Structure and chemical transformations of dipentaerythritol bisbicyclophosphite

Article abstract of DOI:10.1134/S1070363209010083

First data on the chemical properties of dipentaerythritol bisbicyclophosphite and - thionophosphate are presented. The structures of the bisbicyclophosphite and its molybdenum complex are established by X-ray diffraction analysis.

Full text of DOI:10.1134/S1070363209010083

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 1, pp. 49–56. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © D.A. Predvoditelev, M.A. Malenkovskaya, E.V. Strebkova, K.A. Lysenko, E.E. Nifant’ev, 2009, published in Zhurnal Obshchei
Khimii, 2009, Vol. 79, No. 1, pp. 51–58.
Structure and Chemical Transformations
of Dipentaerythritol Bisbicyclophosphite
D. A. Predvoditeleva, M. A. Malenkovskayaa, E. V. Strebkovaa,
K. A. Lysenkob, and E. E. Nifant’eva
a Moscow Pedagogical State University,
Nesvizhskii per. 3, Moscow, 119021 Russia
e-mail: chemdept@mtu-net.ru
b Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Moscow, Russia
Received August 8, 2008
Abstract―First data on the chemical properties of dipentaerythritol bisbicyclophosphite and
-
thionophosphate are presented. The structures of the bisbicyclophosphite and its molybdenum complex are
established by X-ray diffraction analysis.
DOI: 10.1134/S1070363209010083
We earlier reported the synthesis of a new steric
construction: 1,3-bis(2',6',7'-trioxa-1'-phosphabicyclo-
[2.2.2]oct-4-yl)-2-oxapropane [dipentaerythritol bis-
bicyclophosphite (I)] [1]. The aim of this work is
considering chemical features of this compound.
phosphorus-containing rings can be described as twist-
boat with phosphorus and С4 deviating from the
corresponding projection of the plane along the О2–С2
line.
Analysis of the crystal packing showed that the
molecules of bisbicyclophosphite I form chains in
which they are held together by fairly unusual О···Р–О
contacts with the О···Р distances varying in the range
3.194(1)–3.337(1) Å. Therewith, the independent A
and B molecules interact only with each other, forming
two separate sublattices (Fig. 2). The contacts are
specifically directed: The О···Р–О bond angles are
170°–172.7°. These data allow these interactions to be
treated as charge transfer from the oxygen lone pair
onto the antibonding orbital of the Р–О bond (cf. [3]).
We started this work with detailed X-ray structural
analysis of bisbicyclophosphite
I. Compound I
crystallizes as two independent molecules A and B
having the same structures as the parent compound
(Fig. 1). The principal bond lengths and bond angles in
molecules A and B (Table 1) are actually not different
and close to respective parameters in 4-methylene-
2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane isonicoti-
nate (II) [2]. Note that the Р–О bond lengths in both
the independent bisbicyclophosphite I molecules
[1.618(1)–1.634(1) Å] are substantially larger than
respective parameters of compound II [1.604(2)–1.607
(2) Å]. The observed decrease in the Р–О bond lengths
in compound II at room temperature is probably
defined by the absence of libration shortening of bonds
in the C3-symmetrical bicyclic fragment of compound
I. The estimated libration correction in molecule I is
0.005–0.006 Å even at 100 K.
C5'
C5
C1'
C3
O1'
C4
C4'
C2'
O4
O3
C1
C2
C3'
O2'
O1
O3'
P1'
P1
In the crystal of bisbicyclophosphite I, the
symmetry of both independent molecules is close C2
and the conformation of the C4C5O2C4'С5' fragment is
a flat zig-zag (CCОC and CCCО torsion angles
170.2°–178.7°). The conformation of the 6-membered
O2
Fig. 1. General view of one independent molecule of di-
pentaerythritol bisbicyclophosphite I in 50% probability
thermal ellipsoids.
49

50
PREDVODITELEV et al.
