Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ5-phosphane

Article abstract of DOI:10.1080/10426500701696829

The symmetric hydrido-spiro-λ5-phosphane derived from anhydroerythritol (meso-oxolane-3,4-diol, AnEryt), HP(AnErytH- 2)2(3), was prepared by two different synthetic protocols. One route involves a three step synthesis starting from phosphorus trichloride via 2-chloro-tetrahydro-furo[3,4- d][1,3,2]dioxaphosphole (1) and diethyl-(tetrahydro-furo[3,4-d][1,3,2] dioxaphosphol-2-yl)-amine (2) as intermediates. The first intermediate, P(AnErytH- 2)Cl (1), was isolated as a crystalline solid and its structure was determined by single crystal X-ray diffraction. 1 is the first example of a halogeno substituted phosphane derived from an aliphatic diol whose molecular structure in the solid state was determined by X-ray diffraction studies. Alternatively, the title compound can also be obtained in a one-pot procedure starting from tris(N,N-dimethylamino)phosphane. All new compounds were characterized by their physical constants (melting point, refractory index), NMR, IR, Raman, UV/VIS, mass spectrometry, as well as elemental analysis. Some spectroscopic proofs for the spiro nature of the title compound are given. Copyright Taylor & Francis Group, LLC.

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Hydrido-bis(meso-
5
oxolanylen-3,4-dioxy)-λ -
phosphane
a
a
Richard Betz & Peter Klüfers
a
Department of Chemistry and Biochemistry ,
Ludwig Maximilians University , Munich, Germany
Published online: 24 Jun 2008.
To cite this article: Richard Betz & Peter Klüfers (2008) Hydrido-bis(meso-
5
oxolanylen-3,4-dioxy)-λ -phosphane, Phosphorus, Sulfur, and Silicon and the Related
Elements, 183:7, 1615-1629, DOI: 10.1080/10426500701696829
To link to this article: http://dx.doi.org/10.1080/10426500701696829
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Phosphorus, Sulfur, and Silicon, 183:1615–1629, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500701696829
5
Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ -phosphane
Richard Betz and Peter Kl u¨ fers
Department of Chemistry and Biochemistry, Ludwig Maximilians
University, Munich, Germany
5
The symmetric hydrido-spiro-λ -phosphane derived from anhydroerythritol (meso-
oxolane-3,4-diol, AnEryt), HP(AnErytH−2) (3), was prepared by two different syn-
2
thetic protocols. One route involves a three step synthesis starting from phos-
phorus trichloride via 2-chloro-tetrahydro-furo[3,4-d][1,3,2]dioxaphosphole (1) and
diethyl-(tetrahydro-furo[3,4-d][1,3,2]dioxaphosphol-2-yl)-amine (2) as intermedi-
ates. The first intermediate, P(AnErytH )Cl (1), was isolated as a crystalline solid
−2
and its structure was determined by single crystal X-ray diffraction. 1 is the first
example of a halogeno substituted phosphane derived from an aliphatic diol whose
molecular structure in the solid state was determined by X-ray diffraction stud-
ies. Alternatively, the title compound can also be obtained in a one-pot procedure
starting from tris(N,N-dimethylamino)phosphane. All new compounds were char-
acterized by their physical constants (melting point, refractory index), NMR, IR,
Raman, UV/VIS, mass spectrometry, as well as elemental analysis. Some spectro-
scopic proofs for the spiro nature of the title compound are given.
Keywords Alkylenedioxyphosphane; crystal structure; phosphorus; spiro compounds
INTRODUCTION
Phosphorus plays a key role in biochemistry as important part of
the desoxyribonucleid acid, adenosine triphosphate and many other
compounds in living organisms. The metabolism of nutrients involves
1
several phosphorylation steps. Based on the work of Westheimer
2
,3
et al., the possible intermediacy of a pentavalent phosphorus dur-
ing phosphoryl transfer reactions has been extensively discussed in
4
,5
the literature, and recently, the structure of an intermediate from
Received 12 September 2007; accepted 21 September 2007.
The authors thank Dr. Peter Mayer for professional help during crystal structure
analysis and Prof. T. M. Klap o¨ tke for generous allocation of measurement time on the
Raman spectrometer. Tobias Kerscher, M. Sc., is thanked for keen and swift assistance
during the preparation and performance of DFT calculations.
Address correspondence to Peter Kl u¨ fers, Department of Chemistry and Biochem-
istry, Ludwig Maximilians University, Butenandtstraße 5–13, 81377 Munich, Germany.
E-mail: kluef@cup.uni-muenchen.de
1615

