1,2-Bis-N-[2′-(diphenylphosphanyl)benzoyl]diaminobenzene, a new chelating ligand with versatile coordination properties

Article abstract of DOI:10.1002/ejic.200300360

1,2-Bis-N-[2′-(diphenylphosphanyl)benzoyl] diaminobenzene (dppbH; 1) was prepared by peptidic coupling and shown to exist, in the solid state, in the form of hydrogen-bonded dimers by single-crystal X-ray structure analysis. As expected, 1 reacts with [MCl₂(cod)] (M = Pd, Pt; cod = cyclooctadiene) to form square-planar complexes. However, in the case of palladium [PdCl₂(dppbH)] (2) is obtained, while in the case of platinum [Pt(dppb)] (3) is formed. Thus, the nature of the metal induces a completely different coordination mode: In 2, the dppbH ligand only coordinates through the two phosphorus atoms, while in 3 a dppb ligand, formed by deprotonation of the two amino functions in dppbH, coordinates through the two phosphorus atoms and through the two nitrogen atoms. The single-crystal X-ray analyses of the two square-planar complexes reveal 2 to contain the two phosphorus atoms in a trans coordination mode and 3 to contain the two phosphorus atoms in a cis coordination mode. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

Full text of DOI:10.1002/ejic.200300360

SHORT COMMUNICATION
1,2-Bis-N-[2Ј-(diphenylphosphanyl)benzoyl]diaminobenzene, a New Chelating
Ligand with Versatile Coordination Properties
Sylvain Burger,[a] Bruno Therrien,[a] and Georg Süss-Fink*[a]
Keywords: Palladium / Platinum / N,P ligands / Ligand design
1,2-Bis-N-[2Ј-(diphenylphosphanyl)benzoyl]diamino-
benzene (dppbH; 1) was prepared by peptidic coupling and
shown to exist, in the solid state, in the form of hydrogen-
two phosphorus atoms, while in 3 a dppb ligand, formed by
deprotonation of the two amino functions in dppbH, coordin-
ates through the two phosphorus atoms and through the two
bonded dimers by single-crystal X-ray structure analysis. As nitrogen atoms. The single-crystal X-ray analyses of the two
expected, 1 reacts with [MCl2(cod)] (M = Pd, Pt; cod = cyclo-
octadiene) to form square-planar complexes. However, in the
case of palladium [PdCl2(dppbH)] (2) is obtained, while in
the case of platinum [Pt(dppb)] (3) is formed. Thus, the nature
of the metal induces a completely different coordination
mode: In 2, the dppbH ligand only coordinates through the
square-planar complexes reveal 2 to contain the two phos-
phorus atoms in a trans coordination mode and 3 to contain
the two phosphorus atoms in a cis coordination mode.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2003)
Introduction
at the aryl groups have a higher catalytic potential than
those with para and meta substituents. It has been suggested
that mononuclear trans bidentate complexes are more stable
with large metallacycles than with medium-size metalla-
cycles due to the increased flexibility of the larger ring
size.[9] In general, the stability of the trans monomer in-
creases with increasing chain length and reaches a maxi-
mum for a metallacycle containing 15 ring members.[10]
Herein, we report the synthesis of a new diphosphane
ligand containing an ortho-phenylene spacer group for the
synthesis of trans-dicoordinate as well as cis-tetracoordinate
square-planar palladium() and platinum() complexes.
