Unusual reaction of 8-chloro-2-cyclohexyl-4-phenylbenzo[e]-1,2-oxaphosphinine-2-oxide with tetramethylenebis(magnesium bromide)

Article abstract of DOI:10.1016/j.mencom.2008.05.012

The reaction of 8-chloro-2-cyclohexyl-4-phenylbenzo[e]-1,2-oxaphosphinine-2-oxide with ethyl- and phenylmagnesium bromides and tetramethylenebis(magnesium bromide) is a versatile approach to the synthesis of unsymmetrical phosphine oxides. With the latter Grignard reagent, an unusual phosphorus-carbon cleavage also occurs to yield a pentacoordinate phosphorus derivative, 2,3,8,9-bis(4-chlorobenzo)-6-cyclohexyl-6,9-diphenyl-1,7-dioxa-6-phosphaspiro[5.5]deca-1,9-diene.

Full text of DOI:10.1016/j.mencom.2008.05.012

Mendeleev
Communications
Mendeleev Commun., 2008, 18, 147–149
Unusual reaction of 8-chloro-2-cyclohexyl-4-phenylbenzo[e]-1,2-oxa-
phosphinine-2-oxide with tetramethylenebis(magnesium bromide)
Dmitry A. Tatarinov,a,b Vladimir F. Mironov,*a,b Elena N. Varaksina,a Dmitry B. Krivolapov,a
Igor A. Litvinov,a Rashid Z. Musin,a Boris I. Buzykina and Alexander I. Konovalova,b
a A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Centre of the Russian Academy
of Sciences, 420088 Kazan, Russian Federation. Fax: +7 843 275 5322; e-mail: mironov@iopc.knc.ru
b A. M. Butlerov Chemical Institute, Kazan State University, 420008 Kazan, Russian Federation
DOI: 10.1016/j.mencom.2008.05.012
The reaction of 8-chloro-2-cyclohexyl-4-phenylbenzo[e]-1,2-oxaphosphinine-2-oxide with ethyl- and phenylmagnesium
bromides and tetramethylenebis(magnesium bromide) is a versatile approach to the synthesis of unsymmetrical phosphine oxides.
With the latter Grignard reagent, an unusual phosphorus–carbon cleavage also occurs to yield a pentacoordinate phosphorus
derivative, 2,3,8,9-bis(4-chlorobenzo)-6-cyclohexyl-6,9-diphenyl-1,7-dioxa-6-phosphaspiro[5.5]deca-1,9-diene.
Achiral (R3P=O), prochiral (R2R1P=O) and chiral (R1R2R3P=O)
phosphine oxides are the main precursors in the syntheses of
corresponding phosphines,1–11 which are widely used as ligands
in metal complex catalysts2,4,6,10,12 and neutral extracting agents
for rare-earth metals.13–17 Phosphine oxides can also be used as
ligands in reactions catalysed by palladium and molybdenum
complexes.18–20 The syntheses of phosphine oxides include
reactions of organolithium and organomagnesium compounds
with acyclic derivatives of tetracoordinate phosphorus containing
alkoxy groups or chlorine atoms21–23 or addition of hydrophos-
phoryl compounds to C=C bonds.24 Reactions of organolithium
and organomagnesium compounds with phosphorus derivatives
containing both alkoxy groups and chlorine atoms are charac-
terised by medium or low chemoselectivity. The use of Grignard
reagents results in phosphine oxide mixtures, which are difficult
to separate.
