Synthesis, characterization, and structures of palladium(II) and platinum(II) complexes containing N,N-bis(diphenylphosphanyl)naphthylamine

Article abstract of DOI:10.1002/zaac.201200069

The reaction of 1-naphthylamine with two equivalents of chlorodiphenylphosphine in the presence of triethylamine gave the ligand C ₁₀H₇-1-N(PPh₂)₂ (1). Reaction of 1 with PdCl₂(CH₃CN)₂

Full text of DOI:10.1002/zaac.201200069

ARTICLE
DOI: 10.1002/zaac.201200069
Synthesis, Characterization, and Structures of Palladium(II) and
Platinum(II) Complexes Containing N,N-Bis(diphenylphosphanyl)
Naphthylamine
Harbi Tomah Al-Masri*[a]
Keywords: Aminophosphine; Molecular structure; Chlorodiphenylphosphine; Platinum; Palladium; Amines
Abstract. The reaction of 1-naphthylamine with two equivalents of
chlorodiphenylphosphine in the presence of triethylamine gave the li- Compounds 1–3 were identified and characterized by multinuclear
gand C10H7-1-N(PPh2)2 (1). Reaction of 1 with PdCl2(CH3CN)2 or
NMR (1H, 13C, 31P NMR) and IR spectroscopy. Crystal structure deter-
PtCl2(cod) (1:1 molar ratio) afforded the complexes cis-[PdCl2{C10H7- minations of complexes 2 and 3 were carried out.
1-N(PPh2)2}] (2) and cis-[PtCl2{C10H7-1-N(PPh2)2}] (3), respectively.
N,N-bis(diphenylphosphanyl)-1-naphthylamine (1): Chlorodiphen-
Introduction
ylphosphine (4.89 g, 22.20 mmol) was added dropwise to a solution
of 1-naphthylamine (1.95 g, 11.10 mmol) and triethylamine (2.25 g,
22.20 mmol) in THF (100 mL) at room temperature with vigorous stir-
ring. After completion of the addition, the reaction mixture was stirred
at room temperature for 12 h. Afterwards, the white precipitate (trieth-
ylamine hydrogen chloride) was filtered off through a sintered Schlenk
tube. The volume was reduced to 50 mL, the reaction mixture was
cooled to 0 °C, and a white solid was obtained that was recrystallized
from a 1:4 dichloromethane/n-hexane solution (v/v) at 0 °C to give the
product as colorless crystals in 85% yield. M.p. 121–122 °C. 1H NMR
(400.13 MHz, CDCl3): δ = 6.60–8.10 (m, 27, C10H7 and 4C6H5) ppm.
13C NMR (100.63 MHz, CDCl3): δ = 110.60, 120.08, 124.27, 125.45,
126.43, 127.84, 128.33, 129.14, 130.52, 131.16, 132.22, 133.03,
134.50, 135.36 (C10H7 and 4C6H5) ppm. 31P NMR (161.98 MHz,
CDCl3): δ = 63.46 (s, 2P) ppm. IR (selected bands, KBr): ν˜ = 1439
(P–Ph), 910 (P–N) cm–1.
The importance of aminophosphines with direct P–N bonds
and their derivatives in the fight against cancer[1–4] and also on
the subject of catalysis for industrially important reactions,[5–7]
as well as herbicidal, neuroactive and antimicrobial agents[8–10]
has prompted us to extend our studies on the synthesis and
solid-state structures of chelated N,O and N,N complexes[11] to
synthesize new chelating phosphorus(III) ligands containing
P–N linkages for transition metal chemistry and catalytic appli-
cations.[12]
As a part of our research program on this subject, we herein
report the synthesis and spectroscopic properties of C10H7-1-
N(PPh2)2 (1) ligand, the corresponding square planar complexes
cis-[PdCl2{C10H7-1-N(PPh2)2}] (2) and cis-[PtCl2{C10H7-1-
N(PPh2)2}] (3) and the crystal structures of 2 and 3.
