The synthesis and chemistry of fluorovinyl-containing phosphines and the single crystal X-ray structure of SPPr2i(CF=CF 2)

Article abstract of DOI:10.1039/b316099h

The first perfluorovinyl alkyl-containing phosphines of the type PR ₂(CF=CF₂) (R = Et, ⁱPr, Cy) are reported. The reactivity of these air- and moisture-stable materials has been explored, both at the phosphorus centre and at the fluorovinyl moiety. When PR ₂(CX=CF₂) (X = F, Cl) is reacted with LiAlH₄ a mixture of PR₂(CX=CFH) isomers and other defluorinated materials are produced, but the reaction with LiAlH(OBu_t)₃ affords the single products Z-PR₂(CF=CFH) or E-PR₂(CCl=CFH), respectively, in high yields. Reaction of the fluorovinyl alkyl phosphines with hydrogen peroxide, elemental sulfur or selenium yields fluorovinyl-containing phosphine oxides, sulfides and selenides, respectively. The phosphine sulfide SPPr₂ⁱ(CF=CF₂) is the first perfluorovinyl phosphorus(v) compound to be characterised crystallographically and it exhibits an unusually short [1.9358(9) A] P=S bond. Reaction of fluorovinyl phosphines with XeF₂ results in compounds of the type F ₂PR₂(CF=CF₂), identified on the basis of multinuclear NMR studies. These compounds decompose in the presence of moisture to yield the respective phosphine oxides. Reaction of OPPh₂(CF= CF₂) with Br₂ results in bromine addition across the double bond to give OPPh₂(CFBrCF₂Br).

Full text of DOI:10.1039/b316099h

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P A P E R
The synthesis and chemistry of fluorovinyl-containing phosphines and
i
=
the single crystal X-ray structure of SPPr2(CF CF2)
Nicholas A. Barnes, Alan K. Brisdon,* F. R. William Brown, Wendy I. Cross, Ian R. Crossley,
Cheryl Fish, James V. Morey, Robin G. Pritchard and Lakhdar Sekhriy
Department of Chemistry, UMIST, PO Box 88, Manchester, UK M60 1QD.
E-mail: alan.brisdon@umist.ac.uk
Received (in Montpellier, France) 9th December 2003, Accepted 24th February 2004
First published as an Advance Article on the web 9th June 2004
i
=
The first perfluorovinyl alkyl-containing phosphines of the type PR2(CF CF2) (R ¼ Et, Pr, Cy) are reported.
The reactivity of these air- and moisture-stable materials has been explored, both at the phosphorus centre and
=
at the fluorovinyl moiety. When PR2(CX CF2) (X ¼ F, Cl) is reacted with LiAlH4 a mixture of
t
PR2(CX CFH) isomers and other defluorinated materials are produced, but the reaction with LiAlH(OBu )3
=
=
=
affords the single products Z-PR2(CF CFH) or E-PR2(CCl CFH), respectively, in high yields. Reaction of the
fluorovinyl alkyl phosphines with hydrogen peroxide, elemental sulfur or selenium yields fluorovinyl-containing
i
=
phosphine oxides, sulfides and selenides, respectively. The phosphine sulfide SPPr2(CF CF2) is the first
perfluorovinyl phosphorus(V) compound to be characterised crystallographically and it exhibits an unusually
˚
short [1.9358(9) A] P S bond. Reaction of fluorovinyl phosphines with XeF2 results in compounds of the type
=
=
F2PR2(CF CF2), identified on the basis of multinuclear NMR studies. These compounds decompose in the
=
presence of moisture to yield the respective phosphine oxides. Reaction of OPPh2(CF CF2) with Br2 results
in bromine addition across the double bond to give OPPh2(CFBrCF2Br).
=
PPh3 ꢀ x(CF CF2)x (x ¼ 1, 2), were prepared by Horn and
Introduction
co-workers in yields ranging from 2 to 21%.12
There is considerable interest in the synthesis and chemistry of
phosphorus(III) compounds containing fluorinated organic
fragments, in part due to their utility as ligands that exhibit
a combination of steric and electronic parameters for which
there are few analogues in traditional, hydrocarbon-phosphine
chemistry.1 Equally significant is the widespread use of related
vinyl-containing phosphines as versatile building blocks in syn-
thetic organic chemistry.2 Historically, the first important
fluorocarbon-containing phosphine was P(CF3)3 , prepared
from the reaction between CF3I and elemental phosphorus,
or CF3 sources and PCl3 .3 Amongst the numerous synthetic
methods available, the most prevalent approach to perfluor-
oalkyl and perfluoroaryl phosphines has relied upon Grignard
or lithium reagents derived from chloro-, or more usually,
bromofluorocarbons. This route has been widely used for
the synthesis of poly- and pentafluorophenyl-substituted phos-
phines4,5 and, more recently, for perfluoroalkyl systems.6,7
However, the number of reported examples of phosphines con-
taining fluorocarbon groups is still small compared to hydro-
carbon analogues; in particular, there is a dearth of examples
of phosphines containing fluorovinyl groups. Vinyl phosphines
It is not now possible to rely upon chloro- and bromofluoro-
carbons as sources of fluoro-organo Grignard and lithium
reagents, given the reduced availability of these materials, as
a result of their ozone-depleting properties. More recent work
has thus applied alternative methodologies such as the use, by
Ichikawa et al., of 2,2,2-trifluoroethyl triflate in the synthesis
of 2,2-difluorovinyl phosphine derivatives.13 We have pre-
viously reported an improved synthesis for the phosphines
=
PPh3 ꢀ x(CF CF2)x (x ¼ 1, 2, 3) and their chloride analogues