In this work, we attempted to obtain unsymmetrical phosphine
oxides containing dissimilar substituents at the phosphorus atom,
viz., six-membered phosphorus-containing heterocycles with one
phosphorus–oxygen bond, such as 2,8-dichloro-4-phenylbenzo[e]-
1,2-oxaphosphinine-2-oxide 1. Compound 1 also contains an
active phosphorus–chlorine bond and can be easily obtained
by the reaction of phenylacetylene with 2,2,2-trichlorobenzo-
1,3,2-dioxaphosphole.25 Phosphinine 1 selectively reacts with
cyclohexylmagnesium bromide to give only 8-chloro-2-cyclo-
hexyl-4-phenylbenzo[e]-1,2-oxaphosphinine-2-oxide 2, in a high
yield. Note that introduction of the second cyclohexyl radical
does not occur due to the sterical effect of this substituent in the
Grignard reagent. The structure of compound 2 was confirmed
by NMR spectroscopy and mass spectrometry.† Derivative 2
containing a chiral phosphorus atom is capable of reacting with
Grignard reagents obtained from non-branched alkyl halides or
aryl halides; this reaction affords phosphine oxides 3, 4 with
three different substituents through the cleavage of the oxaphos-
phinine heterocycle (Scheme 1).†
The reaction of 8-chloro-2-cyclohexyl-4-phenylbenzo[e]-
1,2-oxaphosphinine-2-oxide with tetramethylenebis(magnesium
bromide) is unusual. The formation of diphosphine oxide deriva-
tive 5 is not the major pathway of the reaction (Scheme 2).‡ The
main pathway is the unexpected formation of spirophosphorane
derivative 9 (its content is 47% in the reaction mixture after
hydrolysis). We failed to find data on a similar behaviour of
Grignard reagents toward phosphorus derivatives, though examples
of sulfur–carbon bonds cleavage were reported.26
1
O
8
O
i, C6H11MgBr
ii, H+, H2O
2
O
O
8a
4a
13
7
P
P
Cl
85–90%
3
6
15
14
Cl
Cl
16
4
5
9
Ph
10
11
1
12
OH
O
2
i, RMgBr
ii, H+, H2O
R
P
Cl
85–90%
Ph
3 R = C17H2C18H3
18
19
17
20
4 R =
Scheme 1
†
Melting points (uncorrected) were measured with a Boetius melting
Scheme 2 shows a possible pathway for the formation of this
compound, which involves a reaction of phosphinine oxide 2
with an organomagnesium compound to yield organodimagnesium
derivative 6 or its cyclic form 6a (examples of similar organo-
dimagnesium derivatives are known27). A similar reaction may
be considered as the ligand replacement of the basic radical by
more acidic one at a magnesium atom. This process should also
give a molecule of 2-cyclohexyltetrahydrophosphole-2-oxide 7,
which has not been isolated. However, its presence follows from
the chemical shift of the corresponding signal in the 31P NMR
spectrum (dP 78.2 ppm) of the reaction mixture, which agrees
with the corresponding values for similar compounds, containing
point apparatus. NMR spectra were recorded with Bruker Avance-600
(1H, 600 MHz; 13C, 150.9 MHz), Bruker Avance-400 (1H, 400 MHz;
13C, 100.6 MHz) and Bruker CXP-100 (31P, 36.48 MHz) spectrometers.
The dH and dP values were determined relative to internal (HMDS) or
external (H3PO4) standards. The IR spectrum was recorded with a Bruker
Vector-22 instrument in Nujol. EI mass spectra were obtained with a
TRACE MS Finnigan MAT instrument; the ionization energy was 70 eV
and the ion source temperature was 200 °C. The samples were introduced
into the ion source via a direct inlet system. The evaporating ampoule
was heated from 35 to 150 °C at a rate of 35 K min–1. The mass spectro-
metric data were processed using the Xcalibur program.
For syntheses and characteristics of compounds 2–4 see Online
Supplementary Materials.
– 147 –
© 2008 Mendeleev Communications. All rights reserved.

Mendeleev Commun., 2008, 18, 147–149
three P–C bonds.28 Presumably, organomagnesium compound 6
C(7)
C(6)
C(8a)
C(4a)
C(4)
C(14)
subsequently reacts with phosphinate 2 to give magnesium-
containing phosphine oxide 8; the signal with dP 49.9 ppm
(diethyl ether/benzene) in the 31P NMR spectrum, which disappears
after treatment of the reaction mixture with water, can be assigned
to compound 8. After water treatment, final compound 9 appears;
it has a characteristic peak with dP –65.0 ppm (benzene) in the
31P NMR spectrum.