Dichloro{N,N-bis(diphenylphosphanyl)-1-
naphthylamine}palladium(II) (2): To a solution of PdCl2(CH3CN)2
(0.24 g, 0.93 mmol) (generated in situ by heating PdCl2 in CH3CN to
Experimental Section
General Remarks: All experiments were carried out in purified dry reflux for 4 h) in CH3CN (80 mL) was added dropwise to a solution
nitrogen using standard Schlenk and vacuum line techniques. Solvents of 1 (0.47 g, 0.93 mmol) in CH3CN (50 mL) and the reaction mixture
were dried and freshly distilled under nitrogen.[13] PdCl2(CH3CN)2 was stirred at room temperature for 4 h. The solution was concentrated
was prepared according to the literature.[14,15] The chemicals chlorodi-
phenylphosphine, 1-naphthylamine and [PtCl2(cod)] (cod = /cycloocta-
to 10 mL, and THF (10 mL) was added. Cooling this solution to 0 °C
gave 2 as yellow crystals in 80% yield. M.p. 194–196 °C. H NMR
1
1,5-diene) were used as purchased. Infrared spectra were recorded with (400.13 MHz, CDCl3): δ = 6.58–7.89 (m, 27 H, C10H7 and 4C6H5)
a Perkin–Elmer System 2000 FT-IR spectrometer between 4000 and
400 cm–1 using KBr disks. The NMR spectra were recorded at 25 °C
with a Bruker AVANAC II 400 MHz NMR spectrometer operating at
the appropriate frequencies using tetramethylsilane for 1H and 85%
H3PO4 for 31P as external standards. Melting points were carried out
with a Gallenkamp Model apparatus with open capillaries.
ppm. 13C NMR (100.63 MHz, CDCl3): δ = 123.49, 124.80, 125.63,
126.41, 127.34, 127.61, 128.07, 129.06, 129.96, 130.25, 133.23,
134.35, 134.56, 136.06 (C10H6 and 4C6H5) ppm. 31P NMR
(161.98 MHz, CDCl3): δ = 37.78 (s, 2P) ppm. IR (selected bands,
KBr): ν˜ = 288 and 310 (Pd–Cl), 1441 (P–Ph), 840 (P–N) cm–1.
Dichloro{N,N-bis(diphenylphosphanyl)-1-
naphthylamine}platinum(II) (3): To a solution of [Pt(cod)Cl2]
(0.29 g, 0.76 mmol) in 50 mL of CH2Cl2, a solution of 1 (0.40 g,
0.76 mmol) in CH2Cl2 (50 mL) was added dropwise and the reaction
mixture was stirred at room temperature for 4 h. The solution was
concentrated to 5 mL, and acetone (5 mL) was added. Cooling this
solution to 0 °C gave 3 as white crystals in 80% yield. M.p. 290–
* Dr. H. T. Al-Masri
Fax: +966-4-9739319
E-Mail: hmasri@taibahu.edu.sa
[a] Faculty of Applied Sciences
Department of Applied Chemistry
Taibah University
Madinah 1343, KSA
Z. Anorg. Allg. Chem. 2012, 638, (᭿), 1–7
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
1

H. T. Al-Masri
ARTICLE
292 °C. 1H NMR (400.13 MHz, DMSO): δ = 6.55–7.95 (m, 27 H,
C10H7 and 2C6H5) ppm. 13C NMR (100.63 MHz, DMSO): δ = 121.42,
122.89, 124.85, 125.29, 126.16, 127.13, 127.90, 128.78, 128.94,
129.67, 129.91, 132.33, 133.30, 133.77 (C10H6 and 2C6H5) ppm. 31P
with selected transition metals (Pd and Pt) was explored. The
palladium(II) dichloride complex 2 was formed by direct reac-
tion of ligand 1 in THF with PdCl2(CH3CN)2 (1:1 molar ratio).
Moreover, the reaction of ligand 1 with one equivalent of
PtCl2(cod) (cod = 1,5-cyclooctadiene) in dichloromethane
gave the corresponding platinum(II) complex 3. It has been
found that the solvent (THF) for the synthesis of ligand 1 has
a significant influence on the reaction rate and on the reaction
product.
Compounds 1–3 were isolated from the reaction solution
and fully characterized by IR and multinuclear NMR spec-
troscopy. Furthermore, the molecular structures of 2 and 3
were elucidated by single-crystal X-ray diffraction.
