Bisphosphorylated ligands based on isomeric N,N'-phenylenedibenzimidoyl dichlorides

Article abstract of DOI:10.1007/s11172-009-0100-9

The Arbuzov reaction of N,N'-phenylenedibenzimidoyl dichlorides furnished new tet radentate ligands, viz., N,N'-bis[(diphenylphosphoryl)phenylmethylidene] benzenediamines, which form complexes with lanthanides.

Full text of DOI:10.1007/s11172-009-0100-9

Russian Chemical Bulletin, International Edition, Vol. 58, No. 4, pp. 817—822, April, 2009
817
Bisphosphorylated ligands based on isomeric
N,N´ꢀphenylenedibenzimidoyl dichlorides
E. V. Matveeva,a K. A. Lyssenko,a P. V. Petrovskii,a G.ꢀV. Röshenthaler,b and I. L. Odinetsa
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (499) 135 5085. Eꢀmail: odinets@ineos.ac.ru
bInstitute of Inorganic and Physical Chemistry, Bremen University,
Germany*
The Arbuzov reaction of N,N´ꢀphenylenedibenzimidoyl dichlorides furnished new tetꢀ
radentate ligands, viz., N,N´ꢀbis[(diphenylphosphoryl)phenylmethylidene]benzenediamines,
which form complexes with lanthanides.
Key words: phenylenediamines, imidoyl chlorides, the Arbuzov reaction, phosphonates,
phosphine oxides, complexes, lanthanides.
Imidoyl chlorides are useful as building blocks in the
synthesis of imidates,1 amidines,2—4 imidoyl cyanides,4
alkylated imines,5 ketimines,6 as well as various heterocyꢀ
clic compounds possessing biological activity, since the
chlorine atom in them can be easy enough substituted for
the nitrogen or sulfur atom under the action of, for examꢀ
ple, NH and SH nucleophiles. For Nꢀarylimidoyl chloꢀ
rides activated with a perfluoroalkyl substituent, the corꢀ
responding phosphonates (IA) have been obtained by
the Arbuzov reaction,7 which exhibit anticholinesterase
activity.7a
stituents in the azomethine fragment is possible. Such
compounds are characterized by diverse coordinating beꢀ
havior allowing one to obtain monoꢀ, biꢀ, and multinucleꢀ
ar complexes of the chelate and molecular types, as well as
metalꢀcontaining polymeric structures.9 It could be sugꢀ
gested that imidoyl chlorides can be used for the synthesis
of ligands of various types too, including phosphorusꢀconꢀ
taining ones. Nevertheless, the only example for the synꢀ
thesis of bidentate ligands (IB) based on imidoyl chlorides
has been described,2 where palladium complexes proved
to be efficient in the Suzuki and Heck reactions.
RF = CF3, C2F5, C3H7
R = 4ꢀMe, 3ꢀMe, H, 4ꢀCl, 3ꢀCl, 3ꢀCF3
A detailed study of the reactivity of imidoyl chlorides
in the Arbuzov reaction revealed8 that compounds with
electronꢀwithdrawing substituents at the carbon atom reꢀ
act more readily, with the products being able to undergo
various elementotropic transformations.
Currently, a C=N bond as a functional group comꢀ
petes with a C=O bond in its importance in organic chemꢀ
istry. In the era of metal complex catalysis, this is much
due to the interesting coordinating and catalytic properꢀ
ties of the ligands containing an imine functional group
(Schiff bases), where wide variation of the nature of subꢀ
It should be noted that the most data on the reactivity
of imidoyl chlorides obtained by now are related to their
mono derivatives, whereas investigations of their bisꢀanaꢀ
logs comprise only the reactions with NH (see Refs 2—4)
and OH nucleophiles,1,10 sodium azide,11 and malonic
ester dianion.12
Known methods for the synthesis of imidoyl chlorides
are based on the reaction of the corresponding acid
amides with various chlorinating agents, such as phosꢀ
phorus pentachloride (in solvents,3,4 including thionyl
chloride13), thionyl chloride,14 phosgene,15 and a tripheꢀ
nylphosphine—carbon tetrachloride system.16 Here, even
in the case of mono derivatives, the target imidoyl chloꢀ
* Institut für Anorganische und physikalische Chemie, Univerꢀ
sität Bremen, Germany.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 800—805, April, 2009.