Compound 5 contains two chiral centres and might be
expected to form two diastereomers (d,l- and mezo-). However,
the signals of its atoms in NMR spectra are broadened, which
does not allow us to conclude on the process stereoselectivity.
Only one diastereoisomer was isolated after crystallization
from CHCl3.
The structures of compounds 5 and 9 were confirmed by
NMR spectroscopy, mass spectrometry‡ and single-crystal
X-ray diffraction.§ Figures 1 and 2 show the geometry of the
molecules.
Diphosphine oxide 5 (mezo-form, PSPR) was isolated as a
solvate with thichloromethane and water (Figure 1). The phos-
phorus atoms have a slightly distorted tetrahedral configuration.
The butylene fragment with two phosphorus atoms is almost
planar. The cyclohexyl substituents have a chair conformation.
In the crystal of compound 5, intramolecular OH···O hydrogen
bonds between the phosphorus-containing molecules and solvate
water were revealed. As a result, infinite hydrogen-bonded
C(8)
O(2b)
H
Cl(6)
C(5)
C(13)
O(1)
P(2b)
C(21b)
C(12)
C(9)
C(11)
C(10)
C(4b)
C(3b)
C(10b)
C(11b)
C(22b)
Cl(3)
H
O(20)
C(21)
C(3)
P(2)
H
C(4ba)
H
C(50)
C(15)
C(16)
C(12b)
C(13b)
Cl(1)
C(8ba)
C(22)
C(17)
Cl(2)
O(1b)
C(19)
C(20)
C(6b)
Cl(6b)
O(2)
H
C(18)
C(8b)
C(7b)
Figure 1 Molecular geometry of compound 5 in a crystal (a solvate with
CHCl3 and water). Selected bond lengths (Å): C(3)–C(4) 1.338(5), C(3)–
P(2) 1.792(4), C(4)–C(9) 1.483(6), C(4)–C(4a) 1.503(5), C(15)–P(2)
1.801(4), C(21)–C(22) 1.528(6), C(21)–P(2) 1.791(4), C(22)–C(22b)
1.523(8), O(2)–P(2) 1.501(3); bond angles (°): C(4)–C(3)–P(2) 131.6(3),
C(9)–C(4)–C(4a) 116.5(3), C(22)–C(21)–P(2) 113.4(3), C(22b)–C(22)–
C(21) 112.0(4), O(2)–P(2)–C(21) 111.4(2), O(2)–P(2)–C(3) 109.9(2),
C(21)–P(2)–C(3) 107.6(2), O(2)–P(2)–C(15) 111.9(2), C(21)–P(2)–C(15)
106.8(2), C(3)–P(2)–C(15) 109.2(2).
chains are formed along the 0c crystal axis. The hydrogen bond
parameters are as follows: O(1)–H(1A)···O(20)' (–x, –1/2 + y,
3/2 – z), d(O–H) 0.83(6) Å, d(H···O') 1.88(6) Å, d(O···O')
2.692(5) Å, Ð(O–H–O') 166(6)°; O(20)–H(201)···O(2)' (–x,
1/2 + y, 1/2 – z), d(O–H) 0.86(5) A, d(H···O') 1.93(5) Å, d(O···O')
2.777(4) Å, Ð(O–H–O') 174(8)°; O(20)–H(202)···O(2)' (x, 1/2 – y,
1/2 + z), d(O–H) 0.9(1) Å, d(H···O') 2.02(11) Å, d(O···O')
2.853(5) Å, Ð(O–H–O') 163(8)°.
OH
HO
The phosphorus atom in 9 (a solvate with two benzene
molecules, Figure 2) has an almost regular trigonal-bipyramidal
O
O
P
P
Cl
Cl
‡
1,10-Bis(5-chloro-2-hydroxyphenyl)-3,8-bis(cyclohexyl)-1,10-diphenyl-
Ph
Ph
3,8-diphosphadeca-1,9-diene-3,8-dione 5. The Grignard reagent obtained
from magnesium (0.48 g, 0.02 mol) and 1,4-dibromobutane (1.2 ml,
0.01 mol) in diethyl ether (15 ml) was added dropwise to a heated
solution (78 °C) of compound 2 (1.8 g, 0.005 mol) in benzene (10 ml).