1
NMR (161.97 MHz, DMSO): δ = 22.34 (s, 2P, JPt–P = 1666.77 Hz)
ppm. IR (selected bands, KBr): ν˜ = 290 and 312 (Pt–Cl), 1438 (P–
Ph), 810 (P–N) cm–1.
Data Collection and Structure Determination: Crystallographic data
are given in Table 1. Data were collected with a Rigaku Mercury375R/
M CCD (XtaLAB mini) diffractometer using graphite monochromated
Mo-Kα radiation (λ = 0.71075 Å), equipped with a Rigaku low tem-
perature gas spray cooler. In these cases, data were processed with the
Rigaku CrystalClear software.[16] The data were corrected for Lorentz
and polarization effects.[17] All calculations were performed using the
Crystal Structure crystallographic software package,[18] except for re-
finement, which was performed using SHELXL-97.[19] All structures
were solved by direct methods and refined by full-matrix least-squares
on F2 with anisotropic displacement parameters for all non-hydrogen
atoms.
1H, 13C, and 31P NMR Spectra
Due to the presence of naphthyl and phenyl groups and cou-
pling with 31P, the 1H and 13C NMR spectra of 1–3 were com-
plex and difficult to fully interpret, especially in the aromatic
Crystallographic data (excluding structure factors) for the structures
in this paper have been deposited with the Cambridge Crystallo-
graphic Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ,
UK. Copies of the data can be obtained free of charge on quoting
the depository numbers CCDC-850261 for 2 and CCDC-850262
for 3 (Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk,
http://www.ccdc.cam.ac.uk).
1
region.[20] The H NMR spectra of 2–3 have the expected sig-
nals characteristic for the organic ligand 1. The resonances cor-
responding to the phenyl and naphthyl protons display over-
lapped multiplet signals in the region 6.50–8.52 ppm.
The 31P NMR spectrum of 1 shows a singlet resonance at
δ = 63.46 ppm, indicating two equivalent phosphorus atoms.
The value is in agreement with those reported in the litera-
ture.[6] The 31P NMR signals of 2 and 3 appear as singlet sig-
nals at δ = 37.78 ppm (2) and δ = 22.34 ppm (3). The phospho-
rus resonances of 2 and 3 are shifted downfield by ca. 26 and
41 ppm, respectively, in comparison with the parent organic
ligand 1. The 31P NMR signal in 3 is shifted upfield compared
to that of 2, which reflects the electronic influence of the
amino group.
Results and Discussion
Synthesis
Scheme 1 summarizes the synthesis of 1–3. Ligand 1 was
previously used in the chromium-catalyzed tri- and tetrameri-
zation of ethylene. With the exception of 13P NMR spec-
troscopy, ligand 1 was not structurally characterized.[6] The
reaction of 1-naphthylamine with two equivalents of chlorodi-
phenylphosphine in the presence of triethylamine, proceeds in
tetrahydrofuran at room temperature under nitrogen to give
C10H7-1-N(PPh2)2 (1) in good yield (85%). The compound is
an air-stable solid but gradually undergoes decomposition on
exposure to moisture. The coordination chemistry of ligand 1
The 31P NMR signal of 3 is flanked by two 135Pt satellites
1
with JPt,P coupling constant of 1666.77 Hz. This latter value
is a clear indication of cis coordination of the diphosphine to
the platinum(II) atom, yielding cis-[PtCl2(1)] (3). The magni-
1
tude of the JPt,P = 1666.77 Hz is typical for a bisphosphine
ligand trans to chloride and thus in agreement with the pro-
posed cis coordination of the ligand to PtII.[21–23]
IR Spectra and Yields
The IR spectra of 1–3 show bands in the range of 1438–
1441 cm–1 and 810–910 cm–1 due to ν(P–Ph) and ν(P–N)
stretching, respectively.[22] The ν(P–N) frequencies were ob-
served at 840 cm–1 for 2 and 810 cm–1 for 3. These ν(P–N)
frequencies for the complexes were shifted toward lower fre-
quencies compared to those of the free ligand 1. In their IR
spectra compounds 2 and 3 show bands that can be assigned
to ν(Pd–Cl) (288 and 310 cm–1 ) and ν(Pt–Cl) (290 and
312 cm–1), respectively, which suggest that the ligand coordi-
nates in a cis arrangement and therefore the complex has a
four-membered MPNP (M = Pd or Pt) chelate ring.[24,25] This
fact may be related to a decrease in the ν(P–N) bond strength
upon coordination. Compounds 1–3 were obtained in a 80–
85% yield.