1066ꢀ5285/09/5804ꢀ0817 © 2009 Springer Science+Business Media, Inc.

818
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 4, April, 2009
Matveeva et al.
C(19)
C(18)
C(12)
C(13)
C(20)
Cl(2)
C(15)
C(11)
C(10)
Cl(1)
C(8)
C(7)
C(17)
C(14)
C(16)
C(9)
C(2)
C(5)
C(3)
N(2)
N(1)
C(1)
C(6)
C(4)
Fig. 1. General view of the Z,Zꢀisomer of compound 2a. Main bond distances (Å): Cl(1)—C(7) 1.783(2), Cl(2)—C(14) 1.778(1),
N(1)—C(1) 1.418(2), N(1)—C(7) 1.254(2), N(2)—C(3) 1.417(2), N(2)—C(14) 1.255(2); main bond angles (deg): C(2)—C(1)—C(7)—N(1)
71.0(1), C(2)—C(3)—C(14)—N(2) 68.2(1).
rides frequently are not isolated in the individual state and
are used in subsequent reactions without additional purifiꢀ
cation. Moreover, diimidoyl dichloride obtained from
mꢀphenylenediamine is found to be unstable.3
ene (reflux, 10 h) was used as a solvent. Diimidoyl dichloꢀ
rides 2a,b formed precipitate state the reaction mixtures
after cooling and can be isolated in the individual form by
simple filtration, though this is accompanied by the loss of
the target compounds due to their partial solubility in tolꢀ
uene (the yield was ~75%). Evaporation of the volatile
components in vacuo and washing of products 2a,b with
light petroleum seems an optimum method for the isolaꢀ
tion of such compounds (the yields were 95 and 97% for
2a and 2b, respectively).
The structures of stable in the individual state diimidoyl
dichlorides 2a,b were confirmed not only by the spectral
methods and elemental analysis, but also by a single crysꢀ
tal Xꢀray diffraction.* General views of the diimidoyl
dichlorides molecules 2a and 2b are given in Figures 1
and 2, respectively. In the crystal, mꢀdiimidoyl dichloride
2a exists as the Z,Zꢀisomer (relative to the double bonds).
pꢀDiimidoyl dichloride 2b occupies a particular position,
the center of symmetry, and is also characterized by
the Z,Zꢀisomerism of the multiple bonds. The main
geometrical parameters of structures 2a and 2b are close.
Due to the steric reasons, the C=N groups are not coplaꢀ
nar with the central plane of the arene ring with the turn
angles equal to ~70 and 50° in 2a and 2b, respectively. In
turn, the absence of conjugation of the C=N bonds leads
to the fact that their distances correspond to the values
It could be assumed that the Arbuzov reaction in
the series of diimidoyl dichlorides, synthesized in turn
from isomeric phenylenediamines, would lead to new types
of oligodentate ligands containing the oxygen atom of the
phosphoryl group and the sp2ꢀhybridized nitrogen atom as
the coordinating sites. Dibenzamides 1a,b, obtained from
pꢀ and mꢀphenylenediamines, gave rise to diimidoyl
dichlorides 2a,b (Scheme 1). For the synthesis of comꢀ
pounds 2a,b, we applied a modified procedure using phosphoꢀ
rus pentachloride as a chlorinating agent. It differs from the
known versions by milder conditions, in particular, toluꢀ
Scheme 1
* It should be noted that the melting point for pꢀdiimidoyl dichloꢀ
ride 2b obtained by us, whose structure was confirmed by eleꢀ
mental analysis and physicoꢀchemical methods, considerably
differs from the data of other authors (see Experimental).
This can be explained by the fact that earlier the authors obꢀ
tained a mixture of diimidoyl dichloride, amide, and products
of their resinification under significantly more severe reacꢀ
tion conditions.
Here and further: a, metaꢀisomer, b, paraꢀisomer.

Phosphorylated diimidoyl dichlorides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 4, April, 2009
819
Cl(1)
C(1)
C(13)
C(12)
C(7)
N(1)
C(3A)
C(2A)
C(10A)
C(8)
N(1A)
C(9A)
C(8A)
C(11)
C(9)
C(10)
C(1A)
C(2)
C(3)
C(7A)
C(11A)
C(12A)
C(13A)
Cl(1A)
Fig. 2. General view of the Z,Zꢀisomer of compound 2b. Main bond distances (Å): Cl(1)—C(7) 1.777(2), N(1)—C(7) 1.257(2),
N(1)—C(1) 1.417(2); the bond angle C(7)—N(1)—C(1)—C(3A) 54.2(1)°.