Table 1. Principal bond lengths and bond angles in bisbicycle I
Molecule A Molecule B
Molecule A
angle
Molecule B
d
d
bond
bond
ω
angle
ω
P1–O3
P1–O2
P1–O1
P1'–O2'
P1'–O1'
P1'–O3'
O1–C1
O1'–C1'
O2'–C2'
O2–C2
O3–C3
O3'–C3'
O4–C5'
O4–C5
1.6212(10)
1.6293(10)
1.6293(10)
1.6180(10)
1.6220(12)
1.6338(11)
1.4529(16)
1.4541(17)
1.4549(15)
1.4550(16)
1.4485(16)
1.4487(16)
1.4233(16)
1.4261(15)
P1A–O1A
P1A–O2A
P1A–O3A
P1A'–O2A'
P1A'–O1A'
P1A'–O3A'
O1A–C1A
O1A'–C1A'
O2A'–C2A'
O2A–C2A
O3A'–C3A'
O3A–C3A
O4A–C5A
O4A–C5A'
1.6246(11)
1.6268(11)
1.6327(10)
1.6223(10)
1.6228(12)
1.6285(11)
1.4532(16)
1.4518(17)
1.4524(16)
1.4560(16)
1.4515(17)
1.4527(16)
1.4202(16)
1.4231(16)
O3P1O2
O3P1O1
O2P1O1
O2'P1'O1'
O2'P1'O3'
O1'P1'O3'
C1O1P1
C1'O1'P1'
C2'O2'P1'
C2O2P1
C3O3P1
C3'O3'P1'
C5'O4C5
100.77(5)
100.55(6)
100.18(5)
101.30(5)
100.12(5)
100.11(6)
116.48(8)
117.29(9)
117.28(8)
116.98(8)
116.08(8)
116.77(8)
112.33(10)
O1AP1AO2A
O1AP1AO3A
O2AP1AO3A
O2A'P1A'O1A'
O2A'P1A'O3A'
O1A'P1A'O3A'
C1AO1AP1A
C1A'O1A'P1A'
C2A'O2A'P1A'
C2AO2AP1A
C3A'O3A'P1A'
C3AO3AP1A
C5AO4AC5A'
100.49(6)
100.19(6)
100.00(5)
100.96(6)
100.34(6)
100.19(6)
116.27(8)
117.03(8)
117.28(8)
116.48(8)
117.19(8)
116.45(8)
113.52(10)
Fig. 2. Fragment of the crystal packing of dipentaerythritol bisbicyclophosphite I. Independent molecules A and В are shown with
balls of different sizes.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 1 2009

STRUCTURE AND CHEMICAL TRANSFORMATIONS
51
The second part of this publication is devoted to
synthetic features of bisbicyclophosphite I. It was
found that this compound satisfactorily reacts with
benzyl bromide under heating at 130°C in a sealed
ampule.
typical triplet and quartet at δ 1.12 and 3.12 ppm;
besides, the spectrum contained a singlet of the CH2Cl
group at δ 3.80 ppm, a double doublet of the
methylene protons of the 1,3-dioxane ring at δ 4.15
and 4.43 ppm, and a signal of the methylene protons of
the molecular backbone (δ 3.42 ppm).
O
O
O
O
We also reacted bisbicycle I with an equimolar
amount of water (рН = 5) in dioxane. The reaction
mixture was slowly heated to 100°C. This reaction
resulted in cleavage of the carcass construction to form
hydrophosphoryl compound V.
P
CCH2OCH2C
P
O
O
I
(1)
O
P
O
1'
O
6'
O
1
2 3
5'
2'
PhCH2Br
O
O
CCH2OCH2C
PCH2Ph
PhCH2
4' 3'
O
O
2 H2O (H+)
O
O
(3)
I
HP
CCH2OCH2C
PH
CH2Br
CH2Br
III
O
O
CH2OH
CH2OH
The reaction progress was monitored by 31Р NMR
spectroscopy. The yield of dibromophosphonate III
was 85%. Phosphonate III is a stable compound and
can be stored in the dark under an inert atmosphere at
room temperature for a long time. The 31Р NMR
spectrum of compound III is a broad singlet at δР
23.52 ppm. In the 1Н NMR spectrum of this compound
contains typical signals of all proton groups. Thus, the
CH2Br methylene protons appear as two singlets with
Δδ 0.08 ppm, and the signals of axial and equatorial
methylene protons in the phosphorinane fragments are
registered as doublets at 3.81–4.30 ppm. The
remaining signals in the spectrum of bisphosphonate
III are consistent with the proposed structure (see
Experimental).
