cl2] (M = Pd, Pt; cod = 1,5-cyclooctadi-
ene) with one equivalent of 1 or 2 in thf solution, cod is replaced by
N,N-bis(diphenylphosphino)isopropylaniline as a bidentate ligand,
yielding the respective [M{(Ph2P)2N-C6H4-CH(CH3)2}Cl2] com-
plexes 1d, 2d, 1e, 2e (M = Pd, Pt, respectively). The reaction of
[Cu(CH3CN)4]PF6 with two equivalents of 1 or 2 gives the expected
complexes [Cu{(Ph2P)2N-C6H4-CH(CH3)2}2]PF6 1f or 2f, respec-
tively. Both reactions are summarized in Scheme 2. The 31P–{1H}
NMR spectra of 1d and 2d exhibit a single resonance at 37.9 and
38.5 ppm, respectively, which are within the range expected for
structurally similar complexes [56–58]. The phosphorus reso-
2.1. Synthesis and characterization
N,N-bis(diphenylphosphino)isopropylanilines (PPh2)2N-C6H4-
CH(CH3)2, having the isopropyl substituent at the carbon 2 (1) or
4 (2) were easily prepared from the reaction of o-H2N-C6H4-
CH(CH3)2 or p-H2N-C6H4-CH(CH3)2, respectively, with two equiva-
lents of chlorodiphenylphosphine in the presence of triethylamine
in thf solution at 0 °C (Scheme 1). Although the existence of com-
pound 1 has been reported by Killian et al., neither the experimen-
tal procedure for the preparation nor characterization data is
available [49]. Hence, the synthesis and full characterization of
compound 1 will be reported herein for the first time. Compounds
1 and 2 were isolated as white solids in high yields (87% and 85%,
respectively) under anaerobic conditions. Attempts to prepare N,N-
bis(diphenylphosphino)-2,6-diisopropylaniline did not succeed,
may be due to the steric repulsion between the two isopropyl
groups and phenyl rings of the phosphine.
In the 1H NMR spectra, both 1 and 2 show multiplets for the
aromatic H-atoms in the regions 6.75–7.53 and 6.58–7.39 ppm,
respectively. The CH signal of the isopropyl group is at 2.99 ppm
for 1 and 2.76 ppm for 2. The methyl groups of the isopropyl sub-
stituent give doublets at 0.75 and 1.15 ppm for 1 and 2, respec-
tively. The 31P–{1H} NMR spectra of 1 and 2 show a single
Scheme 1. Syntheses of N,N-bis(diphenylphosphino)isopropylanilines by the aminolysis reaction of H2N-C6H4-CH(CH3)2 with Ph2PCl (1: 2-CH(CH3)2; 2: 4-CH(CH3)2) and
oxidation of 1 and 2 with aqueous H2O2 (1a, 2a), elemental sulfur (1b, 2b) and grey selenium (1c, 2c).
Scheme 2. Reactions of aminophosphines 1 and 2 with [M(cod)Cl2] (M = Pd, Pt) and [Cu(CH3CN)4]PF6 in thf.

M. Aydemir et al. / Polyhedron 28 (2009) 2313–2320
2315
Table 1
Crystal data and experimental details of the structural analysis of dichloro{N,N-bis(diphenylphosphino)-2-isopropyl aniline}palladium(II) (1d) and dichloro{N,N-bis(diphen-
ylphosphino)-2-isopropyl aniline}platinum(II) (1e).
1d
1e
Empirical formula
Formula weight
Crystal system
Space group
[(Ph2P)2N-(C6H4)-2-CH(CH3)2PdCl2]Á(C2H5)2O
[(Ph2P)2N-(C6H4)-2-CH(CH3)2PtCl2]Á(C2H5)2O
754.97
843.63
monoclinic
P21/c
monoclinic
P21/c
Unit cell dimensions
a (Å)
12.1266(10)
12.170(2)
b (Å)
14.028(2)
14.167(5)
c (Å)
21.617(2)
21.552(2)
b (°)
101.744(7)
3600.3(7)
101.610(11)
3639.7(15)
Volume (Å3)
Z
4
4
Dcalc (Mg/m3)
Absorption coefficient (mmÀ1
F(0 0 0)
1.393
0.782
1552
1.539
4.119
1680
)
h, k, l ranges
À14 ? 15, À17 ? 0, À26 ? 0
À14 ? 15, À17 ? 0, À26 ? 0
7580/7377 [Rint = 0.0432]
w = 1/[r2F20 + 20.0447P)2 + 2.3P = (F02 + 2F2c )/3
401/1
Reflections collected/unique
Refinement on F2
Parameters/restrains
Goodness of fit (GOF) on F2
7483–7284 [Rint = 0.0356]
w = 1/[r2F02 + 20.0701P)2 + 0.0000P], P = (F02 + 2F2c )/3
400/3
0.99
1.025
R indices [I > 2
R indices [all data]
r
(I)]
R1 = 0.0432, wR2 = 0.1046
R1 = 0.1023, wR2 = 0.1237
0.001
0.865 and À0.508
R1 = 0.0315, wR2 = 0.0764
R1 = 0.0572, wR2 = 0.0839
0.002
1.39 and À1.674
(D/r)
max
Largest difference in peak and hole (e/Å3)
nances of 1d and 2d are shifted to lower frequencies by ca. 24 and
30 ppm, respectively, compared to the free ligands. The 31P–{1H}
NMR spectra of complexes 1e and 2e show a singlet at d 23.6
and 20.5 ppm, respectively, accompanied by platinum satellites.