=
=
PCl2(CF CF2) and PCl(CF CF2)2 , in high yields and purity,
via the generation, in situ, of perfluorovinyl lithium from the
commercially available CFC replacement CF3CH2F (HFC-
134a) and BuLi.14 We have now extended this approach to
the synthesis of the first alkyl perfluorovinyl phosphines, of
0
=
=
the type PR2(CF CF2) and PRR (CF CF2). In view of the
wide potential for steric and electronic control afforded by
alkyl phosphines we have also investigated derivatisation of
=
these and related phosphines of the type PR2(CF CF2) where
R ¼ alkyl, aryl. We thus report the synthesis and charac-
terisation of a range of fluoro-organo phosphorus(III) and
phosphorus(V) compounds
=
=
=
of the type P(CH CH2)3 , PR(CH CH2)2 and PR2(CH CH2)
are well-known8 and some, for example with R ¼ Ph, are
commercially available. Following the reports of vinyl phos-
Results and discussion
=
phines, Knunyants and co-workers prepared P(CF CF2)3 ,
=
Synthesis of alkyl perfluorovinyl phosphines
P(NEt2)3 ꢀ x(CF CF2)x (x ¼ 1, 2), the halophosphines
PCl3 ꢀ x(CF CF2)x and PF3 ꢀ x(CF CF2)x (x ¼ 1, 2),9 and
=
=
The low-temperature reaction of perfluorovinyl lithium, gener-
ated from CF3CH2F and two equivalents of n-BuLi,15,16 with
the appropriate alkylchlorophosphines affords, after workup
and distillation, the dialkyl perfluorovinyl phosphines,
1–3 (see Scheme 1), as colourless liquids, in good yields
(60–80%). Similarly, the addition of PhBuPCl, prepared
from PhPCl2 and BuLi, to a solution of perfluorovinyl
lithium results in the synthesis of the P-chiral phosphine
=
(CF2 CF)P(O)(OEt)2 from the unstable Grignard reagent
=
=
CF2 CFMgBr, obtained from CF2 CFBr and elemental
Mg.10 Subsequently, Cowley and Taylor reported the
=
dimethylamino analogues, P(NMe2)3 ꢀ x(CF CF2)x (x ¼
1, 2)11 and, in 1978, two phenyl perfluorovinyl phosphines,
=
PhBuP(CF CF2) (4), albeit in somewhat lower yield.
´
y Permanent address: Universite Ouargle, Ouargle, Algeria.
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
828
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 8 2 8 – 8 3 7

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an oil (5) results. The 19F NMR spectrum of 5 exhibits two
doublet of doublet of triplet resonances at ꢀ132.7 and
ꢀ159.1 ppm, with a large, mutual J(FF) coupling of 141 Hz.
The 31P{1H} NMR spectrum of 5 displays a doublet of doub-
lets at ꢀ27.1 ppm, which is only slightly shifted from that of
1
the parent phosphine (ꢀ26.2 ppm), while the H NMR spec-
Scheme 1 Reaction scheme for the two-stage, one-pot synthesis of
perfluorovinyl phosphines.
trum shows four signals associated with the butyl group, one
of which exhibits coupling to the two fluorine nuclei (J ¼ 23
and 10 Hz). The NMR data is consistent with a 1,2-difluoro-
vinyl-containing compound, also confirmed by the 13C{1H}
NMR spectrum; while the presence of a large, typically trans,
Together, these constitute the first examples of perfluorovinyl-
substituted phosphines containing alkyl groups. All of these
compounds have proven to be air- and moisture-stable for
many months, like the previously reported phenyl counter-
parts.14 This is in contrast to the properties of alkyl-substituted
vinyl phosphines, and alkyl phosphines in general, which are
much more sensitive to oxidation.17
Unambiguous identification of all pure products was
obtained by a combination of elemental analysis, IR and mul-
tinuclear (1H, 19F, 31P{1H} and 13C{1H}) NMR spectroscopy.
The 19F NMR spectra of the alkylperfluorovinyl phosphines 1
to 4 each exhibit three sets of doublets of doublets of doublets
at ca. ꢀ86, ꢀ110 and ꢀ185 ppm, consistent with the expected
AMX spin system for the perfluorovinyl moiety, with addi-
tional coupling to the phosphorus nucleus. These resonances
were assigned to the trans, cis and geminal fluorine nuclei,
respectively, of the perfluorovinyl group, by comparison with
previously recorded data.11,12,14,18,19 The 31P{1H} NMR spec-
tra of 1 to 4 each exhibit a resonance dominated by one large
PF coupling of ca. 55 Hz and two smaller magnitude cou-
plings. The larger coupling constant is also observed for the
19F NMR resonance corresponding to the fluorine nucleus
cis to the phosphorus centre. Although the anticipated magni-
3J(FF) coupling,19 identifies the product as Z-PPh2(CF
=
CFBu). The higher frequency 19F NMR resonance (ꢀ132.7
ppm) is assigned to the fluorine nucleus cis to phosphorus on
the basis of a large J(PF) coupling (89 Hz) and a coupling of
23 Hz to the proximate butyl protons. The lower frequency
resonance (ꢀ159.1 ppm) is therefore assigned to the geminal
fluorine nucleus, which exhibits much smaller J(PF) (5 Hz)
and J(FH) (10 Hz) couplings.
The exclusive formation of the Z isomer of 5 contrasts with
recently reported work on the similar nonfluorinated systems,
=
PPh2(CH CHR) [R ¼ Ph, p-tolyl, p-NO2C6H4 and CH2CH-
(Ph)CH3].23 In these compounds both E and Z isomers were
=
obtained, with cis-PPh2(CH CHR) typically being predomi-
nant. However, the dominance of the trans isomer of 5 concurs
with our previous work on related group 14 compounds.22 The
preference for this isomer can be explained by consideration of
the intermediate species formed during carbolithiation.
