Synthesis of cyclenphosphoranes with polyfluorophenyl substituents; An X-ray structure of N-methyl cyclen-p-(heptafluorotolyl)phosphorane

Article abstract of DOI:10.1016/S0022-1139(99)00052-4

The metathesis reactions between the lithiated derivative of cyclenphosphorane (2) and octafluorotoluene, hexafluorobenzene, pentafluorobenzonitrile, pentafluoronitrobenzene, pentafluoro-n-butylbenzene, pentafluorobenzene and p-(cyanotetrafluorophenoxy-pentafluorobenzene) under reflux conditions gave cyclen-p-(heptafluorotolyl)phosphorane (3), cyclen-p-(pentafluorophenyl)phosphorane (4), cyclen-p-(cyanotetrafluorophenyl)phosphorane (5), cyclen-p-(tetrafluoronitrophenyl)phosphorane (6), cyclen-p-(n-butyltetrafluorophenyl)phosphorane (7), cyclen-p-(tetrafluorophenyl)phosphorane (8) and cyclen-p-(p-cyanotetrafluoro-phenoxytetrafluorophenyl)phosphorane (9), respectively, in good yields. All products were characterized by spectral and analytical techniques. These materials are moderately stable thermally but are moisture sensitive, hydrolyzing to form cyclen phosphine oxide (10). Addition of CH₃I to 3 affords the phosphoammonium iodide (11). The X-ray crystal structure of 11 was obtained. The crystal is triclinic with a space group P1. The unit cell parameters a=7.8652(2) A, b=8.584(2) A, c=22.1573(3) A; α=80.9010(10)°; β=79.2490(10)°; γ=76.9930(10)°; and Z=2.

Full text of DOI:10.1016/S0022-1139(99)00052-4

Journal of Fluorine Chemistry 97 (1999) 223±228
Synthesis of cyclenphosphoranes with poly¯uorophenyl substituents; an
X-ray structure of N-methyl cyclen-p-(hepta¯uorotolyl)phosphorane
O.D. Gupta1, Robert L. Kirchmeier, Jeanine M. Shreeve*
Department of Chemistry, University of Idaho, Moscow ID 83844-2343, USA
Received 3 December 1998; received in revised form 8 February 1999; accepted 8 February 1999
Dedicated to Prof. Yoshiro Kobayashi on the occasion of his 75th birthday
Abstract
The metathesis reactions between the lithiated derivative of cyclenphosphorane (2) and octa¯uorotoluene, hexa¯uorobenzene,
penta¯uorobenzonitrile, penta¯uoronitrobenzene, penta¯uoro-n-butylbenzene, penta¯uorobenzene and p-(cyanotetra¯uorophenoxy-penta-
¯uorobenzene) under re¯ux conditions gave cyclen-p-(hepta¯uorotolyl)phosphorane (3), cyclen-p-(penta¯uorophenyl)phosphorane (4),
cyclen-p-(cyanotetra¯uorophenyl)phosphorane (5), cyclen-p-(tetra¯uoronitrophenyl)phosphorane (6), cyclen-p-(n-butyltetra¯uorophenyl)-
phosphorane (7), cyclen-p-(tetra¯uorophenyl)phosphorane (8) and cyclen-p-(p-cyanotetra¯uoro-phenoxytetra¯uorophenyl)phosphorane
(9), respectively, in good yields. All products were characterized by spectral and analytical techniques. These materials are moderately
stable thermally but are moisture sensitive, hydrolyzing to form cyclen phosphine oxide (10). Addition of CH3I to 3 affords the
phosphoammonium iodide (11). The X-ray crystal structure of 11 was obtained. The crystal is triclinic with a space group P1. The unit cell
Ê
Ê
Ê
parameters aˆ7.8652(2) A, bˆ8.584(2) A, cˆ22.1573(3) A; ꢀˆ80.9010(10)8; ꢁˆ79.2490(10)8; ꢂˆ76.9930(10)8; and Zˆ2. # 1999
Elsevier Science S.A. All rights reserved.