1
616
R. Betz and P. Kl u¨ fers
a phosphoryl transfer reaction containing a pentacoordinate phospho-
6
rus atom was elucidated by means of a single crystal X-ray study.
Being ubiquitous in cellular environments, carbohydrates appear as
attractive bonding partners for pentavalent phosphorus. However, a
definite proof for the structure of such compounds based on data ob-
tained from single crystal X-ray experiments was lacking completely
in the literature up to some years ago. Important progress in solving
this problem was achieved by Holmes and co-workers by incorporation
of the phosphorus atom into a macrocyclic framework. Consequently,
5
a series of carbohydrate-substituted λ -phosphoranes with protected
glucofuranoside and xylofuranoside, β-chloralose and thymidine, was
investigated by single crystal X-ray diffraction showing for some of
these compounds formal hexacoordination by intramolecular donor
7
−9
5
interaction.
However, symmetric λ -phosphanes bearing two car-
bohydrate moieties are still unknown. Additionally, to faciliate bond-
ing of carbohydrates to phosphorus it would be desirable for the fifth
substituent at phosphorus to have a low steric demand. Pursuing the
5
latter strategy, hydrido-spiro-λ -phosphanes appear to be particularly
suitable for this purpose. This class of molecules has attracted some
attention during the 1960s and 1970s,1
0−12
but has been observed
only for a limited number of almost exclusively open-chain diols (ex-
13
cept cis-cyclohexane-1,2-diol ) leaving the question about the pos-
sible extension to carbohydrates as chelating partners unanswered.
5
To test whether hydrido-spiro-λ -phosphanes might, in principle, be
formed with carbohydrates, anhydroerythritol—a vicinal diol repre-
senting a model for furanoid carbohydrates containing cis-configured
hydroxyl groups—was used as a starting material. As of today, only
5
two structures of hydrido-spiro-λ -phosphanes resulting from vicinal
diols (pyrocatechol14 and 2,3-diphenylethane-1,2-diol ) have been elu-
15
cidated by means of single crystal X-ray diffraction.
RESULTS AND DISCUSSION
5
The synthesis of the hydrido-spiro-λ -phosphane with anhydroerythri-
tol as the chelating diol was performed according to two different syn-
thetic protocols described in the literature1
2,16
in a three-step sequence
starting from phosphorus trichloride and in one step starting from
tris(N,N-dimethylamino)phosphane (Scheme 1). Despite of the three
steps the first reaction sequence is of interest since exclusively cheap
starting materials are involved.
2
-Chloro-tetrahydro-furo[3,4-d][1,3,2]dioxaphosphole, P(AnErytH−2)
Cl (1), was obtained by reaction of anhydroerythritol with phospho-
rus trichloride in dichloromethane. It was isolated as a liquid, which

5
Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ -phosphane
1617
O
O
O
O
PCl
3
N,N-diethylamine
O
P
Cl
O
P
N
O
HO
OH
1
2
anhydroerythritol
H
P
N(CH
P
3
)
2
O
O
anhydroerythritol
O
O
(
H
3
C)
2
N
3 2
N(CH )
O
O
3
SCHEME 1 Routes for the preparation of the symmetric hydrido-spiro-λ5-
phosphane 3 derived from anhydroerythritol.
crystallizes on prolonged storage at room temperature. The results
of a single crystal X-ray study prove phosphorus to be part of a five-
membered chelate ring (Figure 1). The phosphorus atom is found at the
top of a trigonal pyramid. Bond lengths and angles around the phospho-
rus atom are in good agreement with the values reported in the liter-
ature for similar compounds derived from aromatic hydroxycarboxylic
acids or aromatic diols.1
7−25
A puckering analysis of the five-membered
rings according to Cremer and Pople shows the chelate ring, as well as
FIGURE 1 Molecular structure of P(AnErytH−2)Cl(1) (50% probability el-
˚
◦
lipsoids). Selected distances (in A) and angles (in ): Cl–P 2.1152(7), P–O13
1.6008(13), P–O12 1.6041(13), O12–C12 1.4459(18), O13–C13 1.4511(19), C12–
C13 1.542(2), O13–P–O12 95.48(6), O13–P–Cl 100.10(5), O12–P–Cl 99.90(5),
C12–O12–P 112.82(9), C13–O13–P 112.99(9), O12–C12–C13–O13 −0.22(16);
9
˚
◦
ring puckering analysis : P–O12–C12–C13–O13 Q
2
= 0.2325(12) A, ϕ
2
= 0.4(4)
˚
◦
(
envelope on P); O11–C11–C12–C13–C14 Q
2
= 0.3840(17) A, ϕ
2
= 0.9(3) (enve-
lope on O11).