The resulting reaction mixture was refluxed for 3 h (78 °C), cooled to
20 °C and treated with water, hydrochloric acid solution (5 ml in 20 ml
of water) to pH 4.0 and water. The aqueous and organic layers were
separated and the organic layer was dried in vacuo (12 Torr, 80 °C). The
resulting viscous oil was twice extracted with diethyl ether. The ether
extract was separated. The residue was crystallized from chloroform.
The crystalline precipitate that formed was filtered off and dried in vacuo
(12 Torr, 100 °C). The yield of compound 5 (as a solvate with chloroform
and water, 1:1:1) was 0.83 g (42%), mp 125–128 °C. 1H NMR (400 MHz,
5
2
i, [BrMg(CH2)2]2
ii, H+, H2O
[BrMg(CH2)2]2
O
O
MgBr
MgBr
Mg
· MgBr2
Cl
Cl
Ph
Ph
6
6a
+
2
CDCl3, 25 °C) d: 6.32 [br. d, H(3), JPCH 15.8 Hz], 6.92 [br. d, H(5),
3
4JH(7)CCCH(5) 2.3 Hz], 7.23 [br. dd, 1H, H(7), JH(8)CCH(7) 8.9 Hz,
3
4JH(5)CCCH(7) 2.3 Hz], 7.05 [br. d, H(8), JH(7)CCH(8) 8.9 Hz], 7.29, 7.35
O
P
2
(2m, Ph), 7.38 (s, CHCl3), 1.92, 1.84, 1.73, 1.54, 1.36, 1.24–1.25
(6br. m, C6H11). 31P-{1H} NMR (36.5 MHz, [2H6]acetone) dP: 45.1 (br. s).
IR (n/cm–1): 3380 (very br., OH), 2722 (very br.), 1588, 1568, 1495, 1413,
1330, 1281, 1219, 1115-1120, 1031, 942, 917, 890, 846, 823, 766, 723,
7
Cl
+
+
·
692, 633, 554, 517, 494, 452. MS, m/z: 774 [M] , 757 [M – OH] , 756
Ph
P
[M - H2O]+, 739 [M – Cl]+, 721 [M – H2O – Cl]+, 673 [M – H2O – C6H11]+,
528 [C30H39ClO2P]+, 445 [C24H28ClO2P]+, 228 [C14H9ClO]+, 212 [C14H9Cl]+
,
OMgBr
83 [C6H11]+, 55 [C4H7]+, 41 [C3H5]+.
OMgBr
O
2,3,8,9-Bis(4-chlorobenzo)-6-cyclohexyl-6,9-diphenyl-1,7-dioxa-6-phos-
phaspiro[5.5]deca-1,9-diene 9. The ethereal extract from the synthesis
of compound 5 was evaporated and the resulting viscous residue was
crystallized from benzene. The yield of compound 9 (as a solvate with
two benzene molecules) was 0.3 g (21%), mp 75 °C. 1H NMR (400 MHz,
CDCl3, 25 °C) d: 7.39–7.41 [m, H(11), H(12)], 7.34 [dd, H(7), 3JH(8)CCH(7)
8.7 Hz, 4JH(5)CCCH(7) 2.6 Hz], 7.10 [m, H(10)], 7.07 [d, H(5), 4JH(7)CCCH(5)
2.6 Hz], 7.02 [d, H(8), 3JH(7)CCH(8) 8.7 Hz], 5.88 [d, H(3), 2JPCH(3) 25.2 Hz],
Cl
Ph
8
– BrMgX
X = Cl, Br
HCl, H2O
2
3
2.68 [dtt, H(15), JPCH(15) 12.7 Hz, JH(16ax)CCH(15) 12.3–12.5 Hz,
3JH(16eq)CCH(15) 2.9–3.0 Hz], 2.06 [dtdd, H(18ax), 2JH(18eq)CH(18ax) 12.6 Hz,
3JH(17ax)CCH(18ax) 12.6 Hz, 3JH(17eq)CCH(18ax) 4.0 Hz, 3JH(19eq)CCH(18ax) 4.3 Hz],
2.30, 1.91, 1.77–1.79, 1.35–1.45 [4m, H(16), H(17), H(19), H(20)].