Scheme 2
typical for of double bonds. In crystals, excluding a number
of weak interactions C—H...π and C—H...Cl, the rest of
contacts correspond to the Van der Waals interactions.
Examination of structural homogeneity of these comꢀ
pounds by Xꢀray powder diffraction showed that the samꢀ
ple of paraꢀisomer 2b corresponds to the structure of
a single crystal, whereas for the sample of metaꢀisomer 2a,
the presence of additional peaks is characteristic, which
indicates the presence of other isomer (or polymorph).
Upon study of the Arbuzov reaction for diimidoyl
dichlorides 2a,b with triethyl phosphite, it was found that,
in contrast to the highly electrophilic perhaloalkylꢀsubstiꢀ
tuted imidoyl chlorides,7,8 under standard conditions, i.e.
upon reflux of a stoichiometric mixture of reagents in benꢀ
zene or toluene, the target products are formed in less than
15% yield even after prolonged (60 h) heating of the reacꢀ
tion mixture. When triethyl phosphite is used as the
solvent, the content of the target product increases
(Scheme 2), but a parallel formation of the phosphorylaꢀ
tion products at both the nitrogen atom and the carbon
atom, 4a,b and 5a,b, is observed. The use of nickel dichloꢀ
ride as a catalyst (5—7 mol.%) leads to the increase in
the yield of all three compounds 3—5 (see Scheme 2).
Note that phosphonates 3 undergo partial transformation
into the products of phosphorotropic rearrangements 4
and 5 also in the process of chromatographic purification,
which does not allow us to isolate these compounds in the
individual states.
The mass spectra of the reaction mixtures exhibit peaks
corresponding to the molecular ions of the compounds
indicated. The illustrative mass spectrum of a mixture of
compounds obtained after chromatographic purification
of product 3b are given in Fig. 3 (m/z: 557 [M]+, 3b;
695 [M´]+, 4b; 833 [M″]+, 5b). The 31Р—{1H} NMR specꢀ
trum of the reaction mixture obtained when the metaꢀ
isomer 2a was used exhibits a broadened singlet signal in
the region δ 6.7, which, apparently, corresponds to prodꢀ
uct 3a and the phosphorus atom at the multiple bond in
compound 4a. The two doublet signals at δ 5.84 (P″N)
and 21.44 (P´CH) with the spinꢀspin coupling constant of
22 Hz correspond to the bisꢀphosphorylated fragment in
compounds 4a and 5a. Similar pattern is observed in the
spectrum of the reaction mixture in the case when triethꢀ
ylphosphite reacts with paraꢀisomer 2b.
At the same time, the Arbuzov reaction of diimidoyl
dichlorides 2a,b with ethyl diphenylphosphinite on reflux
of a stoichiometric mixture of reagents in toluene leads to
the corresponding phosphine oxides, though in not very
high yields (Scheme 3). Taking into account that the
31Р—{1H} NMR spectra of the reaction mixtures exhibit

820
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 4, April, 2009
Matveeva et al.
I (%)
the reaction results in the formation of stable complexes of
the form ML(NO3)3. The coordination shift of the signal
for the phosphorus atom in the 31Р—{1H} NMR spectra
(for the complexes with Pr and Nd in solutions, Δδ = 105
and 117 ppm, respectively) and the shift of the absorption
bands for the C=N and Р=O bonds in the IR spectra of
the complexes formed (Nujol) unambiguously testify the
participation of the ligand phosphorus and nitrogen atoms
in the coordination. In addition, the presence of the abꢀ
sorption bands in the region ~1480 cm–1 (ν(N=O)) and
~1302 cm–1 (νas(NO2)) allowed us to suppose a bidentate
coordination of the nitrate groups. The presence of a small
shoulder in the IR spectrum in the region 1390 cm–1 does
not exclude that one of the nitrate groups either is coordiꢀ
nated by only one oxygen atom or is in the external coorꢀ
dination sphere. It should be also noted that the presence
of a sharp band at 1637 and 3368 cm–1 allowed us to
suggest the presence of water molecules in the coordiꢀ
nation sphere of the metal. The entire identity of the
IR spectra of the praseodymium and neodymium comꢀ
plexes indicates the similarity of their structures. It could
be assumed that in the complexes ML, either the metal
cation is included into the cavity formed by the dentate
fragments and coordinated with the nitrogen atom of the
fragment C=N and the oxygen atom of the phosphoryl
group (A) or, which seems more probable to us, a polymer
chain is formed with the similar type of the metal coordiꢀ
nation (B).