1
618
R. Betz and P. Kl u¨ fers
the oxolane ring to adopt an envelope conformation.26 The oxolane moi-
ety is oriented away from the chlorine atom and syn to the free electron
pair at phosphorus.
A solution of crystals of 1 in CDCl3 shows two signals in the 31P NMR
spectrum and two sets of signals in the 13C NMR spectrum, which is
in accordance with the two possible stereoisomers (syn and anti) for
1
. According to integration of the 31P NMR signals the relative ratio
of the two isomers is about 30:1. A comparison between the carbon
resonances of anhydroerythritol and the corresponding signals in the
1
3
C NMR spectrum of 1 shows that the signal of the CH groups of the
latter in the case of the minor isomer are shifted by 13.4 ppm downfield.
For the major isomer the downfield shift of these carbon atoms is with
11.4 ppm less pronounced. No shift difference for the two isomers is
observed for the resonances attributable to the methylene groups. The
3
1
P NMR resonances at 183 ppm (minor isomer) and 175 ppm (major
2
7
isomer) are typical for trivalent phosphorus compounds of this type.
The proton spectrum of 1 shows the expected high order line pattern
for the ABM-part of an [ABM]2X spin system.
The compound is highly reactive and decomposes rapidly with evo-
lution of white fumes upon exposure to air or moisture.
To avoid halogenido-induced side reactions during the formation of
5
the desired hydrido-spiro-λ -phosphane, the remaining chlorine atom
at phosphorus was substituted for another appropriate leaving group.
Reaction of 1 with N, N-diethylamine in an aprotic solvent yielded the
amino substituted derivative 2, which was isolated by distillation. The
liquid showed no tendency to crystallize at room temperature even after
3
1
13
1
15
a storage period of more than 18 months. The P, C, H, and N NMR
spectra of 2 display each two sets of signals (ratio approximately 1:8),
which suggests the presence of a syn and an anti isomer. A comparison
1
3
of the C NMR chemical shifts of 2 with those of neat anhydroerythritol
shows for the CH carbon atoms in 2 a downfield shift of 8.0 ppm (main
isomer) and of 7.4 ppm (minor isomer). A small downfield shift of 2.0
13
ppm is observed for δ C of the methylene groups (Figure 2).
The coupling constants between 31P and N are nearly identical
15
(
about 90 Hz) for the minor and the major isomer. This is in good
agreement with the values reported in the literature for a similar com-
pound incorporating benzene-1,2-diol as the chelating unit and the
2
8
N, N-dimethylamine moiety bonded to phosphorus. The bonding of
nitrogen to the trivalent phosphorus atom causes a marked shift of the
1
5
15
N NMR signal to lower field as compared to the N resonance of neat
N, N-diethylamine. This shift amounts to 46 ppm for the main isomer
and 43 ppm for the minor isomer (Figure 3). As in the case of 1, the ring
protons in 2 display the ABM-part of an [ABM]2X spectrum.

5
Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ -phosphane
1619
FIGURE 2 13C NMR spectra of 2-chloro-tetrahydro-furo[3,4-d][1,3,2]dioxa-
phosphole (1) (top) and diethyl-(tetrahydro-furo[3,4-d][1,3,2]dioxaphosphol-2-
yl)-amine (2) (bottom) recorded in CDCl . For clarity, only the region containing
3
the resonances attributable to the anhydroerythritol moiety is shown.
Reaction of 2 with one equivalent of anhydroerythritol and sub-
sequent removal of the liberated N, N-diethylamine by distillation
yielded a colorless crystalline solid. The same product was also ob-
tained in a one-step procedure after prolonged heating of tris(N,N-
dimethylamino)phosphane with two equivalents of anhydroerythritol
in toluene.
3
1
1
The P{ H} NMR spectrum of the dissolved crystalline product
shows three resonances around −20 ppm. The values are in the range
5
that was reported in the literature for hydrido-spiro-λ -phosphanes re-
sulting from vicinal diols and provide a first indication for the formation
1
0−12
of 3.
The intensity of the two signals at −20 and −22 ppm is signifi-
cantly larger than that of the third resonance at −18 ppm with a relative
signal ratio of 1:5:4 (from lowest to highest field). As in the case of 2,
the appearance of three distinct resonances is indicative of syn/anti iso-
merism which is caused by the possible orientations of the meso-oxolan
rings with respect to the hydrogen atom at phosphorus. In the proton
3
1
coupled P NMR spectrum the signals split into dubletts with a large
P,H coupling constant and further into different multiplets with much

1
620
R. Betz and P. Kl u¨ fers
FIGURE 3 15N NMR spectra of diethyl-(tetrahydro-furo[3,4-d][1,3,2]
dioxaphosphol-2-yl)-amine (2) (top) and N, N-diethylamine (bottom) as neat
3
1
15
samples. The presence of two isomers as well as the P- N-coupling and the
marked downfield shift of the nitrogen resonance in 2 relative to the pure
amine are clearly visible.
smaller P,H coupling constants. The large P,H coupling constants range
between 820 and 830 Hz, which is typical for compounds of pentacoor-
dinated phosphorus with direct P-H bonds, thus further corroborating
the identity of 3.1
0−12
The proton coupled P NMR spectrum allows for
31
the identification of the syn/syn-, the syn/anti- and the anti/anti-isomer
on the basis of the splitting patterns and the signal intensities. The
signal at −22 ppm with the most complex splitting pattern is caused
by the syn/anti isomer due to the C2 symmetry of this molecule, which
makes the hydrogen atoms at the CH-moieties unequal. For the identi-
fication of the other two isomers, the splitting pattern no longer can be
used as the only discriminating tool due to the Cs symmetry of these two
stereoisomers. It is the marked difference in signal intensities, which
allows for a tentative assignment of the resonances. DFT calculations
2
9
at the B3LYP/aug-CCpVDZ level of theory with Gaussian03 for both
−
1
isomers show the anti/anti isomer to be 10.6 kJ mol more unfavorable
than the syn/syn isomer. Thus the resonance with the higher intensity
at −20 ppm may be attributed to syn/syn isomer.