V
The yield of
a
chromatographically pure
hydrophosphite V is 50%. Its 31Р NMR spectrum
contains a signal at δР 3.67 ppm (1JPH 628.84 Hz). The
1Н NMR spectrum of compound V contains charac-
teristic signals of all proton groups. The Р(О)Н protons
appear as doublets at δ 6.72 ppm (1JPH 638.02 Hz) due
to spin–spin coupling with phosphorus, and the signals
of the 1,3-dioxane protons give a broad multiplet at δ
4.55 ppm. Note that fast hydrolysis of bisbicycle I and
in the presence of even a small excess of water leads to
pentaerythritol. The formation of this hexaol is
1
confirmed by Н NMR and other physicochemical
methods.
Bisbicyclophosphite I readily takes up sulfur to
form bisthionophosphate VI.
With chlorodiethylamine instead of benzyl
bromide, the reaction with bisphosphite I already
occurs at room temperature.
O
O
O
O
O
O
[S]
O
O
I
S
P
CCH2OCH2C
P S
(4)
2 ClNEt2
(2)
PNEt2
I
Et2NP
CCH2OCH2C
O
O
VI
O
O
CH2Cl
CH2Cl
IV
Sulfurization of bisphosphite I was performed for
0.5 h at 60°C in dioxane, yield 87%. Bisthionophos-
phate VI is a crystalline compound stable on storage
under an inert atmosphere for a long time.
Probably, the reaction with benzyl bromide
proceeds along the ionic mode of the Arbuzov
reaction, while with chlorodiethylamine, by the radical
mode. The yield of amidophosphate IV was 79%. The
structure of compound IV was confirmed by
traditional physicochemical methods. The 31Р NMR
spectrum contains a singlet at δР 7.52 ppm, and the 1Н
NMR spectrum shows signals of the N-ethyl protons as
The individuality and structure of bisthiono-
1
phosphate VI were confirmed by TLC and 31Р and Н
NMR spectroscopy. In the 31Р NMR spectrum of
compound VI we observed a singlet signal at δР
1
58.14 ppm. The Н NMR spectrum resembles that of
bisbicycle I [1]. It contains a singlet at δ 3.17 ppm of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 1 2009

52
PREDVODITELEV et al.
the methylene protons of the bridging CН2ОCН2 group
and a doublet at δ 4.58 ppm of the methylene protons
of the bicyclic fragment.
We explored hydrolysis of thionophosphate VI in
the presence of nitrogenous bases, such as triethyl-
amine and cyclohexylamine.
O
O
O
S
S
H2O + NEt3
− P
CCH2OCH2C
P −
O
O
O
[HNEt3]+
CH2OH
VII
[HNEt3]+
CH2OH
VI
(5)
O
O
O
O
S
P −
O
S
H2O + H2NC6H11
− P
O
CCH2OCH2C
[H3NC6H11]+
CH2OH
VIII
CH2OH [H3NC6H11]+
carried out at the ligand:metal carbonyl molar ratio 1:1
in dioxane at 90–100°C in a sealed ampule.
These reactions were carried out in a sealed ampule
in dioxane at 150°C for 14 h at the VI:water:amine
molar ratio of 1:20:20. The terminal hydrolysis
products VII and VIII were isolated as ammonium
salts. The 31Р NMR spectra of salts VII and VIII in the
region characteristic of alkylenebis(thionophosphates)
showed singlet signals at δР 53.97 and 52.96 ppm,
2 Mo(CO)6
C10H16O7P2·2 Mo(CO)5
(6)
I
IX
Molybdenum complex IX was isolated from the
dioxane solution by precipitation to hexane, white
powder, yield 83%. Complex IX could be stored under
an inert atmosphere for a week, after which it got sky-
blue. Its 31Р NMR spectrum contained a signal at δР
1
respectively. The Н NMR spectra of compounds VII
and VIII showed signals characteristic of substituted
ammonium groups. In the case of salt VII, these
signals are a triplet (δ 1.30 ppm) and a multiplet (δ
3.12 ppm) which belong to the methyl and methylene
protons of the N-ethyl groups. In the case of salt VIII,
these are a dublet and a multiplet (δ 1.03–2.37 ppm) of
the axial and equatorial cyclohexyl protons and a
multiplet (δ 3.36 ppm) of the methine proton of the
same fragment. The downfield signals at δ 11.92 (VII)
and 9.40 ppm (VIII) correspond to the hydroxyl
protons.