The synthesis of new, highly active complexes for homo-
geneously catalyzed processes is a challenge in coordination
chemistry. Square-planar complexes of PdII and, to a minor
extent, PtII have long been recognized to play a central role
in catalytic reactions such as the classical Wacker process[1]
and, more recently, in the co-polymerization of carbon
monoxide and olefins.[2] PdII and PtII complexes are used
in organic synthesis reactions such as DielsϪAlder cycload-
ditions,[3] BaeyerϪVilliger oxidation of ketones,[4] hydro-
genolysis[5] or Sonogashira cross-coupling.[6]
Electron-rich ligands have been used to increase the elec-
tron density at the metal center in order to facilitate the
oxidative addition step in a catalytic cycle.[7] Phosphane li-
gands have been extensively studied because of their elec-
tron-donating power. Diphosphane ligands have received
special attention because they form, in general, more-stable
(chelate) complexes than monophosphane ligands under
catalytic conditions.[8] In the co-polymerization of olefins
with carbon monoxide, Dosset et al.[7] showed that the cata-
lytic activity of diphosphanylpalladium() complexes of the
type [PdCl2{Ar2P(CH2)nPAr2}] (n ϭ 1Ϫ3) depends upon
the length of the carbon chain and upon the nature of the
aryl groups. The six-membered chelate (n ϭ 3) is an order
of magnitude more active than the five-membered analogue
(n ϭ 2), while the four-membered chelate (n ϭ 1) is essen-
tially inactive. Complexes containing an ortho substituent
Results and Discussion
2-(Diphenylphosphanyl)benzoic acid, easily available
from Wurtz coupling of sodium 2-chlorobenzoate and so-
dium diphenylphosphide,[11] is an attractive building block
for the synthesis of diphosphane ligands by condensation of
the acid function with diols, diamines or amino alcohols.[12]
Peptidic coupling between ortho-diaminobenzene and two
equivalents of 2-(diphenylphosphanyl)benzoic acid affords
[a]
´
ˆ
Institut de Chimie, Universite de Neuchatel
ˆ
Case postale 2, CH-2007 Neuchatel, Switzerland
Fax: (internat.) ϩ 41-32/7182-511
E-mail: georg.suess-fink@unine.ch
Scheme 1
Eur. J. Inorg. Chem. 2003, 3099Ϫ3103
DOI: 10.1002/ejic.200300360
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3099

S. Burger, B. Therrien, G. Süss-Fink
SHORT COMMUNICATION
1,2-bis-N-[2Ј-(diphenylphosphanyl)benzoyl]diamino-
The crystal structure analysis reveals 1 to exist as a dimer
benzene (dppbH; 1) as a microcrystalline powder in good in the solid state, thanks to hydrogen bonding between an
yield (Scheme 1).
NH and a CO function (see Figure 2). The NϪO distance
˚
The diphosphane ligand 1 is symmetrical and shows only of the hydrogen bond [N(2)ϪH···O(1)] is 2.867(3) A, with
one resonance in the 31P{1H} NMR spectrum at δ ϭ an NϪH···O angle of 164.6°. The intramolecular distance
Ϫ8.83 ppm. In the 1H NMR spectrum, 1 gives rise to a between the two phosphorus atoms is 7.794(1) A. In the
˚
singlet at δ ϭ 8.63 ppm (in CDCl3) corresponding to the crystal structure, there is no significant interaction between
amido protons. The amido function is also easily identified compound 1 and the dichloromethane molecule.
in the IR spectrum by two absorptions at 3324 cmϪ1 (νNH
)
One equivalent of dppbH (1) reacts with [MCl2(cod)]
and 1640 cmϪ1 (νCO). The molecular structure of 1, estab- (M ϭ Pd, Pt; cod ϭ cyclooctadiene) to afford the corre-
lished by single-crystal X-ray structure analysis, is shown sponding complexes [PdCl2(dppbH)] (2) and [Pt(dppb)] (3)
in Figure 1.
in good yield (Scheme 2). The reaction was carried out in
dilute solution to avoid the formation of di- or polynuclear
species as observed for other diphosphane ligands.[13]
Scheme 2
Figure 1. ORTEP view of 1, displacement ellipsoids are drawn at
the 50% probability level, hydrogen atoms are omitted for clarity;
˚
selected bond lengths (A) and angles (°): C(7)ϪO(1) 1.237(3),
C(14)ϪO(2) 1.235(3), C(7)ϪN(1) 1.348(4), C(14)ϪN(2) 1.355(4),
C(13)ϪP(1) 1.847(3), C(20)ϪP(2) 1.853(3); O(1)ϪC(7)ϪN(1)
121.6(3), O(2)ϪC(14)ϪN(2) 121.8(3)
[PdCl2(dppbH)] (2) gives only one singlet at δ ϭ
24.03 ppm in the 31P{1H} spectrum, which is indicative of
the coordination of both phosphorus atoms to the metal.