[N2C6H4]+ [M´ – 2 P(O)(OEt)2 – CPh]+
[Ph]+
100
[M – P(O)(OEt)2 – CPh]+
80
60
40
20
0
[EtO]+
[M´ – P(O)(OEt)2 – CPh]+
[M´ – P(O)(OEt)2]+
[M]+ [M´]+ [M´´ ]+
0
100 200 300 400 500 600 700 800 m/z
Fig. 3. The illustrative mass spectrum of a mixture of compounds
3b, 4b, and 5b.
three singlet signal with different intensities (δР 24.18,
24.45, 24.50 with the ratio of intensities 75 : 15 : 10 for 6a
and δР 24.11, 24.31, 24.40 with the ratio of intensities
70 : 20 : 10 for 6b), one can assume that in the course of
the reaction, all three possible stereoisomers (Z,Z, E,Z,
E,E) of phosphine oxides 6 are formed with one of them,
giving the upfield signal, being predominant (>70%). Afꢀ
ter purification by recrystallization (compounds partially
decompose when purified by chromatography on silica
gel), N,N´ꢀbis[(diphenylphosphoryl)phenylmethylidene]ꢀ
benzenediamines 6a,b, being yellow powders, were isolatꢀ
ed as the individual stereoisomers, whose signals predomꢀ
inated in the reaction mixtures. Unfortunately, since we
failed in growing crystals for such phosphine oxides suitꢀ
able for Xꢀray diffraction analysis, the question about their
exact configuration remains open.
Scheme 3
M = Nd3+, Pr3+; nitrate groups are not shown.
Experimental
NMR spectra were recorded on a Bruker AMXꢀ400 specꢀ
trometer in CDCl3 or DMSOꢀd6 using the signal for the residual
protons of a deuterated solvent as a reference (1H and 13C relaꢀ
tively to Me4Si) and 85% aq. H3РO4 as an external standard
(31P). IR spectra were recorded on a MagnaꢀIR 750 Fourierꢀ
spectrometer (Nicolet), resolution, 2 cm–1, number of scans 128
(KBr pellets or a suspension in Nujol). Mass spectra were reꢀ
corded on a Finnigan LCQ Advantage tandem mass spectromeꢀ
ter in the mode for detection of positively charged ions (the
sensitivity limit, 2000 m/z).
Isomeric N,N´ꢀ(phenylene)dibenzamides 1a,b were syntheꢀ
sized by the reaction of corresponding isomeric diamines with
benzoyl chloride in the presence of pyridine according to the
procedure described earlier,17 their physicoꢀchemical constants
are in agreement with the literature data.
Upon study of complexation of mꢀbisphosphine dioxꢀ
ide 6a with neodymium and praseodymium nitrates in
acetone, it was found that, irrespective of the reagent ratios,

Phosphorylated diimidoyl dichlorides
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 4, April, 2009
821
N,N´ꢀ(mꢀPhenylene)dibenzimidoyl dichloride (2a). A mixture
of N,N´ꢀ(mꢀphenylene)dibenzamide 1a (5 g, 16 mmol) and phosꢀ
phorus pentachloride (6.6 g, 32 mmol) in anhydrous toluene
(100 mL) was refluxed for 10 h. The solvent was evaporated
in vacuo, the residue was washed with anhydrous light petroleum
and dried in vacuo (70 °C, 1 Torr, 4 h). The yield was 5.3 g
(95%), m.p. 89 °C (cf. Ref. 4: m.p. 86 °C). Found (%): C, 68.07;
H, 3.94; N, 8.01. C20H14Cl2N2. Calculated (%): C, 68.00;
H, 3.99; N, 7.93. 1H NMR (CDCl3), δ: 6.69 (br.s, 1 H, NC6H4N);
6.86, 6.88 (both d, 1 H each, NC6H4N, JH,H = 2.0 Hz); 7.42
(s, 1 H, NC6H4N); 7.44—7.57 (m, 6 H, Ph); 8.17—8.19 (m, 4 H,
Ph). IR (KBr), ν/cm–1: 1659 (C=N).