1
138.96 ppm, and the Н NMR spectrum showed all
signals characteristic of ligand I. These findings gave
evidence showing that complex formation did not
destroy the structure of bisbicyclophosphite I.
Steric organization of complex IX was explored by
X-ray diffraction. The general view of the molecule is
depicted in Fig. 3.
According to X-ray diffraction data, compound IX
is a complex of bisbicyclophosphite I with two
Compound I readily reacts with molybdenum
hexacarbonyl to form complex IX. This reaction was
C5
C3
C5'
C2A'
C4'
C4
O3
P1
O7
C8
O2A'
C1'
O4
O7A'
C8A
C1
O2
C2
O8'
C9'
O9
O1'
C3'
O1
P1'
C7
O6
O3'
Mo1
Mo1'
C9
O8
C10'
O9'
Fig. 3. General view of Мо complex IX.
C7'
C6
C6'
O5
O5'
O6'
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 1 2009

STRUCTURE AND CHEMICAL TRANSFORMATIONS
53
Table 2. Principal crystallographic data and refinement parameters for bisbicyclophosphite I and Мо complex IX
Parameter
Brutto formula
Compound I
C10H16O7P2
310.17
100
Compound IX
C20.80H17.60Cl1.60Mo2O17P2
850.09
Molecular weight
T, K
100
Crystal system
Monoclinic
Pn
Monoclinic
C2/c
Space group
Z(Z')
4(2)
8(1)
a, Å
6.0277(5)
21.5136(15)
10.2729(7)
100.559(2)
1309.61(17)
1.573
36.820(4)
6.3465(6)
31.247(4)
119.589(4)
6349.5(13)
1.779
b, Å
c, Å
β, deg
V, Å3
dcalc, g cm–3
μ, cm–1
3.58
10.97
F(000)
648
3357
2θmax, deg
58
58
Total number of reflexes
15714
24829
Number of independent reflexes
6928
8438
Number of reflexes with I > 2σ(I)
6689
5799
Number of refined parameters
344
399
R1
0.0244
0.0621
1.068
0.0506
wR2
0.1725
GOF
1.075
Residual electron density, e Å–3 (dmin/dmax
)
0.350/–0.224
1.244/–0.975
molecules in the crystal hinders correct estimation of
their occupancies. Therefore, the total occupancy 0.8
for the solvate molecules can be considered as
approximate only. Positions of hydrogen atoms were
calculated geometrically and refined isotropically in
the ride-on model. The principal crystallographic data
and refinement parameters are listed in Table 2. The
ligand geometry is only slightly changed by complex
formation. The existence of disorder in the bicyclic
fragment hinders detailed analysis of the geometry of
compound IX. Note that the Mo–P bond lengths of
molybdenum atoms coordinated at two phosphorus
atoms.
Complex IX crystallizes as a chloroform solvates.
The difference electron density analysis revealed
disorder of the solvate chloroform molecules. The
same is characteristic of the CО groups in one of the
Mo(CО)5 fragments and oxygen atoms in one of the
phosphite fragments. Refinement of two positions of
carbonyls and oxygen atoms in the bicyclic phosphite
fragment showed that they have equal occupancies.
The solvate chloroform molecules are disordered over
three positions. Such a strong disordering of solvate
2.404(1)–2.406(7)
Å
are close to those in
pentacarbonyl(4-methyl-2,6,7-trioxa-1-phosphabicyclo
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 1 2009

54
PREDVODITELEV et al.
Fig. 4. Fragment of the crystal packing of Мо complex IX. Solvate molecules are omitted.
[2.2.2]oct-1-yl)molybdenum (2.418 Å) [4]. Molecules
IX in crystal form fairly large (7.15×10.0 Å) channels
filled with solvate molecules (Fig. 4).
100–250 μm (diameter 10 mm), the Rf values were
determined by TLC on Silufol UV-254 plates in ethyl
acetate–acetonitrile, 2:1 (A), benzene–acetonitrile, 2:1
(B), chloroform–methanol, 3:1 (C), chloroform–me-
thanol–water, 65:25:4 (D), and methanol–water, 3:1
(E).