The mass spectrum is in accordance with the presence of a
mononuclear species containing two chloride ligands. The
IR spectrum shows two bands at 3324 (νNH) and 1640 cmϪ1
(νCO) assigned to the amido functions.
The molecular structure of 2 shows the palladium atom
to be in a square-planar geometry, surrounded by two
chlorines and two phosphorus atoms (Figure 3). The chelat-
ing diphosphane ligand adopts a trans coordination ge-
ometry. The ClϪPdϪCl as well as the PϪPdϪP axes are
almost linear, the corresponding angles being 177.03(10)°
and 178.40(9)°, respectively. The two PdϪCl distances are
˚
equivalent [2.310(2) and 2.311(2) A], but interestingly one
˚
PdϪP distance is slightly longer (by 0.042 A) than the other
one. There is no meaningful interaction in the apical posi-
tion of the palladium atom, the shortest distance to another
˚
atom being 2.96 A [Pd(1)ϪO(2)]. In the crystal structure,
only one chloroform molecule interacts with complex 2, for-
ming a weak hydrogen bond with one of the chlorine atoms,
˚
A and the
the Cl(2)ϪC(1S) distance being 3.49(1)
C(1S)ϪH···Cl(2) angle being 150.3(1)°.
The formation of 3 is best monitored by 31P{1H} spec-
troscopy, the complex showing a triplet centered at δ ϭ
6.20 ppm due to the coupling between the two equivalent
phosphorus atoms and the platinum atom (coupling con-
Figure 2. Dimeric structure of compound 1
3100
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
Eur. J. Inorg. Chem. 2003, 3099Ϫ3103

A New Chelating Ligand with Versatile Coordination Properties
SHORT COMMUNICATION
the chelating diphosphane ligand adopts a cis coordination
geometry, with the two nitrogen atoms also coordinating to
the metal. The formation of five- and six-membered chelate
rings imposes a considerable distortion around the platinum
atom. The NϪPtϪP angles [83.47(16) and 89.71(16)°] are
slightly acute due to the bidentate PC6H4C(O)N units. The
atoms Pt(1), P(1), P(2), N(1) and N(2) are almost coplanar,
˚
with an average deviation of 0.0674 A; the metal lies out of
˚
the plane by 0.078(2) A. In the crystal structure, there is no
meaningful interaction between complex 3 and the chloro-
form molecule.
The stability of complex 2 towards base attack and that
of complex 3 towards acid attack has been studied in order
to check the possibility of converting these cis or trans com-
plexes into their corresponding deprotonated or protonated
species. However, complex 2 is not deprotonated by an ex-
cess of triethylamine to give [Pd(dppb)], the 31P{1H} NMR
signal of 2 being unchanged in CDCl3 even after 24 hours
in the presence of NEt3 (100 equiv.). Likewise, complex 3 is
not protonated by concentrated hydrochloric acid to give
[PtCl2(dppbH)], the 31P{1H} NMR signal of 3 being un-
changed in CDCl3 even after 24 hours in the presence of
HCl (100 equiv.).
Figure 3. ORTEP view of complex 2, displacement ellipsoids are
drawn at the 50% probability level, hydrogen atoms and solvent
˚
molecules are omitted for clarity; selected bond lengths (A) and
angles (°): P(1)ϪPd(1) 2.318(2), P(2)ϪPd(1) 2.360(2), Cl(1)ϪPd(1)
2.310(2), Cl(2)ϪPd(1) 2.311(2), C(7)ϪO(1) 1.232(9), C(14)ϪO(2)
1.222(8), C(7)ϪN(1) 1.336(9), C(14)ϪN(2) 1.362(9), C(13)ϪP(1)
1.859(7), C(20)ϪP(2) 1.832(7); Cl(1)ϪPd(1)ϪCl(2) 177.03(10),
Cl(1)ϪPd(1)ϪP(1)
Cl(1)ϪPd(1)ϪP(2)
P(1)ϪPd(1)ϪP(2)
91.91(7),
89.67(8),
178.40(9),
Cl(2)ϪPd(1)ϪP(1)
Cl(2)ϪPd(1)ϪP(2)
O(1)ϪC(7)ϪN(1)
86.27(8),
92.17(8),
123.2(7),
O(2)ϪC(14)ϪN(2) 121.6(7)
stant 3120 Hz). IR spectroscopy shows that there is no νNH
absorption (around 3300 cmϪ1) any more, but a strong νCO
band at 1602 cmϪ1 showing a strong bathochromic effect.