31P-{1H} NMR (36.5 MHz, CDCl3) dP: –65.0 (s). For 13C NMR, IR and
mass spectra of 9 see Online Supplementary Materials.
Cl
O
O
Cl
P
Ph
Ph
9
Scheme 2
– 148 –

Mendeleev Commun., 2008, 18, 147–149
oxaphosphinine rings have a distorted boat conformation con-
taining two planar fragments, viz., O(1)C(8a)C(4a)C(4) and
C(4a)C(4)C(3)P(2) [the P(2) and C(3) atoms deviate by 1.1152(4)
and 0.411(3) Å from the first plane, which is planar to within
0.008(3) Å; the O(1) and C(8a) atoms deviate by –0.985(2)
and –0.545(3) Å from the second plane, which is planar to
within 0.021(3) Å].
Cl(6)
C(6)
C(5)
C(4a)
C(13)
C(14)
C(9)
C(7)
C(8)
C(8a)
C(12)
C(4)
C(11)
C(10)
C(3)
Online Supplemetary Materials
Supplementary data associated with this article can be found
in the online version at doi: 10.1016/j.mencom.2008.05.012.
O(1)
ax
eq
eq
eq
P(2)
C(3b)
O(1b)
ax
References
Cl
C(15A)
1
2
3
4
K. M. Pietrusiewicz and M. Zabiocka, Chem. Rev., 1994, 94, 1375.
J. Holz, M. Quirmbach and A. Borner, Synthesis, 1997, 983.
T. Imamoto, S.-i. Kikuchi, T. Miura and Y. Wada, Org. Lett., 2001, 3, 87.
A. G. Tolstikov, T. B. Khlebnikova, O. V. Tolstikova and G. A. Tolstikov,
Usp. Khim., 2003, 72, 902 (Russ. Chem. Rev., 2003, 72, 803).
H.-C. Wu, J.-Q. Yu and J. B. Spencer, Org. Lett., 2004, 6, 4675.
V. V. Grushin, Chem. Rev., 2004, 104, 1629.
I. L. Odinets, N. M. Vinogradova, K. A. Lyssenko, D. G. Golovanov, P. V.
Petrovskii, T. A. Mastryukova, H. Szelke, N. B. Szabo and G. Keglevich,
J. Organomet. Chem., 2005, 690, 704.
Figure 2 Molecular geometry of compound 9 in a crystal (a solvate with
two benzene molecules) (the base of the trigonal bipyramid is shown by
thin lines, the disordered cyclohexyl substituent is shown in one of the two
possible positions only). Selected bond lengths (Å): P(2)–O(1) 1.778(2),
P(2)–C(3) 1.783(3), P(2)–C(15A) 1.801(6), P(2)–O(1b) 1.778(2), P(2)–C(3b)
1.783(3), O(1)–C(8a) 1.360(4), C(3)–C(4) 1.347(4), C(4)–C(4a) 1.487(4);
bond angles (°): O(1)–P(2)–C(3) 90.8(1), O(1)–P(2)–C(15A) 90.03(7),
O(1)–P(2)–O(1b) 179.8(1), O(1)–P(2)–C(3b) 89.2(1), C(3)–P(2)–C(15A)
118.2(1), O(1b)–P(2)–C(3) 89.2(1), C(3)–P(2)–C(3b) 123.7(2), O(1b)–
P(2)–C(15A) 90.03(7), C(3b)–P(2)–C(15A) 118.2(1), O(1b)–P(2)–C(3b)
90.8(1), P(2)–O(1)–C(8a) 118.3(2), P(2)–C(3)–C(4) 124.9(2), C(3)–C(4)–
C(4a) 119.7(3); torsion angles (°): O(1)–P(2)–C(3)–C(4) 37.1(3), P(2)–
O(1)–C(8a)–C(4a) 43.7(4), P(2)–O(1)–C(8a)–C(8) –136.9(3), C(3)–C(4)–
C(4a)–C(8a) –22.0(5), C(3)–C(4)–C(9)–C(10) –44.5(5), C(9)–C(4)–C(4a)–
C(5) –24.8(5), C(4a)–C(4)–C(9)–C(14) –46.7(4).