Keywords: Substituted cyclenphosphoranes; Cyclenphosphine oxide
1. Introduction
cyclic structure that demonstrates the unexpectedly strong
basicity of the phosphorus-bonded apical nitrogen atoms
[9±12]. Action of protic acids on 1 answered questions about
P±N bond cleavage, i.e., alteration of the tetracyclic struc-
ture, and about the numbers and location of nitrogen atoms
that can be protonated [13]. It has also been shown that it is
possible to synthesize a series of polycyclic tetrakis (sub-
stituted amino)phosphonium ions which can be dimerized
when the phosphorus atom is constrained from displaying
tetrahedral geometry [14,15].
The intriguing chemistry of cyclenphosphorane
(cyclenPH) (1) arises from several factors including
1. the lability of the P±N and P±H bonds;
2. the nucleophilicity of the lone pairs on the axial nitrogen
atoms; and
3. the rigidity of the 12-membered tetraaza macrocyclic
ring.
The insertion of phosphorus atoms into macrocyclic
polyamines [16] leading to tetraaminophosphoranes has
provided a novel synthetic route to new classes of phos-
phorus compounds [17,18]. The structure of the ®rst P(V)±
P(V) compound formed from the coupling reaction between
the lithiated derivative of 1 and cyclen¯uorophosphorane
was con®rmed by X-ray analysis [19,20].
Our interest in the synthesis, structure and reactivity of
poly¯uorophenylphosphoranes led us to explore the reac-
tions of 1 with poly¯uoro/per¯uoro benzenes. We report
herein the results of this study as well as the X-ray crystal
structure of the CH3I derivative of 3, compound 11.
While metal complexes were the usual products when 1 was
reacted with metal compounds, e.g., cyclenPM via metathe-
tical reactions at the P±H bond [1±7], the deprotonation
reaction of 1 with n-butyllithium led to a polymeric phos-
phoramide (R4P ) species, [Li(THF)cyclenP]x. The latter
has a lithium bridged structure that forms chains through
bonding at the axial nitrogen atoms of the ring [8]. With
diborane, 1 formed cyclenphosphorane-bis(borane), a poly-
*Corresponding author. Tel.: +1-208-885-6651; fax: +1-208-885-6198;
e-mail: jshreeve@uidaho.edu
1Department of Chemistry, University of Rajasthan, Jaipur, India.
0022-1139/99/$ ± see front matter # 1999 Elsevier Science S.A. All rights reserved.
PII: S 0 0 2 2 - 1 1 3 9 ( 9 9 ) 0 0 0 5 2 - 4

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O.D. Gupta et al. / Journal of Fluorine Chemistry 97 (1999) 223±228
2. Results and discussion
attack and thus substitution at the position para to the ring
substituent.
Lithiation of cyclenphosphorane (1) to form 2 was readily
accomplished by addition of an equimolar amount of n-
butyllithium (1.6 M) in hexane to a stirred slurry of cyclen-
phosphorane in anhydrous tetrahydrofuran (THF) at 788C.
After warming to 258C, the substituted poly¯uorobenzene
was added with stirring. The ¯uoroaryl-substituted products
were removed after 12 h at re¯ux. The substituted cyclen-
phosphoranes 3±9 obtained are shown in the following
equation:
These reactions were carried out under nitrogen in the
presence of dry solvent (THF) on a 0.5 mmol scale. A
minute trace of moisture or air led to the formation of
cyclenphosphine oxide (10) instead of the desired product.
In fact during the reaction either the tetracoordinate phos-
phorus anion could be oxidized or the product hydrolyzed.
Each of the products 3±9 formed 10 in high yield when
treated with NaOH solution (aqueous/CH3CN) for 12 h
under re¯ux conditions. All attempts to recover the ¯uor-
When 2 was not utilized immediately after warming
from 788C, a brown color began to form indicating
that decomposition was taking place. Reaction with the
poly¯uorobenzenes did not occur. In every reaction, an
uncharacterized polymeric solid material invariably
formed.
ine-containing residue failed due to the very small scale of
the reactions. The solid material (10) was characterized and
the data obtained are in
This class of compounds that contains a bond between
pentacoordinate phosphorus and ¯uorine-containing substi-
tuents demonstrates the stabilization of unusual valence
states for phosphorus in cyclenphosphorane derivatives
3±9. The coupling of lithiated derivative 2 with the
¯uorinated substituents occurred via straightforward
agreement with the literature values [21].