Nucleophilic attack would be favoured at the b-carbon, since
this is expected to be the more electron-deficient centre. Addi-
tionally, the resulting intermediate carbanion on the a-carbon
centre would be the least destabilised by þIp effects from the
adjacent fluorine atoms. The trans arrangement of the large
PPh2 and Bu groups minimises steric repulsions, thus subse-
quent syn elimination of LiF would give rise to the observed
Z isomer.24
tude of bond-mediated couplings in
a vinyl group is
J(PFtrans) > J(PFcis), we observe a large J(PFcis) coupling con-
stant, which is consistent with lone-pair-assisted through-space
coupling.20
The approximate 31P NMR chemical shifts of tertiary
phosphines can be predicted using the empirical formula:21
i¼1
Reaction with hydride reagents. There are no readily avail-
able CFC replacements that easily allow for the facile genera-
tion of hydrofluorovinyl ligands directly from lithium reagents
and relatively few such compounds have been reported pre-
viously. However, such phosphines should be accessible via
reaction of perfluorovinyl compounds with nucleophilic
sources of hydride. We have thus explored the reactions of
X
d ¼ ꢀ62 þ
sp
3
where sP is a constant for a given alkyl or aryl group attached
to the phosphorus centre. This relationship has not previously
been applied to fluorovinyl systems; however, based upon the
=
data reported herein we conclude that for the CF CF2 group
=
sP ¼ ꢀ3 and þ5 for the CCl CF2 group.18 We note that while
=
=
PPh2(CF CF2) and PPh2(CCl CF2) with LiAlH4 , which in
each case resulted in the isolation of a number of species.
The 31P{1H} NMR spectrum obtained from the reaction of
sP values for most alkyl and aryl substituents are positive, the
=
negative value for the CF CF2 group is consistent with those
=
PPh2(CF CF2) and LiAlH4 indicates the presence of two
for other highly fluorinated, electron-withdrawing groups,
such as C6F5 , where sP ¼ ꢀ5.
major products, characterised by a multiplet at ꢀ27.5 ppm
(dd, J ¼ 74, 8 Hz) and a singlet at ꢀ39 ppm, in an approxi-
mately 1:1 ratio. The resonance at ꢀ27.5 ppm is consistent
with formation of a 1,2-difluorovinyl-substituted phosphine.
The 13C{1H} NMR spectra of 1 to 4 show the expected peaks
due to the alkyl groups as well as two complex multiplets at
ca. 127 and 160 ppm, which are assigned to the a- and b-per-
fluorovinyl resonances, respectively, on the basis of J(CF)
magnitudes.
=
The geometry of this product is assigned as Z-PPh2(CF CFH)
(6) on the basis of the magnitudes of coupling constants
1
observed in the 19F and H NMR spectra. This interpretation
is also consistent with the data recorded after LiAlH4 is reacted
with group 14 perfluorovinyl compounds.22 The lower fre-
quency signal observed in the 31P NMR spectrum is assigned
to PPh2PH on the basis of literature data,25 confirmed by
acquisition of a proton-coupled 31P NMR spectrum, where
this resonance appears as a doublet of quintets (J ¼ 218,
7 Hz). It therefore appears that the excess of LiAlH4 used in
these reactions, required to ensure complete consumption of
the starting phosphine, causes cleavage of the phosphorus-
perfluorovinyl P–C bond, resulting in Ph2PH as a significant
by-product. We note that no resonances consistent with
Reactivity of perfluorovinyl phosphines
Reactions with n-butyl lithium. Previously, it has been
=
reported that when an excess of CF2 CFLi is present during
the preparation of perfluorovinyl-containing phosphines,
nucleophilic attack occurs, to generate species of the type
12
PR2(CF CF–CF CF2). We have found no evidence for
=
=
=
this, despite routinely using an excess of CF2 CFLi in order
to ensure high yields. However, we have previously reported
that carbolithiation of group 14 perfluorovinyl compounds
t
with RLi (R ¼ Me, nBu, Bu, Ph), occurs readily to afford
new difluorovinyl-based products.22 In view of this success,
we have now extended this work to phosphorus derivatives.
PhPH(CF CF2) were observed, which suggests that the P–C
bond to the perfluorovinyl group is preferentially cleaved
under these conditions. A number of lower intensity signals
=
n
ꢁ
=
Thus, when PPh2(CF CF2) is reacted with BuLi at ꢀ90 C
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 8 2 8 – 8 3 7
829

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are also observed in the 31P{1H} NMR spectrum (see Experi-
is more rapid when R is an alkyl group than when R ¼ Ph.