5
6
7
8
9
G. Baccolini, C. Boga and M. Mazzacurati, J. Org. Chem., 2005, 70, 4774.
M. Oliana, F. King, P. N. Horton, M. B. Hursthouse and K. K. Hii, J. Org.
Chem., 2006, 71, 2472.
10 H. Shimizu, I. Nagasaki and T. Saito, Tetrahedron, 2005, 61, 5405.
11 E. Bergin, C. T. O’Connor, S. B. Robinson, E. M. McGarrigle, C. P.
O’Mahony and D. G. Gilheany, J. Am. Chem. Soc., 2007, 139, 9566.
12 A. Grabulosa, J. Granell and G. Muller, Coord. Chem. Rev., 2007, 251, 25.
13 G. G. Talanova, End. Eng. Chem. Res., 2000, 39, 3550.
14 X.-M. Gan, E. N. Duesler and R. T. Paine, Inorg. Chem., 2001, 40, 4420.
15 L. J. Charbonniere, R. Ziessel, M. Montalti, L. Prodi, N. Zaccheroni,
C. Boehme and G. Wipff, J. Am. Chem. Soc., 2002, 124, 7779.
16 A. S. Aloy, N. B. Sapozhnikova, A. G. Anshitz, K. G. Kudinov, M.V.
Burdin, T. D. Tranter, D. A. Knekht, T. A. Todd and L. A. Bechfild,
Russian Patent, 2251168 (2005).
17 H. H. Dam, D. N. Reinhoudt and W. Verboom, Chem. Soc. Rev., 2007,
36, 367.
18 C. Wolf and R. Lerebours, Org. Lett., 2004, 6, 1147.
19 N. Kato, D. Tomita, K. Maki, M. Kanai and M. Shibasaki, J. Org.
Chem., 2004, 69, 6128.
configuration. The base of the trigonal bipyramid lies in the
C(3)C(3b)C(15A)P(2) plane, and the O(1) and O(1b) atoms
occupy apical positions [the bond lengths P(2)–O(1) and
P(2)–O(1b) are 1.778(2) Å]. The bond angles O(1)P(2)C(3),
O(1)P(2)C(15A), O(1)P(2)C(3b), O(1b)P(2)C(3b), O(1b)P(2)-
C(15A) and O(1b)P(2)C(3) are within 89.2(1)–90.03(7)°; and
the O(1)P(2)O(1b) bond angle equals 179.8(1)°. The sum of the
C(3)P(2)C(3b), C(3)P(2)C(15A) and C(3b)P(2)C(15A) bond
angles at the base of the bipyramid amounts to 360.1(2)°. The
§
X-ray diffraction data for compounds 5 and 9 were collected at 20 °C
using Bruker Kappa Apex2 (graphite-monochromator CuKα radiation
for 5) and Bruker Smart Apex2 (graphite-monochromator MoKα radiation
for 9) diffractometers. The images were indexed, integrated and scaled
using the APEX2 data reduction package.29 All raw data were corrected
for absorption using the SADABS30 program. The structures were solved
by the direct method using the SHELXS31 program and refinement was
carried out with SHELXL32 using anisotropic thermal parameters for all
non-hydrogen atoms. Hydrogen atoms were added to the structure
model at calculated positions and refined as fixed atoms. The hydrogen
atoms of OH groups for compound 5 were included from ∆r maps and
refined isotropically. All calculations were performed on a PC using the
WinGX33 program. All figures were made using the PLATON program.34
20 D. V. Denbel, J. Sundermeyer and G. Frenking, Org. Lett., 2001, 3, 329.
21 The Chemistry of Organophosphorus Compounds, ed. F. R. Hartley,
John Wiley & Sons, Chichester, 1992, vol. 2.