Scheme 1. Preparation of 1–3.
2
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 1–7

PdII and PtII Complexes with Bis(diphenylphosphanyl)naphthylamine
Molecular Structures of 2 and 3
formation of two four-membered metallacycles, i.e., P–N–P–
Pd and P–N–P–Pt, respectively, that are nearly planar with tor-
sion angles P–N–P–Pd of 1.8(7)° in 2a [2.3(7)° in 2b] and P–
N–P–Pt of 3.3(2)° in 3 with smaller P–Pd–P [2a: 72.4(3); 2b:
72.6(3)°] and P–Pt–P [3: 72.53(7)°] bite angles and larger P–
N–P [2a: 101.3(8); 2b: 98.4(9); 3: 99.5(3)°] bond angles.
A comparison of the structural data of the P–Pd–P, P–Pt–P,
and P–N–P bond angles in 2a, 2b, and 3 (Table 2) with those
of the four-membered rings in palladium(II) complexes 4–12
and platinum(II) complexes 13–20 (Table 3) shows that the P–
Pd–P bite angles in 2a and 2b are larger than those in 4–10
and smaller than the one in 11, whereas the P–Pt–P bite angle
in 3 is larger than those in 13 and 14 and smaller than those
in 15–20. The P–N–P bond angle in 3 is larger than those in
13–15 and 20 and smaller than those in 16–19. Additionally,
the P–N–P bond angle in 2a (Table 2) is larger than those in
4–12, whereas the P–N–P bond angle in 2b is larger than those
in 4, 8 and 10 and smaller than those in 5–7, 9, 11, and 12.
The P–N–P [2a: 101.3(8); 2b: 98.4(9); 3: 99.5(3)°] bond
angles are significantly smaller than those in the free diphos-
phinoamine ligands.[22,28] due to the formation of a strained
four-membered chelate ring.
The C-naphthyl skeletons in 2a, 2b, and 3 are almost planar
and virtually perpendicular to the P–N–P–Pd and P–N–P–Pt
planes. A planar environment would be expected for the three-
coordinate nitrogen atoms in 2a, 2b, and 3, and the sums of
bond angles in 2a, 2b, and 3 are indeed close to 360° (Table 2).
The distorted tetrahedral arrangement at the central phos-
phorus atoms [2a: 91.4(7)–123.8(6); 2b: 94.2(8)–120.0(6); 3:
93.59(13)–123.9(3)°] dictates that the phenyl groups are spread
above and below the P–N–P–Pd and P–N–P–Pt planes, and
ring stacking (face-to-face association) is thus prevented. Ap-
parently, the presence of the naphthyl and phenyl groups de-
creases the P–Pd–P and P–Pt–P bite angles, presumably as a
result of steric reasons, as the relatively bulky naphthyl and
phenyl groups occupy much of the lateral space surrounding
the P–N–P–Pd and P–N–P–Pt rings, which led to a distorted
square-planar arrangement around the palladium and platinum
atoms with the aminophosphine moieties coordinated in a mut-
ual cis fashion, in agreement with the spectroscopic data.
Despite the difference of the two metal atoms, the P–Pt–P
[3: 72.53(7)°] and P–Pd–P [2a: 72.4(3); 2b: 72.6(3)°] bite
angles are close to each other and significantly lower than the
ideal 90° in a regular square-planar arrangement.
Crystals of 2 and 3 were obtained as described in Experi-
mental Section. Complexes 2 and 3 crystallize in the mono-
clinic space group Cc and C2/c, respectively. Crystallographic
data are given in Table 1 and selected interatomic distances
and angles are collected in Table 2. The molecular structures
are depicted in Figure 1 and Figure 2.
Table 1. Crystal data and structure refinement for 2 and 3.