N,N´ꢀ(pꢀPhenylene)dibenzimidoyl dichloride (2b) was obꢀ
tained similarly. The yield was 97%, m.p. 168 °C (cf. Ref.: m.p.
213 °C (see Ref. 1); 176 °C (see Ref. 4)). Found (%): C, 68.07;
H, 3.94; N, 7.91. C20H14Cl2N2. Calculated (%): C, 68.00;
H, 3.99; N, 7.93. 1H NMR (CDCl3), δ: 7.13 (s, 4 H, NC6H4N);
7.47—7.56 (m, 6 H, Ph); 8.18—8.21 (m, 4 H, Ph). IR (KBr),
ν/cm–1: 1649 (C=N).
Table 1. Main crystallographic data and refining parameters for
the structures 2a and 2b
Parameter
2a
2b
Molecular formula
Molecular weight
T/K
C20H14Cl2N2 C20H14Cl2N2
353.23
120
353.23
120
Crystal system
Space group
Z (Z´)
Monoclinic
P21/n
Monoclinic
P21/c
2 (0.5)
3
4 (1)
a/Å
b/Å
c/Å
8.941(2)
8.5598(18)
22.345(5)
100.152(4)
1683.3(6)
1.394
18.0005(13)
5.9999(4)
7.5480(5)
93.505(2)
813.67(10)
1.442
β/deg
V/Å3
dcalc/g cm–3
μ/cm–1
3.88
4.02
F(000)
728
364
2θmax/deg
Number of measured
reflections
Number of independent
60
15199
58
5698
N,N´ꢀBis[(diphenylphosphoryl)phenylmethylidene]ꢀ1,3ꢀbenzꢀ
enediamine (6a). A mixture of mꢀdiimidoyl dichloride 2a (2.2 g,
0.006 mol) and ethyl diphenylphosphinite (2.9 g, 0.012 mol) in
anhydrous toluene (30 mL) was refluxed for 3 h. A precipitate
formed was filtered off and recrystallized from EtOH to obtain
the target product (0.6 g, 14%) as a light yellow powder, m.p.
247 °C. A sample for elemental analysis was prepared by recrysꢀ
tallization from CH2Cl2. Found (%): C, 73.50; H, 4.85; N, 3.85;
P, 8.52. C44H34N2O2P2•0.5CH2Cl2. Calculated (%): C, 73.47;
H, 4.52; N, 3.95; P, 8.81. 31Р (CDCl3): δ 23.08. 1H NMR
(CDCl3), δ: 6.10 (s, 1 H, NC6H4N); 6.23, 6.26 (both br.s, 1 H
4881 [0.0248] 2147 [0.0274]
reflections [Rint
]
Number of reflections
with I > 2 σ(I)
Number of refining
parameters
R1
wR2
3852
273
1662
137
0.0431
0.0968
1.059
0.0427
0.0972
1.020
3
GOF
each, NC6H4N); 6.89 (t, 1 H, NC6H4N, JH,H = 7.8 Hz);
Residual electron
density/e Å–3 (ρmin/ρ
0.419/–0.296 0.537/–0.272
7.05—7.07, 7.14—7.22, 7.44—7.55, 7.84—7.89 (all m, 4 H + 6 H +
+ 12 H + 8 H, 6 Ph). 13C NMR (CDCl3), δ: 112.44 (s, C(2));
116.49 (s, C(4), C(6)); 128.00 (s, pꢀPhP); 128.30 (d, mꢀC, PhP,
3JP,C = 12.0 Hz); 128.84 (s, C(10), C(12), C(17), C(19)); 128.96
(s, C(5)); 129.43 (s, C(11), C(18)); 131.14 (d, ipsoꢀC, PhP,
)
max
dioxide 6a (50 mg, 0.07 mmol) was dissolved upon heating in
acetone (5 mL) followed by addition of Pr(NO3)3•6H2O (32 mg,
0.07 mmol). After 24 h, the solvent was half evaporated, a preꢀ
cipitate formed was filtered off. The yield was 38 mg (52%), m.p.
218 °C (decomp.). Found (%): C, 51.12; H, 4.17; N, 6.58.