nucleophilic substitution, i.e., the attack of the tetracoordi-
nate phosphorus anion at the ¯uorine-carbon bond with
concomitant loss of ¯uoride ion. 19F NMR spectra con®rm
The action of one equivalent of methyl iodide on 3 gave
an essentially quantitative yield of the phosphoammonium
iodide 11. The formulation of 11 was con®rmed by mass

O.D. Gupta et al. / Journal of Fluorine Chemistry 97 (1999) 223±228
225
spectrometry. In the 1H NMR spectrum, a doublet at
2.65 ppm assigned to the methyl group attached to a nitro-
3
gen atom with JH-Pˆ10 Hz was observed. The
31P‰HŠ NMR spectrum showed a single peak at ꢃˆ21 ppm
in the region associated with pentacoordinate P(V). Excess
CH3I did not lead to further alkylation under the experi-
mental conditions used.
Compound 3 did not react with CF3I at 258C in CCl3H
under similar conditions in a sealed ¯ask. The reaction was
also attempted at 508C and 808C, each for 12 h but all of 3
was recovered. Reaction with C2F5I was also tried but the
starting materials were recovered. Based on the difference
of reactivity of CH3I and RfI towards 3, it was tempting to
study the reactivity of poly¯uorocarbon iodides in a similar
mode. Unfortunately the latter compounds do not react with
3. Based on other work in these laboratories, it is somewhat
surprising that the poly¯uorocarbon iodides do not behave
more like their hydrocarbon analogues.
Fig. 1. Molecular structure of 11.
nated alkyl iodides were also reacted with 1 under a variety
of conditions but, surprisingly, these also did not react and 1
was recovered. These results are being examined further
with the thought of new methodology for the synthesis of
hydro¯uorocarbons.
It has been reported that 1 reacted with CH3I and CF3I to
form the stable but moisture sensitive compounds [14], viz.
2.1. X-ray structure of 11
A well-formed multifaceted crystal of 11, was mounted
inside a thin-walled glass capillary tube which was sealed.
Preliminary investigations using a Siemens 3-circle auto-
mated diffractometer and graphite monochromated MoKꢀ
Ê
radiation (ꢄˆ0.71073 A) indicated a triclinic crystal sys-
tem. A survey of the Cambridge Crystal Structure Data base
(CCSD) revealed that only a few cyclenphosphoranes have
been structurally characterized. However, there are no
structures known of compounds such as 11. Compound
11 crystallizes in a noncentrosymmetric space group P1
and its absolute con®guration was determined reliably as
indicated by the value of Flack's parameter at 0.00(8). The
structure of 11 is illustrated in Fig. 12. Iodide anion and
water of hydration are present.
The pentacoordinate phosphorus atom is bonded to axial
nitrogens, N(1) (four coordinate with distorted tetrahedral
geometry) and N(3) (tricoordinate). The phosphorus atom
adopts a distorted trigonal bipyramid (tbp) geometry with
N(2), N(4) and C(10) at the equatorial positions. The N(2)±
P(1)±N(4) angle of 129.7(7)8 is slightly larger than normal
for a tbp while the other two equatorial angles of 115.3(6)8
[N(2)±P(1)±C(10)] and 113.8(6)8 [N(4)±P(1)±C(10)] are
contracted signi®cantly from the ideal angle of 1208. The
Methyl iodide formed the N-alkylated product (12), while
CF3I formed the cyclenphosphonium iodide salt (13) and
CF3H. In order to learn if the latter mode of behavior was
observed with higher homologs, we extended the study of
¯uorinated alkyl iodides with 1 and isolated the hydro¯uor-
ocarbon products.
211: A 0.45Â0.25Â0.15 mm colorless crystal was examined by using
Mo Kꢀ radiation (ꢅ<28.298) with SMART software using a Siemens three-
circle platform. Relevant data: triclinic, P1, aˆ7.8652(2), bˆ8.64660(10),
Ê
cˆ16.14750(10) A, ꢀˆ80.9010(10)8, ꢁˆ79.2490(10)8, ꢂˆ76.9930(10)8;
Ê 3
Vˆ1043.42(3) A , R1ˆ0.0358, Rwˆ0.0857 for 6699 unique reflections of
The hydro¯uorocarbon compounds (14 and 15) were
isolated and characterized by mass spectrometry. It is
apparent that per¯uorinated alkyl iodides of higher mole-
cular weight will behave in a similar manner. Poly¯uori-
which 5522 had I>2ꢆ(I); 544 variable parameters were used for the
anisotropic refinement. All calculations were performed by using the
SHELXTL (Siemens) package. Additional information can be found in
Section 4.