It appears that the formation of 3 is accompanied by
the loss of two equivalents of HCl. Unlike
[Pt{Ph2PC6H4NC(O)C6H4}2],[14] complex 3 does not give
the dichloroplatinum complex [PtCl2(dppbH)] in the pres-
ence of HCl.
Conclusion
We have synthesized a new diphosphane ligand, 1,2-
bis-N-[2Ј-(diphenylphosphanyl)benzoyl]diaminobenzene
(dppbH; 1), which shows a different coordination pattern
towards palladium() and platinum(): it reacts with
[MCl2(cod)] (M ϭ Pd, Pt; cod ϭ cyclooctadiene) to form
the square-planar complexes [PdCl2(dppbH)] (2) and
[Pt(dppb)] (3), respectively. In 2, the dppbH ligand is coor-
dinated by the two phosphorus atoms in a trans configura-
tion, while in 3 the two phosphorus atoms are coordinated
in a cis configuration, the two nitrogen atoms of the dppb
ligand being coordinated as well.
The molecular structure of 3 shows the platinum atom in
a distorted square-planar geometry (Figure 4). Unlike in 2,
Experimental Section
General Remarks: Dichloromethane was dried and distilled under
nitrogen prior to use. All reactions were carried out under nitrogen,
using standard Schlenk techniques. All other reagents were pur-
chased (Aldrich, Fluka) and used as received. NMR spectra were
recorded using a Varian Gemini 200BB instrument and referenced
to the signals of the residual protons in the deuterated solvents.
Electrospray mass spectra were obtained in positive-ion mode with
an LCQ Finnigan mass spectrometer. IR spectra were recorded
with a PerkinϪElmer Spectrum One FTIR spectrometer. Microan-
alyses were carried out by the Laboratory of Pharmaceutical
Chemistry, University of Geneva, Switzerland.
Figure 4. ORTEP view of complex 3, displacement ellipsoids are
drawn at the 35% probability level, hydrogen atoms and solvent
˚
molecules are omitted for clarity; selected bond lengths (A) and
angles (°): P(1)ϪPt(1) 2.243(2), P(2)ϪPt(1) 2.234(2), N(1)ϪPt(1)
Preparation of 1,2-Bis-N-[2Ј-(diphenylphosphanyl)benzoyl]diamino-
1.240(9), C(7)ϪN(1) 1.367(8), C(14)ϪN(2) 1.356(10), C(13)ϪP(1) benzene (dppbH; 1): A solution of 2-diphenylphosphanylbenzoic acid
2.035(6), N(2)ϪPt(1) 2.067(5), C(7)ϪO(1) 1.215(8), C(14)ϪO(2)
1.830(6), C(20)ϪP(2) 1.820(7); N(1)ϪPt(1)ϪN(2) 80.3(2),
(1.0 g,
3.26 mmol),
N,N-dicyclohexylcarbodiimide
(2.7 g,
N(1)ϪPt(1)ϪP(1)
N(1)ϪPt(1)ϪP(2)
P(1)ϪPt(1)ϪP(2)
83.47(16),
169.92(15),
106.26(6),
N(2)ϪPt(1)ϪP(1)
N(2)ϪPt(1)ϪP(2)
O(1)ϪC(7)ϪN(1)
161.74(18),
89.71(16),
125.2(6),
13.05 mmol), 4-(dimethylamino)pyridine (100 mg, 0.82 mmol), 4-
pyrrolidinopyridine (100 mg, 0.68 mmol), and 1,2-diaminobenzene
(175 mg, 1.62 mmol) in CH2Cl2 (40 mL) was allowed to stand at
O(2)ϪC(14)ϪN(2) 122.8(7)
Eur. J. Inorg. Chem. 2003, 3099Ϫ3103
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3101