=
mental). These include E-PPh2(CF CFH), the identity of
Oxidation with hydrogen peroxide is typically complete after
30 min, whilst longer reaction times are needed for the sele-
nides (2 to 3 h) and sulfides (6 to 24 h). In contrast, complete
which was confirmed by the corresponding 19F and 1H
NMR resonances, which appear in regions typical of
26
cis-CF CFH substituted compounds of phosphorus and
=
=
oxidation of PPh(CF CF2)2 could not be obtained, even with
sulfur.27
hydrogen peroxide. This illustrates the increased stability of
the phosphorus centre towards oxidation upon substitution
of a second electron-withdrawing perfluorovinyl group and is
consistent with previous reports of the oxidation of P(CF3)3
and P(C6F5)3 with elemental sulfur,32 where complete conver-
sion to the phosphine sulfides required temperatures of 160–
200 ꢁC for up to 8 days. Generally the phosphine selenides
are somewhat less stable than the sulfides or oxides, especially
=
Exclusive production of Z-PPh2(CF CFH), 6, with no
attendant P–C bond cleavage can, however, be achieved if
=
t
PPh2(CF CF2) is reacted with LiAlH(OBu )3 in place of
LiAlH4 . The formation of a single isomer allows for identifica-
tion of the vinylic resonance in the 1H NMR spectrum (7.6
ppm), the chemical shift of which is typical for a proton
attached to an electron-deficient fluorovinyl system, and is
consistent with observations for related silicon, germanium
and tin compounds.22,28–30 The 13C{1H} NMR spectrum of 6
displays resonances between 126 and 132 ppm, assigned to
the aromatic carbons, and two doublet of doublet of doublets
at 149.7 and 152.8 ppm. The former is assigned as the b-vinyl
carbon and the latter as the a-vinyl carbon, on the basis of the
DEPT-135 spectrum and magnitude of the J(PC) and J(CF)
coupling constants.
=
SePEt2(CF CF2), which decomposed completely over
a
period of a few hours, thus precluding satisfactory elemental
analysis.
In all cases retention of the perfluorovinyl group in the final
product was confirmed by 19F NMR spectroscopy, signals for
the products being shifted only slightly from the starting phos-
phines, although significant changes were observed in J(PF)
coupling constants. This is to be expected since there is a
change in oxidation state and angles around the phosphorus
centre in the phosphorus(V) species as compared to the free
phosphines. Additionally, the absence of a lone pair on the
phosphorus atom in 8 to 19 results in a reduction in the mag-
=
The analogous reactions of PPh2(CCl CF2) with hydride
reagents have also been explored, with comparable results.
Thus, with LiAlH4 several species were again observed,
=
E-PPh2(CCl CFH) and Ph2PH being the major products,
formed in admixture with trace species, which include
3
nitude of the J(PFcis) coupling constant for all the phosphor-
13
=
=
PPh2(CH CF2) and E-PPh2(CH CFH). The presence of
both of these species is consistent with displacement of the
geminal chlorine atom being more facile than the correspond-
us(V) compounds, compared to the parent phosphines.
The 31P{1H} NMR spectra of the phosphine selenides show
additional low-intensity satellite peaks, due to coupling to the
spin-active selenium nucleus (77Se, 7.58%, I ¼ 21) from which
absolute values for 1J(SeP) of between 730 and 848 Hz are
obtained. These values lie intermediate between those observed
for trialkyl and triaryl phosphine selenides (680 to 735 Hz) and
trialkyl phosphite selenides (over 900 Hz).33 The magnitude
of the phosphorus-selenium coupling constant is dependent
on the electronic characteristics of the compound rather than
there being any strong correlation between the steric demand
of the phosphine, as measured by its cone angle. For example,
the P–Se coupling constant for SePCy3 (cone angle 170ꢁ) is 673
Hz, whilst that for SePMe3 (cone angle 118ꢁ) is little different
at 684 Hz.34 However, the presence of electron-withdrawing
substituents attached to the phosphorus centre does have a sig-
nificant effect, as displayed by the increase in J(SeP) coupling
=
ing fluorine atom of PPh2(CF CF2). Once again, use of the
milder hydride reagent LiAlH(OBut)3 results in isolation of
=
E-PPh2(CCl CFH), 7 without the presence of by-products.
Perfluorovinylphosphine chalcogenides
Oxidation of perfluorophosphines. The stability of perfluoro-
vinyl phosphines towards aerial oxidation has prompted us to
study this aspect of their behaviour in some detail and to this
end a series of reactions was undertaken (see Scheme 2).
Oxidation reactions were performed with H2O2 , elemental
sulfur and elemental selenium. The reactions with hydrogen
peroxide were effected at 0 ꢁC, whilst those with sulfur or sele-
nium powder required prolonged periods of reflux in toluene,
with an excess of the powdered element.
from SePPh3 (736 Hz)35 to SePPh2(CF CF2) (785 Hz) and
=
=
The progress of the oxidation reactions was monitored by
31P{1H} NMR spectroscopy; in each case the resonances
assigned to the starting phosphines were replaced by a new
peak, observed at higher frequencies of between 45 and 75
SePPh(CF CF2)2 (848 Hz). Coupling to the spin-active sele-
nium nuclei was sometimes also resolved in the 19F NMR spec-
trum, with satellites most often observed to the Fcis nucleus.
In general the products of these reactions were isolated as
i
=
=
oily materials; however, in the case of SPPr2(CF CF2), 13,
ppm, and assigned to the E ¼ PR3 ꢀ x(CF CF2)x species
(E ¼ O, S, Se), the chemical shifts being consistent with those
reported for 4-cooordinate phosphorus(V) compounds.31 The
rates of conversion were highly dependant upon the groups
small X-ray quality crystals slowly developed. Compound 13
adopts the anticipated 4-coordinate geometry around
phosphorus (Fig. 1); selected bond distances and angles are
summarised in Table 1.
=
bound to phosphorus; in general, oxidation of PR2(CF CF2)
i
=
Fig. 1 The molecular structure of SPPr2(CF CF2), 13 (thermal
Scheme 2 Oxidations of perfluorovinyl phosphines with H2O2 , S
and Se.
ellipsoids are plotted at 30% level and hydrogens have been removed
for clarity).