226
O.D. Gupta et al. / Journal of Fluorine Chemistry 97 (1999) 223±228
N(1)±P(1)±N(3) angle is 172.6(6)8 which is signi®cantly
different from that expected in a regular tbp. As expected the
axial P±N bonds are longer than the equatorial bonds.
Ê
However, the P(1)±N(1) axial bond is 2.038(9) A, which
Ê
is 0.324 A longer than the P(1)±N(3) axial bond. This
signi®cant difference arises from the presence of the methyl
group on N(1). Interestingly, both the P(1)±N(1) and P(1)±
N(3) axial bonds in cyclen PH23‡ are about 1.87 A whereas
Ê
in cyclen PH.HZnCl3, the P±N axial bonds are 1.940(4) and
Ê
1.790 A and the signi®cant difference was attributed to the
greater polarizing effect of the proton relative to ZnCl3 [22].
The cyclenPCH3 unit in compound 11 adopts a staggered
conformation with respect to the CF3C6F4 bonded at phos-
phorus presumably to minimize steric interactions. Struc-
tures of the two other cyclenPX derivatives are known,
cyclenPF [16] and cyclenP±Pcyclen [20]. The details of the
cyclenPF structure are somewhat sketchy; however, the
geometry about phosphorus is midway between a tbp and
square pyramid (sp) and the sum of the angles about the
nitrogen atoms are 3528 (Neq) and 3478 (Nax). Both P atoms
in cyclenP±Pcyclen are identical and are 32.9% distorted
along the Berry coordinate from tbp to sp.
three-circle platform. A monochromated Mo Kꢀ radiation
Ê
(ꢄˆ0.71073 A) from a ®ne-focused tube is employed for
data collection. The x-axis on this platform is ®xed at
54.748, and the diffractometer is equipped with a CCD
detector maintained near 548C. The unit cell parameters
were determined by least-squares re®nement of 60 frames
collected at 10 s intervals by using SMART software and
®nally by the least-squares re®nement of all of the observed
re¯ections by the SAINT software [23]. A complete hemi-
sphere of data was scanned on ! (0.38) with a run time of 10
or 30 s per frame at the detector resolution of 512Â512
pixels. A total of 1271 frames are collected in three sets and
a ®nal set of 50 frames, identical to the ®rst 50 frames, are
also collected to determine the crystal decay. The frames are
then processed on a SGI-Indy work station using the SAINT
software to give the h, k, l ®le for corrected Lp/decay. The
structures are solved by the direct method using the
SHELX-90 program [24] and re®ned by least-squares
method on F2, SHELXL-93 [25], incorporated in
SHELXTL-PC V5.03 [26]. All non-hydrogen atoms are
re®ned anisotropically. The hydrogen atoms are located
from the difference of electron density maps and are in-
cluded in the re®nement process in an isotropic manner. The
crystals showed no decomposition during data collection.
3. Experimental
3.3. General procedure for the preparation of
cyclenphosphoranes 3±9
3.1. General procedures
All reactions and manipulations were carried out under an
atmosphere of nitrogen in a dry box or by using standard
Schlenk techniques, unless otherwise indicated. Glassware
was oven dried at 1308C overnight prior to use. Solvents
were dried and distilled under nitrogen atmosphere and used
immediately. The solvents tetrahydrofuran (THF) and
diethyl ether were distilled over sodium prior to use. All
other chemicals are used as received (Aldrich, Fluorochem,
PCR). Infrared spectra were recorded on a Perkin-Elmer
1710FT IR spectrometer between KBr plates as neat liquids
or solids as KBr pellets. 1H, 19F and 31P NMR spectra were
obtained on a Bruker AC 200 or Bruker AC 300 FT multi-
nuclear NMR spectrometer resonating at 200.132 (1H),
81.026 (31P) and 188.313 MHz (19F). The 1H and 31P
chemical shifts are referenced to (CH3)4Si and 85%
H3PO4, respectively. 19F resonances are measured relative
to CCl3F as reference. 31P spectra are proton-decoupled
unless otherwise indicated. Mass spectra are obtained with a
Varian VG7070HS mass spectrometer by using electron
impact (EI) or chemical ionization (CI) techniques. Melting
points were obtained in a nitrogen ®lled tube on a Met-temp.
capillary apparatus.