EXPERIMENTAL
1
The Н NMR spectra were measured on a Bruker
The melting points were measured in a sealed
capillary, heating rate 1 deg min–1.
WM-250 instrument (250 МHz) against internal TMS;
the proton signals were assigned using double
magnetic resonance data. The 31Р–{1Н} NMR spectra
were registered on a Bruker WP–80SY instrument at
the operating frequency 32.4 МHz against external
85% phosphoric acid.
Dipentaerytritol [2',2'',6',6''-tetra(hydroxymethyl)-4-
oxaheptane-1,7-diol] used in the synthesis of bisbi-
cyclophosphite I (from Acros Organics) was initially
recrystallized from water and then kept in a Fischer
gun over Р2О5 in a vacuum (1 mm Hg) at 100°C to
constant weight, mp 222–225°C (cf. the method of
drying with [5]). Bisbicyclophosphite I was prepared
as described in [1].
Elemental analysis was performed on a Perkin–
Elmer 2400 analyzer.
X-ray diffraction investigations of bisbicyclo-
phosphite I and Мо complex IX were carried out on a
SMART APEX II 1000 CCD diffractometer (MoKα
radiation, graphite monochromator, ω-scan). The struc-
tures were decoded by the direct method and refined
by the least-squares technique in the anisotropic full-
matrix approximation on F2hkl. All calculations were
carried out using SHELXTL PLUS program package.
5,5'-Oxydimethylenebis[2-benzyl-5-(bromomethyl)-
1,3,2λ5-dioxaphosphorinane 2-oxide] (III). 0.10 g of
bicycle I and 1.10 g of benzyl bromide (molar ratio
1:20) in 2 ml of anhydrous dioxane was heated in a
sealed ampule at 130°C for 25 h. Benzylphosphonate
III was precipitated from the reaction mixture with
hexane, filtered off, washed with diethyl ether (2×
3 ml), and kept for 1 h at 50°C (1 mm Hg). Yield
All syntheses with trivalent phosphorus compounds
were carried out under dry argon. Adsorption chro-
matography was carried out on a column of silica gel L
1
0.17 g (85%), mp 162–163°C; Rf 0.47 (A). Н NMR
spectrum (CDCl3), δ, ppm: 2.91 br.s (4Н, РCН2Ph),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 1 2009

STRUCTURE AND CHEMICAL TRANSFORMATIONS
55
3.22 s (4Н, CН2ОCН2), 3.26 s and 3.34 s (4Н, CH2Br),
3.81 d (2Нe) and 3.87 d (2Нe), 4.27 d (2Нa) and 4.30 d
(2Нa), [CН2ОР, 2J(НaНe) 11.52 Hz, 3JНР 7.25 Hz], 7.30
m (C6H5). 31Р NMR spectrum (chloroform), δР, ppm:
23.52 br.s. Found, %: C 44.21; Н 4.70; Р 9.69.
C24Н30О7Р2Br2. Calculated, %: C 44.19; Н 4.64; Р
9.50. m 652.
with benzene. Compound VI was eluted with 60 ml of
a 5:1 benzene–acetonitrile mixture. Yield 0.052 g
(87%), mp 284–289°C (decomp.), Rf 0.72 (B). Н
1
NMR spectrum (CD3SOCD3), δ, ppm: 3.17 s (4Н,
3
CН2ОCН2), 4.58 d (12Н, CН2ОР, JНP 6.95 Hz). 31Р
NMR spectrum (pyridine), δР, ppm: 58.14 s. Found, %:
C 32.14; Н 4.33; Р 16.48. C10Н16О7Р2S2. Calculated,
%: C 32.02; Н 4.31; Р 16.55. M 374.
5,5'-Oxydimethylenebis[5-(chloromethyl)-2-(diethyl-
amino)-1,3,2λ5-dioxaphosphorinane 2-oxide] (IV).