5
Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ -phosphane
1621
O
H
O
O
O
O
O
O
O
P
O
O
P
O
OH
FIGURE 4 Equilibrium between the (formal) PV (left) and the PIII (right)
isomer of 3.
The 13C NMR spectrum of 3 further supports the proposed structure.
13
Assignment of the signals is based on a C DEPT-90 experiment. The
number of signals for the methine and methylene moieties observed is
in accord with the presence of the three stereoisomers discussed.
The IR spectrum of 3 shows the absence of free hydroxyl groups thus
3
ruling out the possibilty of 3 being a λ -phosphane. At the same time the
−
1
absorption at 2439 cm in the infrared spectrum and the emission at
−
1
30
2
437 cm in the Raman spectrum, prove the presence of a P-H bond.
◦
A small melting range of only around 2.5 C is observed for 3 even at
◦
a heating rate of only 1 C per min with resolidification occurring almost
instantaneously upon removal from the heating source. Obviously, an
III
V
adjustment of the equilibrium between P and (formal) P (Figure 4)
either does not take place or it proceeds so quickly, that no broad hys-
teresis can be observed for melting or resolidification, as was described
3
1
for the ethylene glycol derived hydrido-spirophosphorane.
Unfortunately, despite of several attempts of recrystallization, the
poor quality of the crystals obtained from 3 precluded the determination
of its molecular structure by means of single crystal X-ray diffraction.
Compound 3 is not stable against prolonged exposure to air or mois-
ture neither in solid state nor in solution. It easily decomposes with
cleavage of the P H and the P O bonds, yielding – predominantly –
phosphates.
CONCLUSION
Using anhydroerythritol as vicinal diol and starting from phosphorus
trichloride a new compound containing a pentacoordinate phosphorus
atom was synthesized in three steps. Its NMR, IR and Raman data
unambiguously identify the compound as a symmetric hydrido-spiro-
5
λ -phosphane. The synthetic protocols reported in the literature for the
5
synthesis of hydrido-spiro-λ -phosphanes with open-chain diols were
thus successfully applied to the synthesis of a cyclopentane-derived
diol.

1
622
R. Betz and P. Kl u¨ fers
The anhydroerythritol was used in this study as a configurationally
stable, non-reducing model compound for important sugars like D-
5
ribose. The formation of the hydrido-spiro-λ -phosphane 3 indicates,
that a an analogous synthetic route might be applied for the prepa-
5
ration of hydrido-spiro-λ -phosphanes derived from carbohydrates as
chelating dioles. The synthesis of symmetric carbohydrate-substituted
5
spiro-λ -phosphanes having a sterically non-demanding hydrogen atom
as the fifth substituent is of great importance. Such compounds would
provide precious information not only about the structures of postulated
hypervalent phosphorus containing intermediates in metabolism, but
also in the field of asymmetric catalysis, where diol-derived hydrido-
5
spiro-λ -phosphanes have already been applied as interesting ligands
for transition metal complexes.3
2,33
EXPERIMENTAL
Phosphorus trichloride (synthesis grade) was obtained from Merck and
used without further purification. Anhydroerythritol was synthesized
34
according to a published procedure. meso-Erythritol was obatined
from Acros and used as received. Resinous ion exchanger Amberlite IR-
120 was obtained from Aldrich in protonated form and applied without
further purification. Toluene, benzene and dichloromethane (all Fluka)
˚
were dried over molecular sieves (4 A) prior to use. N,N-Diethylamine
synthesis grade, Fluka) was stored over potassium hydroxide pellets
(
for several days before use. Tris(dimethylamino)phosphane (Fluka) was
used as received. All manipulations were carried out in flame-dried
glass-ware under an atmosphere of dry nitrogen applying standard
Schlenk-techniques.
1H NMR spectra were measured on a JEOL Eclipse spectrometer
at 270 MHz and are referenced to internal tetramethylsilane or the
respective solvent residual peak.3
5
13
C NMR spectra were obtained
with a JEOL Eclipse spectrometer at 68 MHz and are referenced to
3
5
internal tetramethylsilane or the respective solvent residual peak.
N and N NMR spectra were measured on a JEOL Eclipse spec-
1
4
15
trometer at 29 MHz and 41 MHz, respectively, and are referenced to
external nitromethane. 31P NMR spectra were obtained with a JEOL
Eclipse spectrometer at 109 MHz and are referenced to external 85%
H3PO4. Downfield shifts are indicated by positive values. Unless oth-
erwise stated all signals were detected as singulets. IR spectra were
recorded with a Perkin Elmer Spectrum BX FT-IR spectrometer with
a DuraSamplIR II ATR unit and a Bruker IFS 66v/S FTIR spec-
trometer. Raman spectra were measured with a Perkin Elmer 2000