22 Topics in Phosphorus Chemistry, eds. M. Grayson and E. J. Griffith,
John Wiley & Sons, New York, Chichester, Brisbane, Toronto, Singapore,
1983, vol. 11, pp. 69–295.
23 Organic Phosphorus Compounds, eds. G. M. Kosolapoff and L. Maier,
Wiley-Interscience, New York, London, Sydney, Toronto, 1972, vol. 3,
pp. 341–500.
24 P. Rey, J. Taillades, J. C. Rossi and G. Gros, Tetrahedron, 2003, 44,
6169.
25 V. F. Mironov, A. I. Konovalov, I. A. Litvinov, A. T. Gubaidullin, R. R.
Petrov, A. A. Shtyrlina, T. A. Zyablikova, R. Z. Musin, N. M. Azancheev
and A. V. Il’yasov, Zh. Obshch. Khim., 1998, 68, 1482 (Russ. J. Gen.
Chem., 1998, 68, 1414).
26 R. W. Hoffmann and B. Holzer, J. Am. Chem. Soc., 2002, 124, 4204.
27 Aldrich Handbook of Grignard Reagents, eds. G. Silverman and
P. Rakita, Marcel Dekker, New York, 1996.
28 D. G. Gorenstein, Prog. Nucl. Magn. Reson. Spectrosc., 1983, 16, 1.
29 APEX2 (Version 2.1), SAINTPlus, Data Reduction and Correction Program
(Version 7.31A), Bruker Advanced X-ray Solutions, BrukerAXS Inc.,
Madison, Wisconsin, USA, 2006.
30 G. M. Sheldrick, SADABS, Program for Empirical X-ray Absorption
Correction, Bruker-Nonius, 1990–2004.
Compound 5
: C44H50Cl2O4P2·2CHCl3·2H2O, Mr = 1050.45 g mol–1, mono-
clinic, space group P21/c (molecule in a special position), a = 13.8864(5),
b = 18.6026(7) and c = 9.8699(4) Å, b = 92.673(3)°, V = 2546.85(17) Å3,
Z = 2, dcalc = 1.37 g cm–3, m(CuKα) = 5.000 mm–1, reflections: 14098
collected, 3908 unique, Rint = 0.0653, R1 = 0.0635, wR2 = 0.1563 for 2293
independent reflections with F2 ³ 4s (GOOF = 1.018). The thichloro-
methane solvent in the crystal is disordered.
Compound 9: C34H29Cl2O2P·2C6H6, Mr = 716.57 g mol–1, monoclinic,
space group C2/c (the molecule is in a special position on axis 2), a =
= 15.2147(13), b = 10.4610(9) and c = 24.038(2) Å, b = 92.118(1)°,
V = 3823.3(6) Å3, Z = 4, dcalc = 1.245 g cm–3, m(MoKα) = 0.249 mm–1,
reflections: 8340 collected, 4093 unique, Rint = 0.0496, R1 = 0.0577,
wR2 = 0.1519 for 1991 independent reflections with F2 ³ 4s (GOOF =
= 0.876). Cyclohexyl groups in molecule are disordered; they were refined
isotropically.
31 G. M. Sheldrick, SHELXS-97, Program for Crystal Structure Solutions,
University of Göttingen, Germany, 1997.
32 G. M. Sheldrick, SHELXL-97-2, Program for Crystal Structure Refinement,
University of Göttingen, Germany, 1997.
33 L. J. Farrugia, J. Appl. Crystallogr., 1999, 32, 837.
34 A. L. Spek, Acta Crystallogr., Sect. A, 1990, 46, 34.
CCDC 665576 and 665577 contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
For details, see ‘Notice to Authors’, Mendeleev Commun., Issue 1, 2008.
Received: 21st November 2007; Com. 07/3046
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