The large 1J(135Pt–31P) coupling constants of 3325 and 3310 Hz
for 1e and 2e, respectively, are indicative of a cis arrangement of
phosphines around a platinum(II) center [59]. The 31P–{1H} NMR
chemical shifts of 1f and 2f are also within the expected range,
89.4 and 87.6 ppm, respectively, for structurally similar complexes
[43,54,60,61]. The phosphorus resonances of complexes 1f and 2f
show a coordination shift to higher frequencies by ca. 27 and
19 ppm, respectively, compared to those of the free ligands.
Single crystals of [Pd{(Ph2P)2N-C6H4-2-CH(CH3)2}Cl2] (1d) and
[Pt{(Ph2P)2N-C6H4-2-CH(CH3)2}Cl2] (1e) suitable for X-ray diffrac-
tion studies were obtained by slow diffusion of diethylether into
a solution of the complexes in dichloromethane. Both complexes
were crystallized as 1:1 solvent adducts and the crystallographic
tion of the isopropyl groups. The coordination geometry around
the Pd and Pt atoms is distorted square–planar, involving two P
and two Cl atoms. In the coordination environment, the Pd–P
and Pt–P bond lengths are 2.2045(11)–2.2068(10) and
2.1925(12)–2.1936(12) Å, respectively. The Pd–Cl and Pt–Cl coor-
dination bond lengths are 2.3600(11)–2.3553(11) and
2.3462(13)–2.3510(13) Å, respectively. The coordination bond
lengths of the Pt atom are slightly smaller than the Pd atom. The
palladium(II) complex 1d and the platinum(II) complex 1e have
coordination angles around the Pd and Pt atoms in the range
71.93(4)–96.96(5)° and 72.52(4)–97.36(5)°, respectively. Despite
the difference of the two metal atoms, the P–Pd–P angle and P–
Pt–P angles are close to each other (71.93(4)° and 72.52(4)°,
respectively). The fact that these angles are much smaller than
the ideal value of 90° in a regular square planar geometry can be
attributed to the strain in the diphosphine ligands: the bite dis-
tance in these ligands is obviously small. Indeed, the P1ÁÁÁP2 dis-
tances are 2.5908(14) Å for Pd complex and 2.5942(16) Å for Pt
complex. The Pd and Pt atoms are at distance of 0.0538(3) and
data
of
[Pd{(Ph2P)2N-C6H4-2-CH(CH3)2}Cl2]Á(C2H5)2O
and
[Pt{(Ph2P)2N-C6H4-2-CH(CH3)2}Cl2]Á(C2H5)2O are listed in Tables 1
and 2 for 1d and 1e. A perspective view of the molecules is given
in Fig. 1.
These two crystal structures are isomorphous. The key bond
lengths and angles of complexes 1d and 1e in the solid state are
very similar, with minimal structural differences due to the reloca-
Table 2
Selected bond lengths (Å) and bond angles (°) for the solid state structure of 1d and
1e. M = Pd and Pt, respectively.
1d
1e
1d
1e
M–P1
M–P2
M–Cl1
M–Cl2
P1–N
2.2045(11)
2.2068(10)
2.3600(11)
2.3553(11)
1.722(3)
1.710(3)
1.797(4)
1.794(5)
1.795(4)
2.1925(12)
2.1936(12)
2.3462(13)
2.3510(13)
1.719(4)
1.724(4)
1.799(5)
1.808(5)
1.798(5)
P1–M–P2
Cl1–M–Cl2
P1–M–Cl1
P1–M–Cl2
P2–M–Cl1
P2–M–Cl2
P1–N–P2
M–P1–N
71.93(4)
96.96(5)
167.26(4)
95.37(4)
95.62(4)
167.14(4)
98.02(16)
94.68(11)
94.96(11)
126.2(3)
127.6(3)
72.52(4)
92.92(5)
97.15(5)
169.76(5)
169.55(5)
97.36(5)
97.82(17)
94.71(12)
94.53(12)
126.6(3)
127.5(3)
P2–N
P1–C1
P1–C7
P2–C13
P2–C19
P1ÁÁÁP2
N–C25
M–P2–N
C25–N–P1
C25–N–P2
1.799(4)
2.5908(14)
1.459(5)
1.809(4)
2.5942(16)
1.454(5)
Fig. 1. ORTEP drawing of the compounds 1d and 1e with the atomic numbering
scheme. H atoms have been omitted for clarity, where M = Pd and Pt, respectively.