5
Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ -phosphane
1623
NIR-FT spectrometer. UV/VIS spectra were measured with a CARY 50
Bio UV-Visible spectrometer in quartz glass cuvettes; extinction coeffi-
cients were not determined. Elemental analyses were performed with
a Vario Elementar EL apparatus. Determination of the chlorine con-
tent was done according to the procedure of Sch o¨ niger with the help
of a Metrohm Titroprocessor.3
6,37
The phosphorus content was deter-
mined by ICP-AES on a Varian-VISTA Simultan spectrometer. Melt-
ing points were obtained on a B u¨ chi-540 apparatus and are uncor-
rected. Refractory indices were measured on a Schmidt-Haensch DUR
◦
W2 apparatus at 25 C; thermostatization was achieved by means of a
Haake B5 waterbath operated with a Haake F6 control device. Sin-
gle crystal X-ray studies were performed on a Nonius Kappa CCD
diffractometer.
Due to the sometimes scarce information in the literature, detailed
experimental information is given also for the literature procedures
followed.
Synthesis of Anhydroerythritol
In a round-bottomed flask (250 mL), equipped with a Vigreux-column-
equipped distillation head, meso-erythritol (50.00 g, 409 mmol) and Am-
berlite IR-120 (5.04 g) were thoroughly mixed by shaking. The mixture
was then molten by means of an electrical heating device and the ob-
tained crude product continuously removed from the reaction vessel by
◦
distillation (3.5 mbar, 113 C at the top of the distillation head). For
drying, the crude product was dissolved in dichloromethane (150 mL),
˚
and the colorless solution was stored over molecular sieves (35 g, 4 A)
for three days. After filtration the solvent was removed under reduced
pressure and the residue was once again distilled (identical conditions
as given above). A colorless and odorless viscous liquid was obtained,
◦
which solidified upon storage at 4 C. Yield: 31.29 g, 301 mmol, 73.6%. ρ
−
3
1
◦
=
1.38 g·cm . H NMR (DMSO-d6, 270.2 MHz, 24 C): δ = 4.71 (d, J=
3
3
.8 Hz, 2H, OH), 4.04–3.96 (m, 2H, CHOH), 3.76–3.71 (m, 2H, CH2O),
.47–3.42 (m, 2H, CH2O). 13C{ H} NMR (DMSO-d6, 67.9 MHz, 26 C):
1
◦
δ = 72.1 (CH2O), 70.9 (CHOH). Elemental analysis: Found (calculated
+
for C4H8O3): C 45.99% (46.15%), H 7.89% (7.75%). MS (DEI ) m/z (rel.
+
+
+
intensity): 105 (48, [M + H] ), 104 (13, [M] ), 87 (43, [M−OH] ), 70
+
(
0.4, [M−OH−OH] ). IR (KBr): ν = 3381 (s), 2949 (s), 2877 (s), 1466
(
9
m), 1416 (m), 1364 (m), 1335 (m), 1213 (m), 1128 (s), 1058 (s), 992 (m),
−
1
04 (m), 874 (m), 736 (w), 661 (w), 558 (w), 418 (w) cm . Raman (neat):
ν = 3363 (22), 2954 (100), 2880 (81), 1478 (51), 1294 (28), 1215 (37),