2
3
Formula
C34H27Cl2NP2Pd·
1.5C4H8O
797.01
213
monoclinic
Cc
37.31(3)
12.144(10)
16.700(14)
90
C34H27Cl2NP2Pt·
1.134C3H6O
843.32
173
monoclinic
C2/c
36.881(13)
12.118(4)
16.740(6)
90
100.257(4)
90
7362(5)
8
1.522
3330
4.058
Mr
Temp. /K
Crystal system
Space group
a /Å
b /Å
c /Å
α /°
β /°
99.572(8)
90
7461(11)
8
1.419
3264
0.760
31304
13087
0.1012
760
γ /°
V /Å3
Z
ρcalcd. /Mg·m–3
F(000)
Abs coeff /mm–1
No. of rflns coll.
No. of indep. rflns
Rint
25421
8454
0.0869
464
0.0478
0.1195
1.260
No. of params
R1 [I Ͼ 2σ(I))
wR2 (all data)
(Δ/ρ)max /e·Å–3
(Δ/ρ)min /e·Å–3
0.0835
0.2612
2.840
–1.430
–2.030
Table 2. Selected bond lengths /Å and bond angles /° for 2a, 2b, and 3.
M = Pd (2a)
M = Pd (2b)
M = Pt (3)
M–Cl(1)
M–Cl(2)
M–P(1)
M–P(2)
P(1)–N
P(2)–N
P–M–P
∑ angles at N
Cl–M–Cl
P–N–P
M–P(1)–N
M–P(2)–N
P(1)–M–Cl(1)
P(1)–M–Cl(2)
P(2)–M–Cl(1)
P(2)–M–Cl(2)
2.363(10)
2.338(11)
2.249(9)
2.189(9)
1.72(2)
1.67(2)
72.4(3)
360.0
94.9(3)
101.3(8)
91.4(7)
94.8(8)
94.2(4)
170.4(4)
98.5(4)
166.6(4)
2.357(11)
2.341(10)
2.216(9)
2.223(9)
1.73(2)
1.74(2)
72.6(3)
359.9
94.2(3)
98.4(9)
94.7(8)
94.2(8)
93.8(4)
171.3(4)
99.5(4)
166.4(4)
2.3566(17)
2.3566(17)
2.1987(16)
2.2201(16)
1.714(6)
1.710(6)
72.53(7)
359.8
91.08(6)
99.5(3)
94.22(18)
93.59(18)
95.99(6)
172.27(6)
100.38(6)
168.51(6)
The P–Pd–Cl trans angles of 2a [166.6(4) and 170.4(4)°],
2b [166.4(4) and 171.3(4)°], and the P–Pt–Cl trans angles of
3 [168.51(6) and 172.27(6)°] differ significantly from 180°.
The variations of the trans angles [2a: 3.8(4); 2b: 4.9(4); 3:
3.76(6)°] are larger than those of 4 [168.87(6)–166.46(6)°], 5
[167.18(10)–165.81(9)°], and 14 [171.69(5)–169.93(4)°].
The Cl–Pt–Cl angle in 3 [91.08(6)°] is smaller than those in
similar platinum(II) complexes 13–17, 19, and 20 and larger
than the one in 18, whereas the Cl–Pd–Cl angles in 2a
[94.9(3)°] and 2b [94.2(3)°] are larger than those in the similar
PdII complexes 4–7 and 9–12 and smaller than that found in
The X-ray structure of 2 contains two crystallographically
independent molecules, 2a and 2b (Figure 1), in the asymmet-
ric unit, along with three THF molecules. They differ in the
orientation of the naphthyl group and are related by a pseudo-
inversion center. The asymmetric unit of complex 3 (Figure 2)
contains about 1.13 molecules of acetone.
The ability of compound 1 to act as bidentate P,PЈ-chelating 8. The Cl–Pt–Cl angle in 3 is smaller than the Cl–Pd–Cl angles
ligand to palladium and platinum metal atoms results in the in 2a and 2b (Table 2).
Z. Anorg. Allg. Chem. 2012, 1–7
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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3

H. T. Al-Masri
ARTICLE
Figure 1. Molecular structure of the two independent molecules 2a (left) and 2b (right) (hydrogen atoms and solvent molecules are omitted for
clarity).