2316
M. Aydemir et al. / Polyhedron 28 (2009) 2313–2320
Table 3
0.0341(3) Å, respectively from the basal plane defined by the
atoms Cl1, Cl2, P1, P2.
Dihedral angles between defined planes of the compounds 1d and 1e.
The P–N bond distances of palladium complex 1d [1.722(3) and
1.710(3) Å] are very similar to those of platinum complex 1e
[1.724(4) and 1.719(4) Å]. They are within the expected ranges in
comparison to similar structures [52–54,58]. The aromatic rings
in the molecules, as expected, have the usual bond lengths and
angles.
Plane 1
Plane 2
Dihedral angle (°) 1d
Dihedral angle (°) 1e
P1/M/P2
P1/M/P2
A
C
E
Cl1/M/Cl2
P1/N/P2
B
D
F
3.69(5)
6.6(2)
61.3(2)
64.2(2)
77.1(1)
2.31(4)
6.7(2)
59.9(2)
64.9(2)
77.1(1)
Notes: Planes A–F are involving the atoms as given (Fig. 2): A: C1/C2/C3/C4/C5/C6,
B: C7/C8/C9/C10/C11/C12, C: C13/C14/C15/C16/C17/C18, D: C19/C20/C21/C22/C23/
C24, E: C25/C26/C27/C28/C29/C30, F: Pt/P1/N/P2. M = Pd, Pt.
It is interesting to note that compounds 1d and 1e crystallized
under similar conditions, both forming 1:1 adduct with solvent
molecules. To get information about the conformation of the com-
plexes 1d and 1e, dihedral angles between the neighboring square
planes in the molecule were calculated with PARST [62]. Some dihe-
dral angles between the planes around the coordination sphere
and phenyl rings (Fig. 2) are given in Table 3. The title molecule
is not planar but the phenyl rings are essentially planar.
cleanly with phenylboronic acid giving high yields of the products
(Table 5).
3. Experimental
2.2. The Heck coupling reactions
All reactions and manipulations were performed under argon
atmosphere using standard Schlenk techniques unless otherwise
stated. Ph2PCl, 2-isopropylaniline and 4-isopropylaniline were
purchased from Fluka and were used as received. Solvents were
dried using the appropriate reagents and distilled prior to use.
The starting materials [MCl2(cod)] (M = Pd, Pt, cod = 1,5-cyclo-
octadiene) [66,67] and [Cu(CH3CN)4]PF6 [68] were prepared
according to the literature procedures. Infrared spectra were
recorded from KBr pellets in the range 4000–400 cmÀ1 on a
Mattson 1000 ATI UNICAM FT-IR spectrometer. NMR spectra were
recorded on a Bruker AC 400 spectrometer (400.1 MHz for 1H,
100.6 MHz for 13C, and 162.0 MHz 31P). Microanalysis was
carried out on a Fisons EA 1108 CHNS-O instrument. GC analyses
were performed on a HP 6890 N Gas Chromatograph equipped
with a capillary column (5% biphenyl, 95% dimethylsiloxane)
The palladium complexes 1d and 2d were tested as catalysts in
one of the most important C–C bond forming processes in syn-
thetic organic chemistry, known as the Heck reaction, the palla-
dium-catalyzed coupling of aryl/vinyl halides with olefins
[63,64]. After optimizing the reaction conditions, we carried out
the coupling reactions of several substrates with styrene. We found
that the use of 0.01 mmol of palladium complexes (1d and 2d)
with two equivalents of K2CO3 in dioxane at 85 °C led to the best
conversion. A control experiment indicated that the coupling
reaction does not occur in the absence of 1d or 2d. Under these
optimum conditions,
a wide range of arylbromides bearing
electron-donating or electron-withdrawing groups (p-bromoaceto-
phenone, p-bromobenzaldehyde, p-bromobenzene, p-bromoani-
sole and p-bromotoluene) react with styrene giving the coupled
products in high yields (Table 4).
(30 m  0.32 mm  0.25
lm).
2.3. The Suzuki coupling reactions
3.1. General procedure for the synthesis of N,N-bis(diphenylphosphino)
isopropylanilines [(Ph2P)2N-(C6H4)-CH(CH3)2] (1, 2)
The palladium complexes 1d and 2d were tested as catalysts in
the Suzuki reaction of aryl/vinyl halides with boronic acid, which is
one of the most efficient methods for C–C bond formation [65]. Fol-
lowing optimization experiments, we found that the use of
0.01 mmol of the palladium complexes (1d and 2d) with Cs2CO3
as the base at 75 °C in dioxane appeared to provide the highest
yield. We initially tested the catalytic activity of the complexes
(1d and 2d) for the coupling of p-bromoacetophenone with phen-
ylboronic acid and the control experiments showed that the cou-
pling reaction does not occur in the absence of the catalyst.