To a solution of 0.20 g of bicycle I in 5 ml of an-
hydrous dioxane, 0.15 g of chlorodiethylamine in 2 ml
of the same solvent (molar ratio 1:2) was added
dropwise at room temperature, and the reaction
mixture was kept at that temperature for 3 h. Dioxane
was then removed in a vacuum, and the precipitate was
triturated with hexane and kept for 4 h at 80°C in a
vacuum (1 mm Hg). Yield 0.27 g (79.4%), mp 157–
Salt VII. A solution of 0.1 g of bicycle VI, 0.096 g
of water, 0.54 g of triethylamine (molar ratio 1:20:20)
in 2 ml of dioxane (рН > 10) was heated in a sealed
ampule at 150°C for 14 h. Dioxane, tri-ethylamine, and
water were removed in a vacuum, and the residual oily
substance was dissolved in 3 ml of dioxane and
reprecipitated with ether (2×3 ml). Salt VII was kept
for 4 h at 80°C (1 mm Hg). Yield 0.11 g (68.8%), nD20
1.5143; Rf 0.00 (D, E). 1Н NMR spectrum (CDCl3), δ,
1
3
159°C; Rf 0.21 (A). Н NMR spectrum (CDCl3), d,
ppm: 1.25 t, 1.35 t {18Н, [HN(CН2CН3)3]+, JНН
3
ppm: 1.12 t (12Н, NCН2CН3, JНН 7.02 Hz), 3.12 q
7.30 Hz}, 3.12 m {12Н, [HN(CH2CН3)3]+}, 3.50 s
(4Н, CН2ОCН2), 3.82 s (4Н, CH2OH), 4.02 d.d (4Нe),
4.34 m (4Нa), [CН2ОР, 2J(НaНe) 11.70 Hz, 3JНР 5.48 Hz],
11.92 br. s (2Н, ОН). 31Р NMR spectrum (chloroform),
δР, ppm: 53.93 s Found, %: C 43.35; Н 8.51; Р 10.28.
C22Н50N2О9Р2S2. Calculated, %: C 43.13; Н 8.23; Р
10.11. M 612.
3
(8Н, NCН2CН3, JНР 11.91 Hz), 3.42 s (4Н,
CН2ОCН2), 3.80 s (4Н, CH2Cl), 4.15 d.d (4Нe), 4.43
2
3
d.d (4Нa), [CН2ОР, J(НaНe) 11.59 Hz, JНР 3.35 Hz].
31Р NMR spectrum (chloroform), δР, ppm: 7.52 s.
Found, %: C 41.03; Н 7.12; Р 11.83. C18Н36Cl2N2О7Р2.
Calculated, %: C 41.15; Н 6.91; Р 11.79. M 524.
5,5'-Oxydimethylenebis[5-(hydroxymethyl)-1,3,2λ5-
dioxaphosphorinane 2-oxide] (V). Bicycle I, 0.15 g,
and 0.02 g of water (рН 5) (molar ratio 1:2) in 2 ml of
anhydrous dioxane was slowly heated in a sealed
ampule to 100–105°C. The reaction mixture was kept
at this temperature for 36 h. The solution was
decanted, and hydrophosphite V was precipitated with
hexane. The target substance was washed consecu-
tively with hexane and ether (2×2 ml) and kept for 1h
at 50°C (1 mm Hg). Yield 0.08 g (50%), begins to melt
at 165–168°C and then solidifies at 200°C, Rf 0.68 (E).
1Н NMR spectrum (CD3SOCD3), δ, ppm: 3.27 s (4Н,
CH2OH), 3.38 s (4Н, CН2ОCН2), 4.55 br.m (4Нa),
Salt VIII was prepared similarly to salt VII from
0.06 g of bicycle VI, 0.06 g of water, and 0.32 g of
cyclohexylamine (molar ratio 1:20:20) in 2 ml of
dioxane (рН > 10). Dioxane, cyclohexylamine, and
water were removed in a vacuum, and the residue was
dissolved in 3 ml of methanol and precipitated with
ether (2×3 ml). Salt VIII was kept for 4 h at 80°C
(1 mm Hg). Yield 0.064 g (66%), mp 189–191°C; Rf
0.00 (D, E). 1Н NMR spectrum (C5D5N), δ, ppm: 1.03
m (2Нa, 4Нe), 1.13 d (2Ha), 1.67 m (8Нe), 2.37 d (4Нa),
[CH(CН23CН2)2CH2, 2J(НaНe) 11.69 Hz], 3.36 m (2Н,
H3NCH, J(НaНe) 10.23 Hz), 3.78 s (4Н, CН2ОCН2),
4.12 s (4Н, CH2OH), 4.35d.d (4Нe), 5.08 d.d (4Нa),
1
2
3
(4Нe) (CН2ОР), 6.72 s [2H, P(O)H, JНP 638.02 Hz].