In a typical procedure, a slurry of cyclenphosphorane (1)
[100 mg (0.5 mmol)] in 10 ml of anhydrous THF was
lithiated by adding an equivalent amount of 1.6 M n-butyl-
lithium in hexane with stirring at 788C. The mixture was
warmed to 258C and 0.5±1.0 mmol of substrate was added
followed by re¯uxing for 12 h under nitrogen. The mixture
is cooled to room temperature, ®ltered under nitrogen and
the solvent was removed under vacuum. This affords a
semisolid/oily residue which was distilled bulb-to-bulb at
ꢀ908C/0.1 mm to give pure products. Yields of the products
3±9 range from 40% to 50%.
3.4. Cyclen-p-(heptafluorotolyl)phosphorane (3) from
C6F5CF3 and 2
The spectral data obtained for 4 are as follows. IR (KBr):
3010 (m), 2941 (vs), 2883 (vs), 1658(s), 1595 (m), 1469
(vs), 1326 (vs), 1277 (s), 1153 (s), 1079 (w), 977 (s), 794
1
1
(w), 735 (m) cm . NMR: H, ꢃ 2.7±3.3 (m, 16H); 19F,
ꢃ 56.1 (m, 3F), 139.8 (m, 2F), 154.8 (m, 2F); 31P,
‡
ꢃ 44.68 MS (EI) [m/e (species) intensity]: 416 (M ) 14,
‡
‡
‡
397 (M ±F) 2, 347 (M ±CF3) 3, 199 (M ±C6F4CF3) 100.
3.2. X-ray crystal structure analysis
3.5. Cyclen-p-(pentafluorophenyl)phosphorane (4) from
C6F6 and 2
Off-white crystals of 11 were grown from a solution of
CHCl3 and C6H12. The X-ray diffraction data for compound
11 are collected with SMART software by using a Siemens
The spectral data obtained for 3 compound are as follows.
IR (KBr pellet): 3019 (m), 2947 (s), 2873 (vs), 1685 (s),

O.D. Gupta et al. / Journal of Fluorine Chemistry 97 (1999) 223±228
227
1511 (m), 1482 (m), 1456 (s), 1392 (s), 1237 (vs), 968 (ms),
1
3.10. Cyclen-p-(p-cyanotetrafluorophenoxytetrafluoro-
phenyl)phosphorane (9) from C6F5OC6F4CN and 2
849 (s), 710 (m) cm . NMR: 1H, ꢃ 2.9±3.2 (m, 16H); 19F,
ꢃ 138.2 (2F, m), 153.3 (m, 1F), 159.8 (m, 2F); 31P,
‡
ꢃ
347 (M ±F) 7, 199 (M ±C6F5)100.
42.28. MS (EI) [m/e (species) intensity]: 366 (M ) 65,
‡
The spectral data obtained for 9 are as follows. IR (KBr
pellet): 3085 (m), 2253 (w), 1657 (m), 1647 (m), 1520 (s),
1510 (s), 1495 (s), 1430 (m), 1321 (m), 1162 (m), 1109 (m),
‡
1
1
1020 (m), 992 (m), 926 (w) cm . NMR: H, ꢃ 2.9±3.1
(m, 16H); 19F, ꢃ 130.9 (m, 2F), 153.5(m, 2F), 155.6
(M, 2F), 160.7 (m, 2F); 31P, ꢃ 43.4. MS (EI) [m/e
3.6. Cyclen-p-(cyanotetrafluorophenyl)phosphorane (5)
from C6F5CN and 2
‡
‡
(species) intensity]: 537 (M ) 30, 199 (M -C13F8ON)
100.
The spectral data obtained for 5 are as follows. IR (KBr):
3080 (m), 2252 (m), 1640 (m), 1528 (s), 1502 (s), 1493 (s),
1402 (m), 1320 (m), 1267 (m), 1240 (m), 1221 (m), 1174 (s),
1146 (s), 1062 (m), 1038 (m), 1001 (s), 954 (s), 842 (m), 802
3.11. Reaction of 3 with CH3I to prepare 11
1
(w), 714 (m), 693 (w), 665 (w) cm . NMR: 1H, ꢃ 2.8±3.2
(m, 16H); 19F, ꢃ 145.5 (m, 2F), 153.3 (m, 2F); 31P,
A 50 ml round-bottomed ¯ask, equipped with a Kontes
Te¯on stopcock, is loaded with 4 (0.1 g, 0.25 mmol) and
10 ml dry tetrahydrofuran was transferred under vacuum
into the ¯ask and cooled at 08C. CH3I was added to
the reaction ¯ask in an equivalent amount and stirred.
