514
KUKHAREVA et al.
deviation of the phosphorus atoms fom the ring planes
of 0.56
and refined in anisotropic isotropic full-matrix appro-
ximation on F. Analysis of the residual electron
density showed that the ethyl group on O(33) in com-
pound V is disordered over two positions with oc-
cupancies of 0.5. The positions of hydrogen atoms
were calculated from geometric considerations and
refined by the rider model. All the calculations were
carried out on an IBM PC/AT computer by means of
the SHELXTL PLUS 5.0 program complex. Absorp-
tion was considered by means of the DIFABS prog-
ram [3].
.
It is evident that fluoroalkyl cyclophosphite co-
ordination systems may present interest as catalysts
for reactions in which electron-acceptor ligands
enhance the catalytic activity of the complexes.
EXPERIMENTAL
The 31P NMR spectra were recorded on a Bruker
WP-80SY instrument (80 MHz). The 1H NMR spectra
were obtained on a Bruker AM250 spectrometer
(250 MHz). The chemical shifts are measured against
internal HMDS (1H) and external 85% phosphoric
acid (31P).
2-[2,2,2-Trifluoro-1-(trifluoromethyl)ethoxy]-
5,5-dimethyl-1,3,2-dioxaphosphorinane (II). 2-Di-
ethylamino-5,5-dimethyl-1,3,2-dioxaphosphorinane
(I), 3 g, and 2.48 g of 2,2,2-trifluoro-1-(trifluoro-
methyl)ethanol were dissolved in absolute benzene,
and the solution was left to stand at room temperature
for 48 h. The solvent was then removed in a vacuum,
and the residue was distilled. Yield 57%, bp 26 28 C
All the syntheses were carried under dry nitrogen
in absolute solvents.
The reaction progress was followed and the indi-
viduality of the products was controlled by TLC on
Silufol plates, elution with 14:1 hexane dioxane (A),
3:1 benzene dioxane (B), 1:1 benzene dioxane (C),
3:1 hexane dioxane (D), 5:1 benzene dioxane (E),
and 3:1 chloroform methanol (F).
(20 mm), Rf 0.8 (A). 31P NMR spectrum:
P
125.1 ppm. H NMR spectrum, , ppm: 0.13 (CHe3,
1
3H), 0.45 (CHa3, 3H), 3.03 (CHe, 1H), 3.92 (CHa, 1H),
4.13 (CH, 1H). Found, %: C 32.16, H 3.45, P 10.30.
C8H11F6PO3. Calculated, %: P C 32.00, H 3.66,
C 10.30.
The X-ray diffraction analysis of single crystals of
V and VI was performed on a Siemens P3/Pc auto-
matic four-circle diffractometer (MoK radiation,
graphite monochromator, /2 scanning, 2 <48 ).
Crystal data for compound V, C28H60Br4Cu4O12P4:
2,2,3,3,4,4-Hexafluoro-1,5-bis(5,5-dimethyl-
1,3,2-dioxaphosphorinan-2-yloxy)pentane (III).
A solution of 3.8 g of 2,2,3,3,4,4,-hexafluoropentane-
1,5-diol in 10 ml of absolute dioxane and 5.4 ml of
anhydrous triethylamine were added dropwise to a
solution of 5.18 ml of 2,2-dimethyltrimethylene phos-
phorochloridite in 100 ml of absolute dioxane. The
reaction mixture was stirred for 1.5 h with cooling.
The triethylamine hydrochloride was filtered off, the
solvent was removed, and the residue was distilled in
monoclinic; at 120 C, a 11.593(4) , b 20.490(3)
,
c 40.712(7)
,
95.47(2) , V 9627(3) 3, Z = 8,
1
5.245 m , F(000) 5120, dcalc 1.775 g/cm3,
M 1286.44, space group C2c. Of 7123 measured
reflections, 6808 unique ones were used in further cal-
culations and refinment. Final divergence factors: wR2
0.1987, GOF 0.983, on all reflections; R1 0.0608, on
3788 reflections with I > 2 (I), refinment on F. The
atomic coordinates and thermal parameters are listed
in Table 1, and the bond lengths and angles are given
in Table 2.
4
a high vacuum. Yield 70%, bp 125 C (10 mm).
Rf 0.84 (D) and 0.82 (C). 31P NMR spectrum:
123.4 ppm. H NMR spectrum, , ppm: 0.2 (CHe3,
1
6PH), 1.04 (CH3a, 6H), 3.07 (CH2e, 4H), 4.02 (CHa2, 4H),
4.04 (CH2, 4H). Found, %: C 38.04, H 4.92, P 13.75.
C15H24F6P2O6. Calculated, %: C 37.82, H 5.04,
P 13.02.
Crystal data for complex VI, C18H30BrCuF9O9P3:
monoclinic; at 25 C, a 14.020(4) , b 16.254(5)
,
1
c 14.866(4) , V 3223(2), Z 4, 2.144 mm , F(000)
1600, dcalc 1.620 g/cm3, M 785.94, space group P21/n.
Of 4546 measured reflections, 4100 unique ones were
used in further calculations and refinement. Final
divergence factors: wR2 0.2013, on all the 4100 ref-
lections; R1 0.0769, GOF 1.032, on 3542 reflections
with I > 2 . The coordinates of non-hydrogen atoms
and their equivalent isotropic thermal parameters are
listed in Table 3, and the bond lengths and angles are
given in Table 4.
2-[2,2,2-Trifluoro-1-(trifluoromethyl)-1-[5,5-di-
methyl-1,3,2-dioxaphosphorinan-2-yloxy]ethyl]-4-
methyl-1-(5,5-dimethyl-1,3,2-dioxaphosphorinan-2-
yloxy)benzene (IV). A solution of 1.8 g of 2-[2,2,2-
trifluoro-1-(trifluoromethyl)-1-hydroxyethyl]-4-me-
thylphenol in 10 ml of absolute benzene and 2 ml of
triethylamine were added dropwise to a solution of
1.5 ml of 2,2-dimethyltrimethylene phosphorochlori-
dite in 100 ml of absolute benzene. The reaction
mixture was stirred with cooling for 2 h, the triethyl-
amine hydrochloride was filtered off, the solvent was
The structures were solved by the direct method
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 71 No. 4 2001