Under these conditions, p-bromoacetophenone, p-bromobenzalde-
hyde, p-bromobenzene, p-bromoanisole and p-bromotoluene react
Ph2PCl (1.63 g, 7.40 mmol) was added slowly to a solution of 2-
or 4-isopropylaniline (0.50 g, 3.70 mmol) and Et3N (0.75 g,
7.40 mmol) in thf (20 mL) at 0 °C. The resulting white suspension
was stirred for 1 h and precipitated triethylamine hydrochloride
was removed by filtration through a sintered Schlenk tube. The
solution was evaporated to dryness under reduced pressure and
white solids of 1 or 2 were obtained.
3.1.1. N, N-bis(diphenylphosphino)-2-isopropylaniline [(Ph2P)2N-
(C6H4)-2-CH(CH3)2] (1)
Yield: 1.62 g, 87%; M.p. 129–131 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.75–7.53(m, 24H, Ar–H), 2.99(m, 1H,
CH(CH3)2, 0.75(d, 3J(H–H) = 6.4 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 146.3, 139.7, 134.9, 132.5,
131.4, 130.5, 128.5, 127.8, 126.6, 125.8 (Carm); 27.5 (–CH(CH3)2);
23.6 (–CH(CH3)2); 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
H3PO4): 62.2 (s); IR (KBr pellet,
m
cmÀ1): 901 (PNP), 1432 (PPh);
Elemental Anal. Calc. for C33H31NP2: C, 78.71; H, 6.21; N, 2.78.
Found: C, 78.46; H, 5.97; N, 2.59%.
3.1.2. N, N-bis(diphenylphosphino)-4-isopropylaniline [(Ph2P)2N-
(C6H4)-4-CH(CH3)2] (2)
Yield: 1.58 g, 85%; M.p. 103–105 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.58–7.39(m, 24H, Ar–H), 2.76(m, 1H,
CH(CH3)2, 1.15(d, 3J(H–H) = 7.2 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 145.8, 139.6, 133.3, 131.3,
128.9, 128.5, 127.9, 126.2 (Carm); 33.5 (–CH(CH3)2); 24.0
(–CH(CH3)2); 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
Fig. 2. Conformation of the compounds 1d and 1e.

M. Aydemir et al. / Polyhedron 28 (2009) 2313–2320
2317
Table 4
The Heck coupling reactions of aryl bromides with styrenea.
1d or 2d (0.01 mmol)
+
Br
R
R
K2CO3, Dioxane, 85 o
C
Entry
R
Catalyst
Yield (%)b
TOF (hÀ1
)
1
2
3
4
5
6
7
8
9
10
COCH3
COCH3
CHO
CHO
H
1d
2d
1d
2d
1d
2d
1d
2d
1d
2d
95.42
93.25
97.12
94.08
88.77
74.93
69.28
57.95
76.53
69.26
63.6
62.2
64.8
62.7
59.2
49.9
46.2
38.6
51.0
46.2
H
OCH3
OCH3
CH3
CH3
a
Reaction conditions: 1.0 mmol of R-C6H4Br-p, 1.5 mmol of styrene, 2.0 mmol K2CO3, 0.01 mmol Pd complex, dioxane (3 mL).
Purity of compounds was checked by NMR and yields are based on aryl bromide, all reactions were monitored by GC, temperature 85 °C, 1.5 h. TOF = (mol product/mol
b
Cat) x hÀ1.
Table 5
The Suzuki coupling reactions of aryl bromides with phenylboronic acida.
1d or 2d (0.01 mmol)
B(OH)2 + Br
R
R
Cs2CO3, Dioxane, 75 o
C
c
Entry
R
Catalyst
Yield (%)b
TOF (hÀ1
)
1
2
3
4
5
6
7
8
9
10
COCH3
COCH3
CHO
CHO
H
1d
2d
1d
2d
1d
2d
1d
2d
1d
2d
94.06
91.72
98.46
95.12
85.80
88.35
70.45
67.08
73.57
61.79
94.1
91.7
98.5
95.1
85.8
88.4
70.5
67.1
73.6
61.8
H
OCH3
OCH3
CH3
CH3
a
Reaction conditions: 1.0 mmol of R-C6H4Br-p, 1.5 mmol of phenylboronic acid, 2.0 mmol Cs2CO3, 0.01 mmol Pd complex, dioxane (3 mL).
b
c
Purity of compounds was checked by NMR and yields are based on aryl bromide, all reactions were monitored by GC, temperature 75 °C, 1 h.
TOF = (mol product/mol Cat) x hÀ1
.
H3PO4): 68.5 (s); IR (KBr pellet,
Elemental Anal. Calc. for C33H31NP2: C, 78.71; H, 6.21; N, 2.78.