1
624
R. Betz and P. Kl u¨ fers
1
125 (29), 989 (26), 907 (54), 859 (89), 735 (22), 562 (43), 388 (32) cm−1.
Refractory index: 1.4733.
Synthesis of 2-Chloro-tetrahydro-furo[3,4-d][1,3,2]
dioxaphosphole (1)
In a three-necked flask (250 mL), equipped with a dropping funnel and
a pressure equalizing valve, phosphorus trichloride (8.75 mL, 13.73 g,
100 mmol) was dissolved in dichloromethane (50 mL). With vigorous
stirring a solution of anhydroerythritol (7.54 mL, 10.41 g, 100 mmol) in
dichloromethane (10 mL) was dropped to this mixture in the course of 30
min; during this time a strong evolution of gaseous reaction products
was observed. After completion of the addition, the reaction mixture
was stirred for 4 h at room temperature and then for additional 30 min
◦
at approximately 40 C (waterbath). All volatile components from the
reaction mixture were removed at room temperature under reduced
pressure. The residue was distilled under reduced pressure over a Vi-
−2
◦
greux column (2.0 × 10 mbar, 59 C at the top of the distillation head).
A colorless, slightly oily liquid with a pungent garlic-like odor was ob-
tained, which solidified after storage for several weeks at room tem-
perature to give a colorless crystalline solid with a pungent odor. Both
liquid and solid samples fumed upon exposal to air. Yield 13.43 g, 79.7
−
3
1
mmol, 79.7%. ρ = 1.44 g cm (as liquid sample). H NMR (CDCl3, 270.2
◦
MHz, 25 C): δ = 5.22–5.17 (m, 2H, HCO), 4.13–4.08 (m, 2H, CH2), 3.60–
1
◦
3
.50 (m, 2H, CH2). 13C{ H} NMR (CDCl3, 67.9 MHz, 26 C): δ = 84.9 (d,
JPC= 11.2 Hz, HCO, minor isomer), 82.9 (d, JPC = 8.0 Hz, HCO, major
31
1
isomer), 72.9 (d, JPC = 2.3 Hz, CH2). P{ H} NMR (CDCl3, 109.4 MHz,
◦
2
5 C): δ = 183 (minor isomer), 175 (major isomer). Elemental analysis:
Found (calculated for C4H6ClO3P): C 28.61% (28.51%) H 3.64% (3.59%),
Cl 16.41% (21.04%); ICP-AES: Found (calculated for C4H6ClO3P): P
17.15% (18.38%); the larger deviations in the case of chlorine and phos-
phorus are due to problems while preparing the highly moisture sen-
+
sitive compound for analysis. MS (EI ) m/z (rel. intensity): 168 (0.7,
+
+
+
[
(
(
(
M] ), 133 (39, [M−Cl] ), 69 (100, [M−PO2Cl−H] ). IR (KBr): ν = 2993
w), 2923 (w), 2902 (w), 2861 (w), 2725 (w), 1784 (w), 1750 (w), 1461
w), 1448 (w), 1337 (m), 1309 (m), 1266 (m), 1230 (w), 1201 (w), 1092
s), 1049 (m), 1028 (m), 1012 (s), 979 (m), 938 (s), 917 (s), 876 (s), 849 (m),
8
5
2
1
1
34 (m), 816 (m), 787 (m), 765 (m), 735 (w), 714 (m), 616 (w), 590 (m),
−1
75 (w), 550 (w), 467 (m), 412 (m) cm . Raman (neat): ν = 2998 (100),
980 (87), 2925 (25), 2904 (21), 2868 (64), 1463 (22), 1449 (25), 1369 (8),
342 (7), 1323 (10), 1317 (11), 1289 (10), 1266 (15), 1229 (13), 1202 (16),
097 (18), 1084 (11), 1049 (8), 1026 (6), 1011 (24), 935 (38), 914 (13), 873