C44H34N5O11P2Pr•(CH3)2CO•2H2O. Calculated (%): C, 51.05;
1JP,C = 102.0 Hz); 131.95 (d, C(9), C(13), C(16), C(20), 3JP,C
=
= 6.9 Hz); 132.01 (d, oꢀC, PhP, 2JP,C = 9.0 Hz); 133.98 (d, C(8),
C(15), 2JP,C = 24.4 Hz); 149.76 (d, C(1), C(3), 3JP,C = 25.6 Hz);
172.72 (d, C(7), C(14), JP,C = 116.0 Hz). IR (KBr), ν/cm–1
:
1
513, 566, 584, 695, 724, 1121, 1182 (P=O), 1437, 1588 (C=N),
3055, 3034 (br). MS (EI, 70 eV), m/z (Irel (%)): 684 [M]+ (5),
484 [M – P(O)Ph2]+ (55), 483 [M – H – P(O)Ph2]+ (100), 283
[M – H – 2 P(O)Ph2]+ (40), 201 [P(O)Ph2]+ (40), 179 [M –
– P(O)Ph2 – NCPh – 2 H]+ (51), 77 [Ph]+ (40), 76 [C6H4]+ (58).
N,N´ꢀBis[(diphenylphosphoryl)phenylmethylidene]ꢀ1,4ꢀbenzꢀ
enediamine (6b) was obtained similarly. The yield was 26%, m.p.
268 °C. Found (%): C, 73.50; H, 4.85; N, 3.85; P, 8.52.
C44H34N2O2P2•0.5CH2Cl2. Calculated (%): C, 73.50; H, 4.57;
H, 4.01; N, 6.33. 31P (DMSOꢀd6): δ 113.31. IR (Nujol), ν/cm–1
:
541, 709, 725, 1089, 1133 (P=O), 1170, 1306 (br), 1377, 1439,
1463, 1485, 1531, 1603 (C=N), 1634, 1705, 3062, 3368 (br).
{N,N´ꢀBis[(diphenylphosphoryl)phenylmethylidene]ꢀ1,3ꢀ
benzenediamine}neodymium trinitrate (7b) was obtained under
similar conditions from compound 6a (40 mg, 0.06 mmol) and
Nd(NO3)3•6H2O (36 mg, 0.06 mmol). The yield was 40 mg
(70%), m.p. 238 °C (decomp.). Found (%): C, 52.32; H, 4.44;
N, 6.37. C44H34N5NdO11P2•2(CH3)2CO•H2O. Calculated (%):
C, 52.26; H, 4.21; N, 6.09. 31P (DMSOꢀd6): δ 137.83. IR (Nujol),
ν/cm–1: 541, 708, 726, 1087, 1132 (P=O), 1169, 1302 (br), 1378,
1439, 1463, 1484, 1533, 1602 (C=N), 1621, 1708, 3061, 3351 (br).
Xꢀray diffraction study of compounds 2a,b was performed
on a SMART 1000 CCD diffractometer (MoꢀKαꢀirradiation,
a graphite monochromator, ωꢀscanning). Crystals for the study
were obtained from Et2O—EtOH. Absorption was accounted
ab initio on equivalent reflections using the Sadabs program. The
structures were decoded by the direct method and refined by the
least squares method in anisotropic fullꢀmatrix approximation
on F2hkl. Hydrogen atoms were localized from the differential
1
N, 3.96; P, 8.28. 31Р (CDCl3): δ 23.15. H NMR (CDCl3), δ:
6.56 (s, 4 H, NC6H4N); 7.20—7.22, 7.29—7.32, 7.51—7.59,
7.92—7.96 (all m, 6 H + 5 H + 13 H + 6 H, 6 Ph). IR (KBr),
ν/cm–1: 520, 543, 578, 696, 723, 774, 834, 1119, 1187 (P=O),
1438, 1489, 1591 (C=N), 1602, 1667, 3056, 3034 (br). MS (EI,
70 eV), m/z (Irel (%)): 684 [M]+ (3), 485 [M + H – P(O)Ph2]+
(40), 483 [M – H – P(O)Ph2]+ (100), 283 [M – H – 2 P(O)Ph2]+
(50), 201 [P(O)Ph2]+ (40), 179 [M – P(O)Ph2 – NCPh – 2 H]+
(60), 77 [Ph]+ (40), 76 [C6H4]+ (36). A sample for elemental
analysis was prepared by recrystallization from CH2Cl2.
{N,N´ꢀBis[(diphenylphosphoryl)phenylmethylidene]ꢀ1,3ꢀ
benzenediamine}praseodymium trinitrate (7a). mꢀBisphosphine

822
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 4, April, 2009
Matveeva et al.