The ¯ask was allowed to warm to 258C and ®lled with
nitrogen gas. The contents were then stirred for 2 h.
Removal of all volatile material under vacuum affords a
pale greenish solid in 90% yield which was further puri®ed
by recrystallization from a mixture of chloroform/
ether(1:1). The spectral data obtained for 11 are as follows.
IR (KBr pellet): 2926 (s), 2888 (ms), 1651 (s), 1594 (w),
1480 (vs), 1327 (s), 1190 (s), 1023 (ms), 977 (ms), 954 (s),
‡
ꢃ 42.6. MS (EI) [m/e (species) intensity]: 373 (M ) 30,
‡
199 (M ±C7F4N) 100. HRMS: Calcd. 373.1079; Found
373.1074.
3.7. Cyclen-p-(tetrafluoronitrophenyl)phosphorane (6)
from C6F5NO2 and 2
The spectral data obtained for 6 are as follows. IR (KBr):
3085 (m), 1634 (m), 1559 (s), 1524 (s), 1505 (s), 1408 (w),
1363 (m), 1028 (m), 951 (s), 927 (m), 840 (w), 822 (m), 770
1
(m), 753 (w), 729 (w), 690 (w) cm . NMR: 1H, ꢃ 2.8±3.2
(m, 16H); 19F, ꢃ 145.5 (m, 2F), 153.3 (m, 2F); 31P,
1
1
‡
793 (w), 657 (ms) cm . NMR: H, ꢃ 2.8±3.1 (m, 16H),
2.62 (d, 3H); 19F, ꢃ 56.73 (m, 3F), 136.37 (m, 4F); 31P,
ꢃ 42.6. MS (EI) [m/e (species) intensity]: 393 (M ) 15,
‡
199 (M ±C6F4NO2) 100.
‡ ‡
19.92. MS (FAB ) [m/e (species) intensity]: 431 (M )
ꢃ
33.
3.8. Cyclen-p-(n-butyltetrafluorophenyl)phosphorane (7)
from C6F5C4H9 and 2
3.12. Reaction of 3 with CF3I, C2F5I, CF3(CF2)5CH2CH2I
and (CF3)2CFCH2CH2I
The spectral data obtained for 7 are as follows. IR (KBr):
3078 (m), 2965 (m), 2939 (m), 2880 (m), 1664 (m), 1611
(w), 1538 (m), 1495 (s), 1420 (w), 1412 (w), 1383 (w), 1338
(s), 1258 (w), 1222 (s), 1187 (s), 1155 (s), 1112 (m), 1088
(m), 1040 (w), 621 (w), cm 1. NMR: 1H, ꢃ 3.5 2.9
(m, 16H), 2.65 (m, 2H), 1.58 (m, 2H), 1.36 (m, 2H),
The reactions were carried out in a manner similar to that
described above and an oil bath was used to carry out the
reaction at 508C and 808C. In each case the course of the
reaction was monitored by 31P NMR spectra. In each reac-
tion, unreacted 3 was recovered.
0.92 (t, 3H); 19F, ꢃ 142.1 (m, 2F), 154.5 (m, 2F); 31P,
‡
ꢃ
41.5. MS (EI) [m/e (species) intensity]: 404 (M ) 30,
‡
199 (M ±C10F4H9) 100. HRMS: Calcd. 404.1753; Found
404.1747.