5
Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ -phosphane
1625
(
(
10), 835 (7), 787 (53), 715 (40), 590 (22), 567 (23), 471 (23), 460 (60), 410
48), 393 (19), 328 (39), 230 (19), 209 (31) cm . UV/VIS (acetonitrile):
−
1
λmax = 259.1, 265.1, 272.0 nm. UV/VIS (cyclohexane): λmax = 260.0,
◦
2
65.5, 272.4 nm. M.p.: 44.6–46.0 C.
Synthesis of Diethyl-(tetrahydro-furo[3,4-d][1,3,2]
dioxaphosphol-2-yl)-amine (2)
In a three-necked flask (500 mL), equipped with a dropping fun-
nel and a pressure equalizing valve, 2-chloro-tetrahydro-furo[3,4-
d][1,3,2]dioxaphosphole (7.61 mL, 10.95 g, 65 mmol) was dissolved in
benzene (150 mL). Under cooling with an ice-bath, a solution of diethy-
lamine (13.46 mL, 9.51 g, 130 mmol) in benzene (20 mL) was added
dropwise to this solution over 30 min. Slowly, a colorless solid started
to precipitate from the reaction mixture. After completion of the addi-
tion, the ice-bath was removed and the colorless suspension was stirred
at room temperature overnight. The opalescing solid was removed by fil-
tration over a coarse-sintered glas disk and from the filtrate all volatile
compounds were removed under reduced pressure. The residue was dis-
−
2
tilled under reduced pressure over a Vigreux-column (2.0×10 mbar,
◦
7
8 C at the top of the distillation head). A colorless, oily liquid with a
garlic-like odor was obtained. Yield: 12.36 g, 60.2 mmol, 92.6%. ρ = 1.16
−
3
1
◦
g cm . H NMR (CDCl3, 270.2 MHz, 23 C): δ = 4.87–4.84 (m, 2H, HCO,
major isomer), 4.64–4.59 (m, 2H, HCO, minor isomer), 4.07–4.02 (m, 2H,
CH2, minor isomer), 3.88–3.84 (m, 2H, CH2, major isomer), 3.49–3.48
(
3
m, 2H, CH2, minor isomer), 3.46–3.39 (m, 2H, CH2, major isomer),
.11–2.99 (m, 4H, N(CH2), minor isomer), 2.97–2.84 (m, 4H, N(CH2),
major isomer), 1.03–0.96 (m, (6+6)H, CH3, major and minor isomer).
1
3
1
◦
C{ H} NMR (CDCl3, 67.9 MHz, 25 C): δ = 79.4 (d, JPC = 10.6 Hz,
HCO, major isomer), 78.8 (d, JPC= 7.3 Hz, HCO, minor isomer), 74.9 (d,
JPC = 2.6 Hz, CH2, major isomer), 74.4 (d, JPC = 1.3 Hz, CH2, minor iso-
mer), 37.9 (d, JPC = 20.5 Hz, N(CH2), major isomer), 36.6 (d, JPC = 22.1
Hz, N(CH2), minor isomer), 15.1 (d, JPC = 2.9 Hz, CH3, major and minor
1
4
1
◦
isomer). N{ H} NMR (neat, 28.9 MHz, 24 C): no distinct resonances
1
5
1
◦
visible. N{ H} NMR (neat, 40.5 MHz, 22 C): δ = −287.6 (d, JPN= 89.3
3
1
1
Hz, major isomer), −291.5 (d, JPN = 89.8 Hz, minor isomer). P{ H}
◦
NMR (CDCl3, 109.4 MHz, 25 C): δ = 163 (13%), 152 (87%). Elemen-
tal analysis: Found (calculated for C8H16NO3P): C 46.43% (46.83%),
H 7.97% (7.86%), N 7.03% (6.83%). ICP-AES: Found (calculated for
+
C8H16NO3P): P 13.98% (15.10%). MS (DEI ) m/z (rel. intensity): 205
+
+
+
(
[
(
16, [M] ), 190 (36, [M−CH3] ), 133 (100, [M−N(CH2CH3)2] ), 72 (26,
+
M−P(C4H6O3)] ). IR (neat): ν = 2969 (m), 2934 (m), 2852 (m), 1461
w), 1376 (m), 1364 (w), 1344 (w), 1322 (w), 1290 (w), 1264 (w), 1227

1
626
R. Betz and P. Kl u¨ fers
(
9
w), 1204 (m), 1182 (m), 1100 (s), 1060 (m), 1036 (m), 1013 (s), 930 (s),
08 (s), 878 (w), 847 (s), 787 (m), 756 (m), 707 (w), 683 (m), 666 (m)
−
1
cm . Raman (neat): ν = 2990 (60), 2934 (100), 2870 (59), 1451 (51),
1
7
101 (19), 1078 (28), 1041 (21), 1016 (16), 932 (35), 853 (29), 760 (30),
−1
09 (38), 668 (69), 560 (17), 325 (25) cm . UV/VIS (acetonitrile): λmax
204.9 nm. UV/VIS (cyclohexane): λmax = 209.0 nm. Refractory index:
.4821.
=
1
Synthesis of Hydrido-bis(meso-oxolanylen-3,4-dioxy)
5
-
λ -phosphane (3)
Method A
A mixture of diethyl-(tetrahydro-furo[3,4-d][1,3,2]dioxaphosphol-2-
yl)-amine (8.84 mL, 10.26 g, 50.0 mmol) and anhydroerythritol (3.78
mL, 5.21 g, 50.0 mmol) was placed in a Schlenk-flask (50 mL) equipped
with a distillation head. The reaction mixture was heated under a
weak steady stream of nitrogen until no more liquid distilled. Dur-
ing the heating period, a growing amount of colorless solid formed in
the Schlenk-flask, which finally completely replaced the liquid phase.
Yield: 11.18 g, 47.3 mmol, 94.6%.
Method B
A solution of tris(N,N-dimethylamino)phosphane (3.64 mL, 3.26 g,
20 mmol) in toluene (10 mL) was mixed with anhydroerythritol (3.02
mL, 4.16 g, 40 mmol) in a Schlenk-flask and heated under reflux for 6 h.
A steady stream of nitrogen was passed through a pressure equalizing
valve located at the head of the reflux condenser throughout the heating
period. Upon cooling to room temperature, a white crystalline solid was
obtained from the colorless reaction mixture. Removal of the solvent
under reduced pressure afforded a white crystalline solid. Yield: 1.42
g, 6.01 mmol, 30.1%.
1
◦
H NMR (CDCl3, 270.2 MHz, 22 C): δ = 7.26 (d, JPH = 832 Hz, 1H,
PH, minor isomer, syn or anti), 7.15 (d, JPH = 831 Hz, 1H, PH, syn/anti),
7
3
2
7
1
1
.13 (d, JPH = 822 Hz, 1H, PH, syn or anti), 4.64–4.53 (m, HCO), 4.09–
13 1
.88 (m, CH2), 3.50–3.41 (m, CH2). C{ H} NMR (CDCl3, 67.9 MHz,
◦
5 C): δ = 75.5 (d, JPC= 1.8 Hz, CH), 74.70 (d, JPC = 3.2 Hz, CH2),
4.66 (CH2), 74.5 (CH), 74.3 (d, JPC = 2.1 Hz, CH2), 74.2 (d, JPC =
3
1
.2 Hz, CH2), 74.1 (d, JPC = 1.2 Hz, CH), 73.8 (CH). P NMR (CDCl3,
◦
1
3
09.4 MHz, 25 C): δ = −18 (dq, JPH= 833 Hz, JPH= 16.4 Hz, syn or
1
3
anti, 11%), −20 (dq, JPH= 822 Hz, JPH= 12.0 Hz, syn or anti, 47%),
1
−
22 (dm, JPH= 832 Hz, syn/anti, 42%). Elemental analysis: Found
(
calculated for C8H13O6P): C 40.65% (40.69%), H 6.26% (5.55%). ICP-
AES: Found (calculated for C8H13O6P): P 12.48% (13.12%); the large