Found: C, 78.62; H, 6.02; N, 2.64%.
m
cmÀ1): 906 (PNP), 1438 (PPh);
132.6, 132.2, 131.9, 128.3, 127.7, 125.9 (Carm); 27.8 (–CH(CH3)2);
23.9 (–CH(CH3)2). 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
H3PO4): 23.9 (s); IR (KBr pellet, m
cmÀ1): 908 (PNP), 1448 (PPh),
1216 (PO); Elemental Anal. Calc. for C33H31NO2P2: C, 74.01; H,
3.2. General procedure for the synthesis of the chalcogenides
5.83; N, 2.62. Found: C, 73.81; H, 5.72; N, 2.46%.
3.2.1. N,N-bis(diphenyloxophosphino)isopropylanilines [(Ph2P(O))2N-
(C6H4)-CH(CH3)2] (1a, 2a)
3.2.3. N,N-bis(diphenyloxophosphino)-4-isopropylaniline
[(Ph2P(O))2N-(C6H4)-4-CH(CH3)2] (2a)
A thf solution (10 mL) of N,N-bis(diphenylphosphino)isopropyl
aniline (0.20 g, 0.40 mmol) and aqueous H2O2 (30% w/w, 0.08 mL)
was stirred for 2 h at room temperature. The solution was filtered
through Celite to remove a small amount of insoluble material. The
filtrate was concentrated in vacuo to ca. 1–2 mL and addition of n-
hexane (10 mL) gave 1a and 2a as white solids which were col-
lected by suction filtration.
Yield: 0.18 g, 85%; M.p. 124–126 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.97–7.81(m, 24H, Ar–H), 3.56(m, 1H,
CH(CH3)2), 0.75(s, 6H, –CH(CH3)2); 13C NMR (100 MHz, [D]CHCl3,
25 °C, TMS): 149.3, 134.1, 133.2, 132.6, 131.6, 128.5, 127.8, 125.6
(Carm); 27.8 (–CH(CH3)2); 24.1 (–CH(CH3)2); 31P–{1H} NMR
(162 MHz, [D]CHCl3, 25 °C, 85% H3PO4): 24.2 (s); IR (KBr pellet,
m
cmÀ1): 910 (PNP), 1446 (PPh), 1199 (PO); Elemental Anal. Calc.
for C33H31NO2P2: C, 74.01; H, 5.83; N, 2.62. Found: C, 73.67; H,
5.48; N, 2.43%.
3.2.2. N,N-bis(diphenyloxophosphino)-2-isopropylaniline
[(Ph2P(O))2N-(C6H4)-2-CH(CH3)2] (1a)
Yield: 0.16 g, 75%; M.p. 202–204 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.98–7.71(m, 24H, Ar–H), 3.59(m, 1H,
CH(CH3)2), 0.65(d, 3J(H–H) = 6.4 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 149.2, 134.6, 134.2, 133.1,
3.2.4. N,N-bis(diphenylthiophosphino)isopropylanilines [(Ph2P(S))2N-
(C6H4)-CH(CH3)2] (1b, 2b)
To a solution of 1 or 2 (0.20 g, 0.40 mmol) in thf (10 mL), S8
(0.025 g, 0.80 mmol) was added and this mixture was refluxed

2318
M. Aydemir et al. / Polyhedron 28 (2009) 2313–2320
for 4 h. The solution was filtered through Celite while hot to re-
move a small amount of insoluble material. The filtrate was con-
centrated in vacuo to ca. 1–2 mL and addition of n-hexane
(15 mL) gave 1b and 2b as light yellow solids which were collected
by suction filtration.
3.3. General procedure for the synthesis of the complexes
3.3.1. Dichloro{N,N-bis(diphenylphosphino)isopropylaniline}palla-
dium(II) (1d, 2d)
A solution of [PdCl2(cod)] (0.227 g, 0.795 mmol) and 1 or 2
(0.40 g, 0.795 mmol) in thf (20 mL) was stirred for 2 h. The
volume was concentrated in vacuum to ca. 1–2 mL and addi-
tion of diethyl ether (15 mL) gave 1d and 2d as yellow solids
which were collected by suction filtration and dried in
vacuum.