S. Burger, B. Therrien, G. Süss-Fink
SHORT COMMUNICATION
˚
room temperature under nitrogen, until the esterification was com-
ated radiation (λ ϭ 0.71073 A) with ϕ range 0Ϫ200°, increment of
plete. The resulting solution was concentrated and filtered three 1.5, 1.4 and 0.8° respectively, 2θ range from 2.0Ϫ26°, DmaxϪDmin ϭ
˚
times to remove N,N-dicyclohexyl urea. The filtrate was then con-
centrated under reduced pressure. The residue was submitted to
12.45Ϫ0.81 A. The structures were solved by direct methods using
the program SHELXS-97.[15] The refinement and all further calcu-
column chromatography on silica, eluting with hexane/acetone lations were carried out using SHELXL-97.[16] The H-atoms were
(3:1). The product was isolated from the third fraction by the evap-
included in calculated positions and treated as riding atoms using
oration of the solvent, giving 1 (550 mg, 0.81 mmol; 50%) as a the SHELXL default parameters. The non-H atoms were refined
1
white solid. H NMR (200 MHz, CDCl3): δ ϭ 8.63 (s, 2 H, NH),
7.5Ϫ6.9 (m, 32 H, ArH) ppm. 13C{1H} NMR (50 MHz, CDCl3): Figures were drawn with ORTEP.[17]
anisotropically, using weighted full-matrix least-square on F2.
δ ϭ 168.12, 143.45, 141.20, 141.00, 140.50, 137.62, 137.39, 134.62,
CCDC-212037 (1), -212039 (2), and -212038 (3) contain the sup-
133.90, 130.84, 129.68, 128.94, 128.80, 128.65 ppm. 31P{1H} NMR plementary crystallographic data for this paper. These data can be
(81 MHz, CDCl3): δ ϭ Ϫ8.83 ppm. IR (KBr): ν˜ ϭ 3324 m (NϪH
obtained free of charge at www.ccdc.cam.ac.uk/conts/retriev-
amide), 1640 s (CϭO amide) cmϪ1. ESI-MS: m/z ϭ 685 [M ϩ Hϩ]. ing.html [or from the Cambridge Crystallographic Data Centre, 12,
C44H34N2O2P2 (684.21): calcd. C 77.2, H 5.0, N 4.1; found C 76.8,
H 4.8, N 4.3.
Union Road, Cambridge CB2 1EZ, UK; Fax: (internat.) ϩ44-1223/
336-033; E-mail: deposit@ccdc.cam.ac.uk].
Preparation of [PdCl2(dppbH)] (2): A solution of [PdCl2(cod)]
(42 mg, 0.15 mmol) and 1 (100 mg, 0.15 mmol) in CH2Cl2 (20 mL)
was allowed to stand for 3 hours at room temperature and then
filtered. The filtrate was concentrated under reduced pressure. The
Acknowledgments
residue was submitted to column chromatography on silica, eluting This work is supported by the Swiss National Science Foundation
with dichloromethane/ethanol (4:1). The product was isolated from
the first fraction by the evaporation of the solvent, giving 2 (95 mg,
0.11 mmol; 79%) as a yellow-orange solid. 1H NMR (200 MHz,
CDCl3): δ ϭ 8.66 (s, 2 H, NH), 8.1Ϫ6.9 (m, 32 H, ArH) ppm.
31P{1H} NMR (81 MHz, CDCl3); δ ϭ 24.03 ppm. IR (KBr): ν˜ ϭ
3302 m (NϪH amide), 1662 s (CϭO amide) cmϪ1. ESI-MS: m/z ϭ
885 [M ϩ Naϩ]. C44H34Cl2N2O2P2Pd (861.51): calcd. C 61.3, H
4.0, N 3.3; found C 61.1, H 4.1, N 3.2.