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
830
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 8 2 8 – 8 3 7

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ꢁ
i
˚
Table 1 Selected bond lengths (A) and angles ( ) for SPPr2(CF CF2),
13
=
solutions of the phosphines, dissolved in CDCl3 in an NMR
tube, which resulted in an immediate, exothermic reaction with
liberation of xenon. Fig. 3 shows the 19F NMR spectra of solu-
P(1)–S(1)
P(1)–C(1)
1.9358(9)
1.809(2)
1.810(2)
1.820(2)
C(1)–C(2)
C(1)–F(1)
1.298(3)
1.353(3)
1.310(3)
=
tions containing PEt2(CF CF2), before and after addition of
XeF2 . It is clear that, following the initial addition of XeF2
(Fig. 3(b)), four new multiplets are observed, in addition to
those of the parent phosphine (labelled *), three of which are
observed in regions characteristic of a perfluorovinyl moiety
(ꢀ81, ꢀ97 and ꢀ180 ppm), though with additional couplings.
The fourth resonance appears at ca. ꢀ43 ppm and displays a
P(1)–C(3)
P(1)–C(6)
C(2)–F(2)
C(2)–F(3)
1.301(3)
C(1)–P(1)–S(1)
C(3)–P(1)–S(1)
C(6)–P(1)–S(1)
113.46(8)
114.13(8)
113.49(8)
C(1)–P(1)–C(3)
C(1)–P(1)–C(6)
C(3)–P(1)–C(6)
101.92(11)
103.95(11)
108.82(11)
1
large doublet coupling suggestive of a J(PF) interaction. On
further addition of XeF2 (Fig. 3(c)), these four resonances
become the dominant species. Due to the complexity of these
resonances the final chemical shifts and coupling constants
were determined by modelling the observed spectra against
The three S–P–C angles are all greater than the idealised tet-
rahedral angle, while the three C–P–C angles are all somewhat
˚
=
smaller. The P S bond length [1.9358(9) A] is shorter than that
typically found in trialkyl or triaryl phosphine sulfides: SPCy3
36
37
=
the spin system of F2PEt2(CF CF2) using the programs
˚
˚
=
=
[d(P S) ¼ 1.966(2) A], SPPh3 [d(P S) ¼ 1.950(3) A] and
MestRe-C47 and Spin.48 The quality of the fit between the
calculated and observed spectra (shown in Fig. 4) allows
confidence in our assignment of the NMR spectrum of this
species.
38
˚
=
=
SPPh2(CH CH2) [d(P S) ¼ 1.953(7) A]. The observed dis-
tance is, however, consistent with that found in the limited
number of crystallographically characterised sulfides of
phosphines possessing fluoro-organo groups: SPPh2(CF2Br)
39
The perfluorovinyl phosphorus(V) difluorides 20 to 24 have
all been characterised in this way, as have the products from
˚
=
=
[d(P S) ¼ 1.9348(11) A],
SPMe2(p–C6F4H) [d(P S) ¼
˚
=
˚
1.943(2) A], SPMe2(p–C6F4Cl) [d(P S) ¼ 1.945(1)/1.936(1) A]
40
=
the reactions of PPh2(CX CFH) (X ¼ F, Cl) with XeF2 to
˚
=
and SPMe2(p–C5F4N) [d(P S) ¼ 1.937(1) A]. The three
14
In both compounds the
yield compounds 25 and 26. The 31P{1H} NMR spectra
recorded for 20 to 26 all show a large triplet-based resonance
between ꢀ19.6 and ꢀ66.6 ppm, as the result of a large
1J(PF) coupling, the magnitude of which varies between 654
and 739 Hz. The chemical shifts for all these compounds are
found in the region typical for five-coordinate phosphorus(V)
species. All compounds of this stoichiometry have previously
been assigned as trigonal bipyramidal, with the fluoride ligands
occupying axial positions, and the NMR data for 20 to 26 is
consistent with this formulation; in all cases equivalence of
the two terminal P–F fluorides is evident.
C–F distances in 13 show some variation, as previously
=
observed for PPh(CF CF2)2 .
Ca–F bond is the longest, although there are no particularly
short intra- or intermolecular interactions to account for this.
In the extended structure, stacks of molecules exhibit inter-
laced perfluorovinyl groups in a fluorinated ‘‘zipper-like’’
arrangement in the b direction (Fig. 2). In this way the per-
fluorovinyl groups of the molecules of two adjacent stacks sit
one above another, resulting in fluorocarbon and hydrocarbon
domains within the crystal.
This work represents the first report of perfluorovinyl-con-
taining phosphorus(V) species of stoichiometry R3PF2 and
=
=
compliments the data for (CF2 CF)PF4 and (CF2 CF)2PF3 ,
which have been previously described.49 It has proven impos-
sible to isolate 20 to 26 in their pure form, due to their propen-
sity to decompose in the presence of moisture to the respective
phosphine oxides, as determined by 31P{1H} and 19F NMR
spectroscopy. This is also consistent with the reported
50
=
tendency of (CF2 CF)PF4 to hydrolyse to (CF2 CF)POF2 .
=
Addition of dihalogens
=
The reactions of the phosphines 1 to 3 and PPh2(CF CF2)
with X2 (X ¼ Cl, Br, I) and SO2Cl2 have been explored. How-
ever, a mixture of products is obtained, as indicated by
31P{1H} NMR studies, due to competition between halogena-
tion of the double bond and oxidation of the phosphorus cen-
tre. In order to preclude the latter, reaction of the phosphine
=
oxide, OPPh2(CF CF2), 10, was explored. Reflux of a chloro-
=
form solution of dibromine and OPPh2(CF CF2) resulted in a
change in the colour of the solution from red-brown to yellow.