3.2.5. N,N-bis(diphenylthiophosphino)-2-isopropylaniline
[(Ph2P(S))2N-(C6H4)-2-CH(CH3)2] (1b)
Yield: 0.17 g, 75%; M.p. 149–151 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.90–8.05(m, 24H, Ar–H), 3.54(m, 1H,
CH(CH3)2), 0.69(d, 3J(H–H) = 6.8 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 151.0, 136.5, 134.7, 134.0,
133.7, 132.2, 131.3, 128.4, 127.4, 125.0 (Carm); 28.3 (–CH(CH3)2);
24.6 (–CH(CH3)2); 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
3.3.2. Dichloro{N,N-bis(diphenylphosphino)-2-isopropylaniline}
palladium(II) (1d)
Yield: 0.44 g, 81%; M.p. 249–251 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.78–7.85(m, 24H, Ar–H), 2.57(m, 1H,
CH(CH3)2), 0.31(d, 3J(H–H) = 6.4 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 147.4, 136.4, 134.8, 134.4,
132.4, 130.6, 130.4, 129.9, 128.6, 126.6 (Carm); 28.7 (–CH(CH3)2);
23.8 (–CH(CH3)2); 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
H3PO4): 68.5 (s); IR (KBr pellet,
m
cmÀ1): 905 (PNP), 1440 (PPh),
650 (PS); Elemental Anal. Calc. for C33H31NS2P2: C, 69.82; H, 5.50;
N, 2.47. Found: C, 69.61; H, 5.31; N, 2.38%.
3.2.6. N,N-bis(diphenylthiophosphino)-4-isopropylaniline
[(Ph2P(S))2N-(C6H4)-4-CH(CH3)2] (2b)
H3PO4): 37.9 (s); IR (KBr pellet,
m
cmÀ1): 890 (PNP), 1438 (PPh);
Yield: 0.19 g, 84%: M.p. 189–191 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.72–8.10(m, 24H, Ar–H), 2.59(m, 1H,
CH(CH3)2), 0.99(s, 6H, –CH(CH3)2); 13C NMR (100 MHz, [D]CHCl3,
25 °C, TMS): 147.8, 136.1, 133.6, 132.9, 132.4, 131.3, 127.5, 125.9
(Carm); 33.4 (–CH(CH3)2); 23.7 (–CH(CH3)2); 31P–{1H} NMR
Elemental Anal. Calc. for C33H31NP2PdCl2: C, 58.21; H, 4.59; N,
2.06. Found: C, 57.94; H, 4.43; N, 1.83%.
3.3.3. Dichloro{N,N-bis(diphenylphosphino)-4-isopropylaniline}
palladium(II) (2d)
(162 MHz, [D]CHCl3, 25 °C, 85% H3PO4): 68.9 (s); IR (KBr pellet,
m
Yield: 0.48 g, 89%; M.p. 250–252 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.79–7.85(m, 24H, Ar–H), 2.58(m, 1H,
CH(CH3)2), 0.3(d, 3J(H–H) = 6.0 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 147.3, 138.1, 134.8, 134.4,
132.1, 130.0, 128.7, 126.6 (Carm); 28.9 (–CH(CH3)2); 23.8
(–CH(CH3)2); 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
cmÀ1): 906 (PNP), 1446 (PPh), 694 (PS); Elemental Anal. Calc. for
C33H31NS2P2: C, 69.82; H, 5.50; N, 2.47. Found: C, 69.68; H, 5.36;
N, 2.36%.
3.2.7. N,N-bis(diphenylselenophosphino)isopropylanilines
[(Ph2P(Se))2N-(C6H4)-CH(CH3)2] (1c, 2c)
H3PO4): 38.5 (s); IR (KBr pellet,
m
cmÀ1): 892 (PNP), 1447 (PPh);
Grey Se (0.063 g, 0.8 mmol) was added to a solution of 1 or 2
(0.20 g, 0.40 mmol) in thf (10 mL) and this mixture was refluxed
for 1 h. The solution was filtered through Celite while hot to re-
move a small amount of insoluble material. The filtrate was con-
centrated in vacuo to ca. 1–2 mL and addition of n-hexane
(15 mL) gave 1c and 2c as light yellow solids which were collected
by suction filtration.
Elemental Anal. Calc. for C33H31NP2PdCl2: C, 58.21; H, 4.59; N,
2.06. Found: C, 57.84; H, 4.37; N, 1.93%.
3.3.4. Dichloro{N,N-bis(diphenylphosphino)isopropylaniline}
platinum(II) (1e, 2e)
A solution of [PtCl2(cod)] (0.298 g, 0.795 mmol) and 1 or 2
(0.40 g, 0.795 mmol) in thf (20 mL) was stirred for 2 h. The volume
was concentrated in vacuum to ca. 1–2 mL and addition of diethyl
ether (15 mL) gave 1e and 2e as white solids which were collected
by suction filtration and dried in vacuum.