Fourierꢀsyntheses of electron density and refined in isotropic
approximation. The main crystallographic data and refining paꢀ
rameters are given in Table 1. All the calculations were perꢀ
formed using SHELXTL PLUS program package.
1987, 57, 1514 [J. Gen. Chem. USSR (Engl. Transl.), 1987,
57, No. 7]; P. P. Onys´ko, T. V. Kolodka, A. A. Kudryavtꢀ
sev, A. D. Sinitsa, Zh. Obshch. Khim., 1993, 63, 1562 [J. Gen.
Chem. USSR (Engl. Transl.), 1993, 63, No. 7].
9. A. D. Garnovskii, I. S. Vasil´chenko, Usp. Khim., 2002, 71,
1064 [Russ. Chem. Rev. (Engl. Transl.), 2002, 71, 943]; A. D.
Garnovskii, I. S. Vasil´chenko, Usp. Khim., 2005, 74, 211
[Russ. Chem. Rev. (Engl. Transl.), 2005, 74, 193].
10. J. W. Schulenberg, S. Archer, J. Am. Chem. Soc., 1960, 82,
2035; J. E. Rowe, Synthesis, 1980, 114.
This work was financially supported by the German
Scientific Society Fund (DFG, Grant 436 Rus 113/766/1ꢀ1).
References
11. T. V. Artmonova, A. B. Zhivich, M. Yu. Dubinskii, G. Kolꢀ
dobskii, Synthesis, 1996, 12, 1428.
1. G. Bock, Chem. Ber., 1967, 100, 2870.
2. K.ꢀM. Wu, C.ꢀA. Huang, K.ꢀF. Peng, C.ꢀT. Chen, Tetraheꢀ
dron, 2005, 61, 9679.
3. J. K. Hutchison, G. Srdanov, R. Hicks, H. Yu, F. Wudl,
J. Am. Chem. Soc., 1998, 120, 2989.
4. H. K. S. Rao, T. S. Wheeler, J. Chem. Soc., 1937, 1643.
5. H. Quast, R. Frank, A. Heublein, E. Schmitt, Liebigs Ann.
Chem., 1979, 83.
12. H. K. S. Rao, T. S. Wheeler, J. Chem. Soc., 1938, 476.
13. G. I. Koldobskii, I. V. Nikonova, A. B. Zhivich, V. A. Ostroꢀ
vskii, V. S. Poplavskii, Zh. Obshch. Khim., 1992, 62, 194
[J. Gen. Chem. USSR (Engl. Transl.), 1992, 62, No. 2].
14. J. von Braun, W. Pinkernelle, Chem. Ber., 1934, 67, 1218;
A. R. Katritzky, A. T. Tods, Heterocycles, 1982, 18, 21.
15. H. von Eilingsfeld, M. Seefelder, H. Weidinger, Angew.
Chem., 1960, 22, 70.
16. R. Appel, K. Warning, K.ꢀD. Ziehn, Chem. Ber., 1973,
106, 3450.
17. V. V. Korshak, T. M. Frunze, L. V. Kozlov, Izv. Akad. Nauk
SSSR, Ser. Khim.., 1962, 2062 [Bull. Acad. Sci. USSR, Div.
Chem. Sci. (Engl. Transl.), 1962, 11].
6. M. Kosugi, M. Koshiba, A. Aton, H. Sano, T. Migita, Bull.
Chem. Soc. Jpn, 1986, 59, 677.
7. V. F. Shchegel´skii, V. V. Sokolov, G. A. Shataeva, V. I.
Fetisov, I. V. Martynov, Khim. Pharm. Zh., 1996, 11, 26
[Pharm. Chem. J. (Engl. Transl.), 1996, 11]; H. Weisheng,
Z. Yixin, Y. Chengye, Phosphorus, Sulfur, Silicon, 1995,
107, 21.
8. A. D. Sinitsa, V. S. Krishtal´, V. I. Kal´chenko, L. N. Markꢀ
ovskii, Zh. Obshch. Khim., 1980, 50, 465 [J. Gen. Chem. USSR
(Engl. Transl.), 1980, 50, No. 2]; P. P. Onys´ko, E. I. Suꢀ
valova, T. I. Chudakova, A. D. Sinitsa, Zh. Obshch. Khim.,
Received November 19, 2008;
in revised form March 13, 2009