The 19F NMR spectrum of the resulting yellow oil (27)
displayed three signals at ꢀ50.6, ꢀ53.0 and ꢀ132.4 ppm
(as shown in Fig. 5). This is consistent with the addition of
bromine across the double bond to generate a 1,2-dibromo-
trifluoroethyl moiety.
Oxidation with XeF2. Oxidative fluorination of phosphines
to give R3PF2 species has been achieved with a variety of
The two resonances associated with the b-fluorine nuclei
(Fb , Fb ) are observed in close proximity, with a large mutual
45
reagents, including SF4 ,41 NF3O,42 COF2 ,43 F2 ,44 XeF2
0
and also via electrochemical methods.46 Of these the use of
XeF2 has a number of advantages to offer, including its ease
of handling, short reaction times and gaseous xenon being
the by-product. Therefore, the reaction of the perfluorovinyl
coupling constant (170 Hz), due to diastereotopism at the
b-carbon centre. This results in a marked departure of these
resonances from first-order behaviour. Notwithstanding, all
couplings are clearly resolved and correlate well with those
observed for0 the unique a-fluorine (Fa) resonance (23 and 18
Hz). The Fb resonance (ꢀ53.0 ppm) additionally exhibits a
further doublet coupling of 3 Hz. Coupling of a similar
magnitude is also observed in the 31P{1H} NMR spectrum,
phosphines PR3 ꢀ x(CF CF2)x (x ¼ 1, R ¼ Et, 1; iPr, 2;
=
=
Cy, 3; Ph; x ¼ 2, R ¼ Ph), Z-PPh2(CF CFH), 6, and
=
E-PPh2(CCl CFH), 7, with xenon difluoride were undertaken.
Under an inert atmosphere, crystals of XeF2 were added to
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 8 2 8 – 8 3 7
831

View Article Online
19
=
F NMR spectra of PEt2(CF CF2) (a), PEt2(CF CF2) and 0.6 equiv. XeF2 (b) and PEt2(CF CF2) and 1.1 equiv. XeF2 (c).
=
=
Fig. 3
3
0
suggesting this to be a J(PFb ) interaction. Significantly, no
such coupling is observed to Fb and we therefore suggest that
the observed interaction is dipolar-mediated and thus localised
due to hindered rotation around the C–C bond. Variable
temperature NMR studies would seem to support this sugges-
tion, the coupling being lost at elevated temperatures.
The 13C{1H} NMR spectrum of 27 displays four aromatic
resonances between 127.5 and 133.9 ppm and two further mul-
tiplets at 104.4 and 120.5 ppm. The resonance at 104.4 ppm
appears as an overlapping doublet of doublet of doublet of
1
doublets, with one large J(CF) coupling of 283.9 Hz, and is
thus assigned to the a-carbon of the CFBrCF2Br group. The
apparent triplet multiplicity of this resonance arises due to
coupling to the two diastereotopic fluorine nuclei
2
2
0
[ J(CFb) ¼ J(CFb ) ¼ 32.8 Hz]; the remaining doublet cou-
1
pling (63.7 Hz) is assigned as a J(CP) interaction. The b-car-
bon resonance (120.5 ppm) exhibits two large 1J(CF) couplings
(313.9 Hz twice) and smaller interactions to the a-fluorine and
phosphorus nuclei.
Conclusion
In conclusion, we have generated a range of new fluorovinyl-
substituted phosphines and have demonstrated methods of
derivatising these compounds stereospecifically to generate
Fig. 4 Calculated (left) and observed (right) 19F NMR signals due to
=
F2PEt2(CF CF2).
Fig. 5 Sections of the 19F NMR spectrum of OPPh2(CFBrCF2Br),
27.
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
832
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 8 2 8 – 8 3 7

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new difluorovinyl phosphines in high yields. We have studied
the oxidation of fluorovinyl-substituted phosphines in detail
and report the first crystal structure of a phosphorus(V)
temperature below ꢀ90 ꢁC. The reaction was left at ꢀ78 ꢁC
for 2 h, after which time it was allowed to attain ambient tem-
perature overnight. Subsequent addition of hexane (100 cm3)
resulted in the precipitation of lithium salts, which were
removed by filtration. The resulting organic phase was dried
over anhydrous MgSO4 and filtered. Distillation of the crude
product under vacuum (56–60 ꢁC, 10 mm Hg), afforded
1 as a clear liquid (1.266 g, 62.8%). (Found: C, 42.3;
H, 5.3%. C6H10F3P requires C, 42.4; H, 5.9%). n/cmꢀ1
i
=
perfluorovinyl compound, SPPr2(CF CF2) 13.