3.2.8. N,N-bis(diphenylselenophosphino)-2-isopropylaniline
[(Ph2P(Se))2N-(C6H4)-2-CH(CH3)2 ] (1c)
Yield: 0.21 g, 80%; M.p. 240–242 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.88–8.04(m, 24H, Ar–H), 3.53(m, 1H,
CH(CH3)2), 0.70(d, 3J(H–H) = 6.8 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 151.2, 136.8, 134.6, 134.4,
132.8, 131.6, 130.5, 127.8, 127.5, 125.0 (Carm); 28.4 (–CH(CH3)2);
24.9 (–CH(CH3)2); 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
3.3.5. Dichloro{N,N-bis(diphenylphosphino)-2-isopropylaniline}
platinum(II) (1e)
Yield: 0.52 g, 85%; M.p. 294–296 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.75–7.81(m, 24H, Ar–H), 2.63(m, 1H,
CH(CH3)2), 0.30(d, 3J(H–H) = 6.8 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 147.7, 139.3, 134.6, 134.2,
132.2, 130.6, 130.2, 129.8, 127.4, 126.4 (Carm); 28.9
(–CH(CH3)2); 23.8 (–CH(CH3)2); 31P–{1H} NMR (162 MHz,
[D]CHCl3, 25 °C, 85% H3PO4): 23.6, J(PtP) = 3325 Hz; IR (KBr pel-
H3PO4): 67.8, J(PSe) = 786.6 Hz; IR (KBr pellet,
m
cmÀ1): 891
(PNP), 1438 (PPh), 563 (PSe); Elemental Anal. Calc. for
C33H31NSe2P2: C, 59.92; H, 4.72; N, 2.12. Found: C, 59.62; H,
4.43; N, 2.01%.
let,
m
cmÀ1): 893 (PNP), 1440 (PPh); Elemental Anal. Calc. for
C33H31NP2PtCl2: C, 51.51; H, 4.06; N, 1.82. Found: C, 51.24;
H, 3.82; N, 1.69%.
3.2.9. N,N-bis(diphenylselenophosphino)-4-isopropylaniline
[(Ph2P(Se))2N-(C6H4)-4-CH(CH3)2] (2c)
Yield: 0.22 g, 84%: M.p. >300 °C (dec.); 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.71–8.15(m, 24H, Ar–H), 2.60(m, 1H,
CH(CH3)2), 1.00(d, 3J(H–H) = 6.8 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 147.6, 136.0, 134.3, 133.4,
132.8, 131.4, 127.5, 125.9 (Carm); 33.4 (–CH(CH3)2); 23.6
(–CH(CH3)2); 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
3.3.6. Dichloro{N,N-bis(diphenylphosphino)-4-isopropylaniline}
platinum(II) (2e)
Yield: 0.55 g, 90%; M.p. >250 °C (dec.); 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.40–7.81(m, 24H, Ar–H), 2.66(m, 1H,
CH(CH3)2), 0.31(d, 3J(H–H) = 6.8 Hz, 6H, –CH(CH3)2); 13C NMR
(100 MHz, [D]CHCl3, 25 °C, TMS): 147.0, 137.6, 134.3, 133.1,
132.2, 130.1, 128.0, 126.6 (Carm); 30.8 (–CH (CH3)2); 25.6
(–CH(CH3)2); 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
H3PO4): 67.3, J(PSe) = 792 Hz; IR (KBr pellet,
m
cmÀ1): 917
(PNP), 1446 (PPh), 542 (PSe); Elemental Anal. Cal. for
C33H31NSe2P2: C, 59.92; H, 4.72; N, 2.12. Found: C, 59.72; H,
4.57; N, 1.98%.
H3PO4): 20.5, J(PtP): 3310 Hz; IR (KBr pellet,
m
cmÀ1): 892 (PNP),

M. Aydemir et al. / Polyhedron 28 (2009) 2313–2320
2319
1438 (PPh); Elemental Anal. Calc. for C33H31NP2PtCl2: C, 51.51; H,
3.6. X-ray diffraction structure analyses
4.06; N, 1.82. Found: C, 51.29; H, 3.94; N, 1.73%.
To determine the crystal structures of 1d and 1e, X-ray dif-
fraction data were collected at room temperature using an En-
raf-nonius CAD4 diffractometer with graphite monochromated
3.3.7. Bis[N,N-bis(diphenylphosphino)isopropylaniline]copper(I)
hexafluorophosphates (1f, 2f)
Mo
parameters and their estimated standard deviations were
determined from least-squares analysis using 25 centered
Ka radiation using the w/2h scan mode. The lattice
To a solution of [Cu(CH3CN)4]PF6 (0.148 g, 0.398 mmol) in thf
(15 mL) was added compound 1 or 2 (0.40 g, 0.795 mmol), and
the resulting solution was stirred for 1 h. The volume was concen-
trated in vacuum to ca. 1–2 mL and addition of diethyl ether
(15 mL) gave 1f and 2f as white solids which were collected by suc-
tion filtration and dried in vacuum.
a
reflections in the range 9.86–17.99° for the Pd complex and
10.15-17.98° for the Pt complex by using CAD4 Express [69].