(grant no. 20Ϫ61227Ϫ00). We thank Professor H. Stoeckli-Evans
for free access to X-ray facilities.
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0.15 mmol) and 1 (100 mg, 0.15 mmol) in CH2Cl2 (20 mL) was al-
lowed to stand for two hours at room temperature and then fil-
tered. The filtrate was concentrated under reduced pressure. The
residue was submitted to column chromatography on silica, eluting
with dichloromethane/ethanol (3:1). The product was isolated from
the first fraction by the evaporation of the solvent, giving 3 (80 mg,
0.09 mmol; 61%) as a yellow-green solid. 1H NMR (200 MHz,
CDCl3): δ ϭ 7.9Ϫ6.7 (m, 32 H, ArH) ppm. 31P{1H} NMR
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[3]
[4]
[5]
1
(81 MHz, CDCl3); δ ϭ 6.20 (t, JPt,P ϭ 3120 Hz) ppm. IR (KBr):
ν˜ ϭ 1602 s (CϭO amide) cmϪ1. ESI-MS: m/z ϭ 878 [M ϩ Hϩ],
900 [M ϩ Naϩ]. C44H32N2O2P2Pt (877.28): calcd. C 60.2, H 3.7,
N 3.2; found C 60.0, H 3.6, N 3.4.
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[6d]
X-ray Crystallographic Study
1·CH2Cl2: C45H36Cl2N2O2P2, M ϭ 769.60 g·molϪ1, triclinic, P1
¯
[6e]
˚
(no. 2), a ϭ 9.2473(8), b ϭ 14.0068(14), c ϭ 14.5320(16) A, α ϭ
S. L. Schreiber, L. L. Kiessling, J. Am. Chem.
[6f]
3
˚
J. L. Mascarenas, L. A. Sarand-
89.904(12), β ϭ 89.630(12), γ ϭ 89.693(11)°, U ϭ 1882.2(3) A ,
T ϭ 153 K, Z ϭ 2, µ(Mo-Kα) ϭ 0.300 mmϪ1, 12481 reflections
measured, 6853 unique (Rint ϭ 0.0607) which were used in all calcu-
lations. The final wR (F2) was 0.1126 (all data).
[6g]
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[7]
[8]
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3343Ϫ3352.
2·2CHCl3: C46H36Cl8N2O2P2Pd, M ϭ 1100.71 g·molϪ1, triclinic,
˚
¯
P1 (no. 2), a ϭ 9.9013(11), b ϭ 15.1734(18), c ϭ 16.7870(18) A,
α ϭ 78.059(14), β ϭ 76.629(13), γ ϭ 78.630(14)°, U ϭ 2370.8(5)
3
A , T ϭ 153 K, Z ϭ 2, µ(Mo-Kα) ϭ 0.950 mmϪ1, 17568 reflections
˚
[9]
measured, 8657 unique (Rint ϭ 0.1286) which were used in all calcu-
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lations. The final wR(F2) was 0.1015 (all data).
[10]
[11]
3·CHCl3: C45H33Cl3N2O2P2Pt, M ϭ 997.11 g·molϪ1, monoclinic,
˚
P21/n (no. 14), a ϭ 12.0140(17), b ϭ 11.259(3), c ϭ 28.720(4) A,
J. E. Hoots, T. B. Rauchfuss, D. A. Wrobleski, Inorg. Synth.
1982, 21, 178Ϫ179.
3
˚
β ϭ 95.026(16)°, U ϭ 3870.0(13) A , T ϭ 153 K, Z ϭ 4, µ(Mo-
Kα) ϭ 3.958 mmϪ1, 20851 reflections measured, 7307 unique
(Rint ϭ 0.0544) which were used in all calculations. The final
wR(F2) was 0.0984 (all data).
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[12c]
The data were measured using a Stoe Image Plate Diffraction sys-
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[12d]
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A New Chelating Ligand with Versatile Coordination Properties
SHORT COMMUNICATION
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Received June 10, 2003
Eur. J. Inorg. Chem. 2003, 3099Ϫ3103
www.eurjic.org
 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
3103