The Pd–P bond lengths are 2.189(9)–2.249(9) in 2a and
2.216(9)–2.223(9) Å in 2b, whereas in 3 the Pt–P bond lengths
are 2.1987(16)–2.2201(16) Å. The two Pd–P bond lengths in
2a or 2b are relatively different. The shorter Pd–P or Pt–P
distance involves the phosphorus atom, which is closer to the
PdC12 or PtCl2 plane. Apparently, the large steric constraints
in the ligand prevent appropriate orbital overlap when the two
Pd–P or Pt–P bonds are equal and coplanar with the PdC12 or
PtCl2 unit.
The Pd–Cl bond lengths are 2.338(11)–2.363(10) Å for 2a
and 2.341(10)–2.357(11) Å for 2b. The longer Pd–Cl bond is
trans to the shorter Pd–P bond, which is in agreement with a
trans effect of the phosphine. The two Pd–P bond lengths in 3
are similar [2.3566(17) Å], apparently, the bi(phosphanyl)
amine ligand in 3 has the best steric fit and equal donor proper-
ties of –Ph2P groups.
The coordination bond lengths of the platinum and palla-
dium atoms (Table 2) are essentially the same and are well
within the range reported for similar palladium(II) 4–12 and
Figure 2. Molecular structure of 3 (hydrogen atoms and solvent mole-
platinum(II) complexes 13–20 (Table 3). It is interesting to
cules are omitted for clarity).
note that the Pd–P and Pt–P bond lengths are smaller than
those in four-membered ring phosphine complex cis-
The P–N bond lengths in 2a [1.72(2) and 1.67(2) Å] and 2b
[1.73(2) and 1.74(2) Å] are essentially similar, but they are
longer than that of the platinum complex 3 [1.714(6) and
1.710(6) Å], although they are within the expected value range
on comparison to similar palladium(II) complexes 4–12 and
platinum(II) complexes 13–20 (Table 3) and smaller than the
sum of Pauling covalent radii (1.77 Å) as expected due to P–
N π-bonding. in agreement with this, the nitrogen atom is ne-
arly planar as evidenced by the sum of angles about nitrogen
being 360.0° for 2a, 359.9° for 2b, and 359.8° for 3. Also, the
average P–N bond lengths in 2a, 2b, and 3 are slightly shorter
than those in the free diphosphinoamine ligands,[22,28] which
[PdCl2{Ph2PCH2PPh2}] [Pd–P = 2.234(1), 2.250(1); Pd–Cl =
2.362(1), 2.365(1) Å][37] and cis-[PtCl2(PMe3)2] [Pt–P =
2.315(10) Å],[38] but the Pd–Cl and Pt–Cl are slightly smaller
than those in these examples. These results suggest that the
basic nitrogen lone pair make the phosphorus atom better do-
nor on the coplanar to the phosphorus atom and the formation
of π bond by back bonding from the metal. We could say that
the ligand 1 exerts a stronger trans effect than the phosphine
ligands and that the platinum and palladium complexes may
be used as catalyst in various organic synthesis such as the co-
polymerization of olefin and CO.[39]
The P–Pd–P and P–Pt–P bite angles are smaller than those
clearly indicate an enhancement of π-bonding in the P–N unit. of the strained five-membered rings in 21–24 and much
4
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Z. Anorg. Allg. Chem. 2012, 1–7

PdII and PtII Complexes with Bis(diphenylphosphanyl)naphthylamine
Table 3. Selected bis(phosphanyl)amine palladium and platinum dichloride complexes.
Complex
No.
Ring
syst.
P–M–P /°
Cl–M–Cl /°
P–N–P /°
Ref.