Experimental
General methods and materials
=
=
=
(neat): 1734 (C C), 1298 ( CF2 asym), 1132 ( C–F), 1042
Syntheses of the tertiary phosphines 1 to 4 were carried out
under an inert atmosphere of argon or nitrogen in flame-dried
glassware. Diethyl ether and THF were dried over sodium wire
for ca. 24 h and subsequently refluxed over sodium/benzophe-
none under a nitrogen atmosphere. CF3CFH2 (HFC-134a. Ineos
Fluor), BuLi (2.5 M in hexanes, Acros), PEt2Cl, PPri2Cl and
3
3
=
( CF2 sym). dP : ꢀ32.3 [dd, J(PF1) ¼ 5 Hz, J(PF2) ¼ 53 Hz],
dF1 trans : ꢀ86.6 [ddd, 2J(F1F2) ¼ 54 Hz, 3J(PF1) ¼ 5 Hz,
3J(F1F3) ¼ 30 Hz], dF2 cis : ꢀ111.6 [ddd, 2J(F1F2) ¼ 54 Hz,
3J(F2F3) ¼ 124 Hz, 3J(PF2) ¼ 53 Hz], dF3 gem : ꢀ187.7 [dd,
3J(F1F3) ¼ 30 Hz, 3J(F2F3) ¼ 124 Hz], dH : 1.58 [dq, (CH2),
2J(PH) ¼ 21.6 Hz, 3J(HH) ¼ 7.5 Hz], 1.13 [dt, (CH3),
PCy2Cl (Aldrich) were used as supplied after verification of
3J(PH) ¼ 16.5 Hz, 3J(HH) ¼ 7.5 Hz], dC
: 15.1 [s,
14
=
=
=
and PPh2(CCl
ethyl
purity. PPh2(CF CF2), PPh(CF CF2)2
2
CF2)18 were prepared as described previously. 19F, 31P{1H}
and 1H NMR spectra were recorded on a Bruker DPX200
spectrometer operating at 188.3, 81.8 and 200.1 MHz, respec-
tively. Peak positions are quoted relative to external CFCl3 ,
85% H3PO4 and TMS, respectively, using the high frequency
positive convention. 13C{1H} NMR spectra (reference TMS)
were recorded on a Bruker DPX 400 spectrometer, operating
at 100.5 MHz. Infrared and Raman spectra were recorded
(CH2), br], 8.7 [d, (CH3), J(PC) ¼ 13.5 Hz], dC a-vinyl : 127.3
[dddd, 1J(PC) ¼ 51.2 Hz, 2J(CF) ¼ 6.8, 47.3 Hz,
1J(CF) ¼ 289.8 Hz], dC b-vinyl : 158.8 [dddd, 2J(PC) ¼ 29.9
2
1
Hz, J(CF) ¼ 43.5 Hz, J(CF) ¼ 282.0, 304.2 Hz].
i
=
PPr2(CF CF2), 2. Synthesis was in an analogous manner to
1, using HFC-134a (3.50 cm3, 0.042 mol), BuLi (33.2 cm3,
0.083 mol) and PPri2Cl (6.28 cm3, 0.042 mol) in 100 cm3 diethyl
ether. Workup and distillation at 65–68 ꢁC (10 mm Hg)
resulted in 2 as a clear liquid (8.025 g, 87%). (Found: C,
48.2; H, 7.4; F, 29.1%. C8H14F3P requires C, 48.5; H, 7.1; F,
on
a
Nicolet-Nexus FT-IR/Raman spectrometer with
OMNIC 5 software. Elemental analyses were performed by
the Departmental Microanalytical Service.
28.8%). n/cmꢀ1 (neat): 1728 (C C), 1294 ( CF2 asym), 1129
=
=
( C–F), 1036 ( CF2 sym). dP : ꢀ7.7 [ddd, 3J(PF1) ¼ 4 Hz,
3J(PF2) ¼ 53 Hz, 2J(PF3) ¼ 7 Hz], dF1 trans : ꢀ86.5 [ddd,
2J(F1F2) ¼ 53 Hz, 3J(PF1) ¼ 4 Hz, 3J(F1F3) ¼ 29 Hz],
dF2 cis : ꢀ110.7 [ddd, 2J(F1F2) ¼ 53 Hz, 3J(F2F3) ¼ 126 Hz,
3J(PF2) ¼ 53 Hz], dF3 gem : ꢀ178.9 [ddd, 3J(F1F3) ¼ 29 Hz,
=
=
X-Ray crystallography
Measurements for 13 were made on a Nonius MACH3 CAD4
diffractometer, using graphite monochromated Mo-Ka radia-
˚
tion (l ¼ 0.71073 A). All the data obtained was corrected
2
3J(F2F3) ¼ 126 Hz, J(PF3) ¼ 7 Hz], dH : 0.92 [br], 1.10 [br],
for Lorentz, polarisation and absorption using the psi-scan
method. X-Ray structural data solution was by direct methods
and refined against F2 using SHELXTL51 or SHELX-9752 with
H-atoms in ideal positions. All non-H atoms were modelled
with anisotropic displacement parameters. The asymmetric
units shown in the figures were produced using ORTEP-3 for
d
C alkyl : 18.6 [s], 18.7 [d, J(PC) ¼ 13.5 Hz], 20.6 [br], dC a-vinyl
:
127.4 [dddd, 1J(PC) ¼ 54.1 Hz, 2J(CF) ¼ 8.7, 46.4 Hz,
1J(CF) ¼ 291.7 Hz], dC b-vinyl : 159.7 [dddd, 2J(PC) ¼ 29.9
2
1
Hz, J(CF) ¼ 43.6 Hz, J(CF) ¼ 281.0, 304.2 Hz].