3.13. Reaction of 1 with C2F5I and CF3(CF2)5CF2I to
form 14 and 15
3.9. Cyclen-p-(tetrafluorophenyl)phosphorane (8) from
C6F5H and 2
A stirred solution of 1 (0.10 g, 0.5 mmol) in dry
chloroform (5ml) was treated with 0.5 mmol C2F5I
or C7F15I. After stirring for 4 h at 258C, the volatile
materials were collected. The remaining white solid
(13) in each reaction was obtained in quantitative
yield and was characterized [14]. The hydro¯uoro-
carbons CF3CF2H (14) and CF3(CF2)5CF2H (15) were
isolated in essentially quantitative yields from the
volatile fraction and characterized by mass spectro-
The spectral data obtained for 8 are as follows. IR (KBr):
3060 (m), 1632 (m), 1525 (s), 1504 (s), 1407 (w), 1365 (m),
1330 (w), 1276 (m), 1242 (w), 1176 (m), 1148 (m), 1135
(m), 1056 (m), 1030 (m), 1012 (m), 952 (s), 928 (m), 717
1
1
(m), 702 (w) cm . NMR: H, ꢃ 7.02 (t, 1H), 2.8±3.2 (m,
16H); 19F, ꢃ 155.6 (m, 2F), 160.7 (m, 2F); 31P, ꢃ 42.8.
‡
‡
MS (EI) [m/e (species) intensity]: 348 (M ) 30, 199
‡
metry, with a parent ion (M ) being obtained in each
case.
(M ±C6F4H) 100.

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O.D. Gupta et al. / Journal of Fluorine Chemistry 97 (1999) 223±228
[3] D.V. Khasnis, M. Lattman, U. Siriwardane, Inorg. Chem. 26 (1989)
681.
3.14. Reaction of 1 with CF3CH2I and
CF3(CF2)5CH2CH2I
[4] E.G. Burns, S.S.C. Chu, P. de Meester, M. Lattman, Organometallics
5 (1986) 2383.
A procedure identical with that used for 14 and 15 except
that CF3CH3I or CF3(CF2)5CH2CH2I was used with 1 at
varying temperatures and times (258C, 12 h; 508C, 12 h;
808C, 12 h). In each case unreacted 1 was recovered quan-
titatively and no hydro¯uorocarbons were detected.
[5] M. Lattman, S.K. Chopra, A.H. Cowley, Organometallics 5 (1986)
677.
[6] P. de Meester, M. Lattman, S.S.C. Chu, Acta Crystallogr. C C43
(1987) 162.
[7] D.V. Khasnis, M. Lattman, U. Siriwardane, S.K. Chopra, J. Am.
Chem. Soc. 111 (1989) 3103.
[8] M. Lattman, M.M. Olmstead, P.P. Power, D.W. Rankin, H.E.
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4. Supplementary material
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1051.
For compound 11, complete bond lengths and bond
angles, tables of data collection and processing parameters,
atomic coordinates, equivalent isotropic and anisotropic
displacement coef®cients, hydrogen atom coordinates and
isotropic displacement coef®cients (nine pages).
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3777.
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107 (1985) 1202.
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1292.
Acknowledgements
We are grateful for the support of British Nuclear Fuels
plc, of NSF CHE-9720635, and ACS-PRF-32613 and for
generous gifts of chemicals by Fluorochem. Dr. B. Krumm
is thanked for a gift of C6F5OC6F4CN. We thank Dr. Gary
Knerr and G. Cao for obtaining mass spectral data and Dr.
Ashwani Vij for solving the crystal structure. The single-
crystal CCD X-ray facility at the University of Idaho was
established with the assistance of the NSF-Idaho EPSCoR
program under NSF OSR-9350539 and the M.J. Murdock
Charitable Trust, Vancouver, WA. One of the authors (ODG)
would like to thank the University of Rajasthan, Jaipur,
India for leave to do this research.
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(1980) 5790.
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[18] J.E. Richman, T.J. Atkins, Tetrahedron Lett. (1978) 4333.
[19] J.E. Richman, R.O. Day, R.R. Holmes, J. Am. Chem. Soc. 102
(1980) 3955.
[20] J.E. Richman, R.O. Day, R.R. Holmes, Inorg. Chem. 20 (1981)
3379.
[21] J.E. Richman, R.B. Flay, O.D. Gupta, ACS Symp. Ser. 171 (1981)
271.
[22] D.V. Khasnis, M. Lattman, U. Siriwardane, Inorg. Chem. 29 (1990)
271.
[23] SAINT V 4.035 software for the CCD Detector System, Siemens
Analytical Instruments Division, Madison, WI (1995).
[24] G.M. Sheldrick, SHELXS-90, Program for the solution of crystal
structure, University of GoÈttingen, GoÈttingen, Germany (1990).
[25] G. M. Sheldrick, SHELXS-93, Program for the refinement of crystal
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