5
Hydrido-bis(meso-oxolanylen-3,4-dioxy)-λ -phosphane
1627
deviation in the case of phosphorus is due to problems while prepar-
+
ing the highly moisture-sensitive compound for analysis. MS (DCI ,
+
+
isobutane) m/z: 237 ([M+H] ), 151 ([M−C4H6O2+H] ). IR (neat): ν =
2
2
1
988 (w), 2940 (m), 2901 (w), 2844 (m), 2725 (w), 2675 (w), 2647 (w),
439 (w), 1463 (w), 1448 (w), 1374 (w), 1352 (w), 1336 (w), 1286 (w),
263 (w), 1233 (w), 1204 (w), 1103 (s), 1060 (m), 1032 (s), 996 (w), 947
(
(
2
(
7
m), 906 (s), 891 (s), 845 (s), 782 (m), 728 (s), 711 (s), 652 (m), 631
−
1
m), 584 (w) cm . Raman (neat): ν = 2995 (100), 2981 (43), 2942 (67),
906 (38), 2845 (44), 2437 (32), 1462 (37), 1337 (14), 1264 (17), 1205
13), 1106 (16), 1057 (22), 945 (31), 913 (38), 869 (22), 817 (8), 757 (41),
−
1
30 (48), 588 (17), 526 (25), 481 (12), 336 (25), 183 (18) cm . M.p.:
10.9–113.5 C.
◦
1
Crystal Structure Determination and Refinement
A single crystal suitable for X-ray diffraction was selected by means of
a polarizing microscope and mounted on the tip of a glass fiber. Data
collection was performed on a Nonius Kappa CCD diffractometer using
˚
graphite-monochromatized MoKα radiation (λ= 0.71073 A). The struc-
38
ture was solved by Direct Methods (SIR 97 ) and refined by full-matrix
2
39
least-squares calculations on F (SHELXL-97 ). Anisotropic displace-
ment parameters were refined for all non-hydrogen atoms. Correct
assignment of space group and search for missed or additional sym-
metry was performed with PLATON to check whether an orthorhombic
setting was chosen correctly over a tetragonal one despite the nearly
40
identical lengths of axes b and c. Molecular graphics were drawn with
4
1
ORTEPIII.
Crystallographic Data for 1
−1
C4H6ClO3P, Mr = 168.51 g mol , colorless platelet, 0.21 × 0.17
0.04 mm, orthorhombic, Pbca, a = 9.5680(2), b = 11.8940(3), c =
×
˚
˚ 3
−3
1
1.8950(2) A, V = 1353.67(5) A , Z = 8, ρ = 1.654 g·cm , T = 200(2)
−1
K, µ(MoKα) = 0.730 mm , multi-scan absorption correction, θ range:
◦
3
.22–27.46 , 2853 refls., 1543 independent and used in refinement, 1322
with I ≥ 2σ(I), Rint = 0.0118, mean σ(I)/I = 0.0156, 83 parameters,
2
R(Fobs) = 0.0303, Rw(F ) = 0.0827, S = 1.069, min. and max. residual
˚
−3
electron density: −0.430/0.332 e A , max. shift/error = 0.001.
Crystallographic data for the structure has been deposited with the
Cambridge Crystallographic Data Centre (1: 655562). Copies of the data
can be obtained free of charge on application to the Director, CCDC, 12
Union Road, Cambridge CB2 1EZ, UK (Fax: int.code+(1223)336–033;
e-mail for inquiry: file-server@ccdc.cam.ac.uk).

1
628
R. Betz and P. Kl u¨ fers
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