cis-[Pd{(Ph2P)2N-C6H4-2-CH(CH3)2}Cl2]·(C2H5)2O
cis-[PdCl2 {Ph2PN(o-C6H4OMe)PPh2}]
cis-[Pd{(Ph2P)2N-C6H3-3,5-OMe}Cl2]
cis-[Pd{(Ph2P)2N-C6H3-2,4-OMe}Cl2]
cis-[Pd{C6H4(o-Ph)N(PPh2)2}Cl2]
cis-[Pd{C6H4(m-CN)N(PPh2)2}Cl2]
cis-[PdCl2{(Ph2P)2N-C6H4-(C2H5)}]
cis-[Pd{(Ph2P)2N-C6H3-3,4-OMe}Cl2]
cis-[Pd{C6H4(p-CN)N(PPh2)2}Cl2]
cis-[PtCl2{(C3H5)N(PPh2)2}]
cis-[Pt{(Ph2P)2N-C6H4-2-CH(CH3)2}Cl2]·(C2H5)2O
cis-[Pt{(Ph2P)2N-C6H3-2,4-OMe}Cl2]
cis-[Pt{(Ph2P)2N-C6H3-3,5-OMe}Cl2]
cis-[Pt{C6H4(m-CN)N(PPh2)2}Cl2]
cis-[PtCl2{(Ph2P)2N-C6H4-(C2H5)}]
cis-[Pt{C6H4(o-Ph)N(PPh2)2}Cl2]
cis-[Pt{C6H4(p-CN)N(PPh2)2}Cl2]
cis-[PdCl2{(PhO)2PN(Et)N(Et)P(OPh)2}]
cis-[PtCl2{(PhO)2PN(Et)N(Et)P(OPh)2}]
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
4
5
5
5
5
7
7
7
7
7
71.93(4)
71.99(5)
71.99(5)
72.20(6)
72.23(3)
72.29(5)
72.30(9)
72.55(5)
72.62(4)
72.10(8)
72.52(4)
72.54(8)
72.59(3)
72.77(3)
72.80(4)
72.95(7)
73.38(4)
82.24(6)
82.55(6)
85.1(2)
96.96(5)
96.36(6)
95.46(5)
96.20(4)
92.39(3)
95.31(5)
98.41(9)
96.57(4)
95.18(4)
91.78(9)
92.92(5)
92.26(8)
91.91(3)
92.03(3)
90.74(4)
91.84(7)
91.23(2)
93.20(6)
91.55(6)
91.0(2)
98.02(16)
99.3(2)
99.4(2)
98.8(3)
97.70(13)
100.2(2)
97.6(4)
99.32(16)
100.1(2)
99.2(4)
97.82(17)
98.7(3)
99.63(2)
99.99(13)
99.72(18)
99.9(3)
98.7(7)
–
–
–
–
–
–
–
–
–
[26]
[27]
[28]
[28]
[29]
[29]
[30]
[28]
[29]
[31]
[26]
[28]
[28]
[29]
[30]
[29]
[29]
[32]
[32]
[32]
[32]
[33]
[34]
[35]
[36]
[33]
cis-[PtCl2{(o-C6H4OCH3)2PN(Me)N(Me)P(o-C6H4OCH3)2}] 23
cis-[PtCl2{(o-C6H4OCH3)2PN(Et)N(Et)P(o-C6H4OCH3)2}]
cis-[PdCl2{Ph2PN(C2H4)2NPPh2}]
cis-[PdCl2{Ph2PN(R)(CH2)2N(R)PPh2}][R = CH(CH3)(Ph)]
cis-[PdCl2{MeC6H3(NHPPh2)2-3,4}]
cis-[PtCl2{iPr2PN(CH2Ph)CH2CH2N(CH2Ph)PiPr2}]
cis-[PtCl2{Ph2PN(C5H10)NPPh2}]
24
25
26
27
28
29
84.9(2)
93.9(2)
96.74(2)
91.31(8)
100.64(3)
97.3(1)
91.1(2)
92.1(2)
90.19(2)
–
86.01(3)
89.1(1)
smaller than those of the seven-membered rings in 25–29
(Table 3). We see that the P–Pd–P or P–Pt–P bite angle is de-
pendent only on the ligand and the angles are virtually iden-
tical in the appropriate pair. The aromatic rings in 3 and 4 as
expected have usual bond lengths and angles.
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Z. Anorg. Allg. Chem. 2012, 1–7
© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
5

H. T. Al-Masri
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Received: February 17, 2012
Published Online: ᭿
6
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© 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2012, 1–7

Z12069TE02
H. T. Al-Masri* .......................................................... 00؊00
Synthesis, Characterization, and Structures of Palladium(II) and
Platinum(II) Complexes Containing N,N-Bis(diphenylphos-
phanyl)naphthylamine