(CН2ОР, J(НaНe) 10.97 Hz, JНР 4.75 Hz), 9.40 br.s
(2Н, ОН). 31Р NMR spectrum (chloroform), δР, ppm:
52.96 s. Found, %: C 43.42; Н 8.17; Р 10.37.
C22Н48N2О9Р2S2. Calculated, %: C 43.27; Н 7.92; Р
10.14. M 610.
31Р NMR spectrum (dioxane ), δР, ppm: 3.67 s (1JНP
628.84 Hz). Found, %: C 34.73; Н 6.01; Р 17.95.
C10Н20О9Р2. Calculated, %: C 34.69; Н 5.82; Р 17.89.
M 346.
4,4'-Oxydimethylenebis[2,6,7-trioxa-1λ5-phospha-
bicyclo[2.2.2]octane 2-sulfide] (VI). A solution of
0.05 g of bicycle I and 0.01 g of finely ground sulfur in
1.5 ml of anhydrous dioxane in the presence of a
catalytic amount of triethylamine was heated for 0.5 h
at 60°C. The white precipitate that formed was filtered
off and applied on a column of silica gel (10 g) filled
Pentacarbonyl[5,5'-oxydimethylenebis[2-benzyl-
5-(bromomethyl)-1,3,2λ5-dioxaphosphorinane 2-oxide]
molybdenum (IX). A solution of 0.08 g of bicycle I
and 0.2 g of molybdenum hexacarbonyl (reagent ratio
1:2) in 5 ml of dioxane was heated in a sealed ampule
for 1.5 h at 90–100°C. Complex IX was precipitated
from the reaction mixture with hexane. The solvents
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 1 2009

56
PREDVODITELEV et al.
were decanted, and the precipitate was washed with
hexane (2×5 ml) and dried for 1 h at 50°C (1 mm Hg).
Yield 0.18 g (85%), Rf 0.35 (C), mp 280°C (decomp.).
1Н NMR spectrum (CDCl3), δ, ppm: 3.12 s (4Н,
REFERENCES
1. Nifant’ev, E.E., Predvoditelev, D.A., Strebkova, E.V.,
and Malenkovskaya, M.A., Dokl. Akad. Nauk, 2007,
vol. 416, no. 2, p. 203.
2. Pike, R.D., Reinecke, B.A., Dellinger, M.E., Wiles, A.B.,
Harper, J.D., Cole, J.R., Dendramis, K.A., Borne, B.D.,
Harris, J.L., and Pennington, W.T., Organometallics,
2004, vol. 23, no. 9, p. 1986.
3. Lobanov, D.I., Aladzheva, I.M., Bykhovskaya, O.V.,
Petrovskii, P.V., Lyssenko, K.A., Antipin, M.Yu.,
Mastryukova, T.A., and Kabachnik, M.I., Phosphorus,
Sulfur, Silicon Relat. Elem., 1997, vol. 128, p. 165.
3
CН2ОCН2), 4.26 d (12Н, CН2ОР, JНР 4.04 Hz). 31Р
NMR spectrum (chloroform), δР, ppm: 138.96 br.s.
Found, %: C 30.95; Н 2.35; Р 8.31. C10Н16О7Р2·
[Мо(CО)5]2. Calculated, %: C 30.71; Н 2.06; Р 7.92.
M 782.
ACKNOWLEDGMENTS
4. Aroney, M.J., Davies, M.S., Hambley, T.W, and
The work was financially supported by the Program
of the President of the Russian Federation for Support
of Leading Scientific Schools of the Russian Federa-
tion (project no. NSh 582.2008.3).
Pierens, R.K., J. Chem. Soc., Dalton Trans., 1994, p. 91.
5. Predvoditelev, D.A., Malenkovskaya, M.A., V’yun-
skovskaya, O.V., and Nifant’ev, E.E., Zh. Obshch.
Khim., 2008, vol. 78, no. 8, p. 1265.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 1 2009