Data reduction was carried out using XCAD 4 [70]. The struc-
tures were solved by the direct method using the solution
program SHELXS97 and refined on F20 using SHELXS97 [71]. In both
complexes, all non-hydrogen atoms were refined, first with
isotropic and then with anisotropic thermal parameters by full
matrix least squares. The hydrogen atom of the CH group in
3.3.8. Bis[N,N-bis(diphenylphosphino)-2-isopropylaniline]copper(I)
hexafluorophosphate (1f)
Yield: 0.41 g, 85%; M.p. 179–181 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 7.11–7.57(m, 24H, ArH), 2.60(m, 1H,
CH(CH3)2), 0.10(d, 3J(H–H):6.4 Hz, 6H, –CH(CH3)2); No 13C NMR
spectrum was obtained due to the low solubility of the complex
in all common solvents; 31P–{1H} NMR (162 MHz, [D]CHCl3,
25 °C, 85% H3PO4): 89.4, PF6: À144.3, J(PF6) = 712 Hz; IR (KBr pellet,
the 2-isopropyl aniline ligand was taken from
a difference
Fourier map. All other hydrogen atoms were positioned geo-
metrically with C–H = 0.93, 0.97 and 0.96 Å for aromatic,
methylene and methyl H, and constrained to ride on their
parent atoms, with Uiso(H) = xUeq(C), where x = 1.5 for methyl
H, and x = 1.2 for others H atoms. Results of the X-ray struc-
ture determination are given in Tables 1–3 for 1d and 1e, and
the ORTEP [72] drawings of the molecules are shown in
Fig. 1.
m
cmÀ1): 898 (PNP), 1446 (PPh); Elemental Anal. Calc. for
C66H62N2P5F6Cu: C, 65.21; H, 5.14; N, 2.30. Found: C, 64.96; H,
4.95; N, 2.18%.
3.3.9. Bis[N,N-bis(diphenylphosphino)-4-isopropylaniline]copper(I)
hexafluorophosphate (2f)
4. Conclusion
Yield: 0.38 g, 79%; M.p. 181–183 °C; 1H NMR (400 MHz,
[D]CHCl3, 25 °C, TMS): 6.77–7.52(m, 24H, ArH), 2.72(br, 1H,
CH(CH3)2), 1.10(s, 6H, –CH(CH3)2); No 13C NMR spectrum was
obtained due to the low solubility of the complex in all com-
mon solvents; 31P–{1H} NMR (162 MHz, [D]CHCl3, 25 °C, 85%
In conclusion, two new bis(diphenylphosphino)amines and
their oxides, sulfides and selenides have been prepared. In addi-
tion, both compounds show similar coordination properties to-
wards Cu, Pd and Pt. The Pd complexes exhibit high catalytic
activity in the Heck and Suzuki cross-coupling reactions. The pro-
cedure for carrying out the catalytic reactions is quite simple and
efficient towards various aryl bromides and does not require an
induction period. Based on these findings, it can be postulated that
1d and 2d offer some distinctive advantages in the C–C coupling
reactions compared to other palladium/aminophosphine systems
[20,50,55,64].
H3PO4): 87.6, PF6: À144.3, J(PF6) = 712 Hz; IR (KBr pellet,
m
cmÀ1): 908 (PNP), 1439 (PPh); Elemental Anal. Calc. for
C66H62N2P5F6Cu: C, 65.21; H, 5.14; N, 2.30. Found: C, 65.02; H,
4.97; N, 2.19%.
3.4. General procedure for the Heck coupling reaction
Heck coupling reactions were conducted as follows: the bis-
phosphinoamine–palladium complexes (1d or 2d) (0.01 mmol),
arylbromide (1.0 mmol), styrene (1.5 mmol), K2CO3 (2.0 mmol)
and 1,4-dioxane (3 mL) were placed in a Schlenk tube and the mix-
ture was heated to 85 °C for 1.5 h. The progress of the reaction was
monitored by GC. Upon completion, the mixture was cooled, and
the product extracted with ethyl acetate/hexane (1:5), filtered
through a pad of silica gel with copious washing, concentrated
and purified by flash chromatography on silica gel. The purity of
the compounds was checked by NMR and GC, and yields are based
on arylbromide.
5. Supplementary data
CCDC 694356 and 69455 contain the supplementary crystallo-
graphic data for 1d and 1e. These data can be obtained free of
charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
Acknowledgements
3.5. General procedure for the Suzuki coupling reaction
Partial support from Turkish Academy of Sciences, Dicle Univer-
sity (Project number: DÜAPK 05-FF-27) and Hacettepe University
(Scientific Research Department, Project number: 04A602004)
are gratefully acknowledged.
Suzuki coupling reactions were conducted as follows: the bis-
phosphinoamine–palladium complexes (1d or 2d) (0.01 mmol),
arylbromide (1.0 mmol), phenylboronic acid (1.5 mmol), Cs2CO3
(2.0 mmol) and 1,4-dioxane (3 mL) were placed in
a small
References
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progress of the reaction was monitored by GC. Upon completion,
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acetate/hexane (1:5), filtered through a pad of silica gel with
copious washing, concentrated and purified by flash
chromatography on silica gel. The purity of the compounds
was checked by NMR and GC, and yields are based on
arylbromide.
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