Windows.53 Crystal data for SPPr2(CF CF2): C8H14F3PS,
i
=
=
PCy2(CF CF2), 3. Prepared as for 1, using HFC-134a (2.50
M ¼ 230.22, triclinic, space group P-1,ꢁ a ¼ 6.6533(10),
cm3, 0.030 mol), BuLi (23.7 cm3, 0.059 mol) and PCy2Cl (6.55
cm3, 0.030 mol) in 100 cm3 diethyl ether. Workup and purifica-
tion by column chromatography (50:50 toluene–hexane)
resulted in 3 as a clear liquid (6.04 g, 72%). (Found: C, 59.9;
H, 7.1; P, 10.1%. C14H22F3P requires C, 60.4; H, 8.0; P,
11.2%). dP : ꢀ16.2 [ddd, 3J(PF1) ¼ 5 Hz, 3J(PF2) ¼ 54 Hz,
2J(PF3) ¼ 8 Hz], dF1 trans : ꢀ86.4 [ddd, 2J(F1F2) ¼ 30 Hz,
3J(PF1) ¼ 5 Hz, 3J(F1F3) ¼ 29 Hz], dF2 cis : ꢀ110.5 [ddd,
2J(F1F2) ¼ 30 Hz, 3J(F2F3) ¼ 127 Hz, 3J(PF2) ¼ 54 Hz],
ꢁ
˚
b ¼ 8.881(2), c ¼ 9.771(2) A, a ¼ 82.31(2) , b ¼ 74.07(2) ,
3
ꢁ
˚
g ¼ 86.98(2) , U ¼ 550.09(19) A , Z ¼ 8, Dc ¼ 1.390 Mg
m
ꢀ3, m(Mo–Ka) ¼ 0.435 mmꢀ1, crystal size 0.25 ꢂ 0.25 ꢂ
0.10 mm3, F(000) ¼ 240, T ¼ 203(2) K, max/min trans-
mission ¼ 0.9578/0.8990; 2115 reflections measured (2.18ꢁ to
24.97ꢁ y range), 1931 unique [R(int) ¼ 0.0109], which were
used in all calculations. The final R1 ¼ 0.0323,
wR2 ¼ 0.0744, R1 (all data) was 0.0472. Max/min residual
electron density ¼ þ0.239 and ꢀ0.226 e Aꢀ3, respectively.z
˚
3
3
d
F3 gem : ꢀ177.3 [ddd, J(F1F3) ¼ 29 Hz, J(F2F3) ¼ 127 Hz,
2J(PF3) ¼ 8 Hz], dH : 1.82 [br], 1.29 [br].
Syntheses
n
BuPhP(CF CF2), 4. nBuPhPCl was prepared by the slow
=
=
PEt2(CF CF2), 1.
A
three-neck round-bottom flask
addition of BuLi (5.6 cm3, 0.014 mol) to a cold (ꢀ100 ꢁC)
n
equipped with magnetic stirrer, and argon inlet and outlet,
was held in an ethanol slush bath (ꢀ80 ꢁC) and diethyl ether
(50 cm3) was added. The temperature was lowered to ca.
ꢀ100 ꢁC and liquid HFC-134a (1.00 cm3, 0.012 mol) intro-
duced. Two equivalents of n-BuLi (9.49 cm3, 0.024 mol) were
added slowly, maintaining the temperature below ꢀ80 ꢁC.
After addition of the BuLi the temperature was raised and
maintained between ꢀ55 ꢁC and ꢀ65 ꢁC for 2 h. The tempera-
ture was then lowered to ꢀ90 ꢁC and a concentrated, cold
solution of PEt2Cl (1.44 cm3, 0.012 mol) dissolved in diethyl
ether (50 cm3) was added dropwise, maintaining the solution
solution of PhPCl2 (2.5 cm3, 0.014 mol) in diethyl ether (100
cm3) under a nitrogen atmosphere. The reaction mixture was
allowed to attain ambient temperature and the precipitated
LiCl removed by filtration. The solvent was reduced to 20
cm3 under vacuum and the resulting material reacted with
3
=
CF2 CFLi, as described for 1, using HFC-134a (1.2 cm ,
0.014 mol), BuLi (11.2 cm3, 2.5 M, 0.028 mol) in 100 cm3
diethyl ether. Workup and purification by column chromato-
graphy (chloroform), followed by distillation (141 ꢁC, 65 mm
Hg), resulted in 4 as a clear liquid (0.95 g, 28%). (Found: C,
52.6; H, 5.2; P, 10.3%. C12H14F3Pꢃ0.33CHCl3 requires C,
51.8; H, 5.1; P, 10.8%). dP : ꢀ37.0 [ddd, 3J(PF1) ¼ 4 Hz,
3J(PF2) ¼ 55 Hz, 3J(PF3) ¼ 8 Hz], dF1 trans : ꢀ82.9 [ddd,
2J(F1F2) ¼ 41 Hz, 3J(PF1) ¼ 4 Hz, 3J(F1F3) ¼ 12 Hz],
z CCDC reference number 232752. See http://www.rsc.org/
suppdata/nj/b3/b316099h/ for crystallographic data in .cif or other
electronic format.
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 8 2 8 – 8 3 7
833

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d
F2 cis : ꢀ106.5 [ddd, 2J(F1F2) ¼ 41 Hz, 3J(F2F3) ¼ 125 Hz,
yellow oil, after purification by column chromatography
(eluent 1:1 hexane–toluene) (0.73 g, 83%). (Found: C, 67.6;
H, 4.3; P, 12.0%. C14H11F2P requires C, 67.8; H, 4.5; P,
3J(PF2) ¼ 55 Hz], dF3 gem : ꢀ176.8 [ddd, 3J(F1F3) ¼ 12 Hz,
3J(F2F3) ¼ 125 Hz, J(PF3) ¼ 8 Hz], dH : 0.92 [br], 1.10 [br],
2
d
C alkyl : 14.0 [s], 22.3 [s], 24.2 [s], 28.2 [s] dC a-vinyl : 127.4 [dddd,
12.5%). n/cmꢀ1 (neat): 3074, 3057 (C–H vinyl), 1647 (C C),
=
1J(PC) ¼ 54.1 Hz, 2J(CF) ¼ 8.7, 46.4 Hz, 1J(CF) ¼ 291.7 Hz],
1151, 1105 (C–F). dP : ꢀ27.5 [dd, 3J(PF) ¼ 74 Hz, 2J(PF) ¼
8 Hz], dF cis : ꢀ159.8 [ddd, 3J(FF) ¼ 144 Hz, 3J(PF) ¼ 74
Hz, 3J(FH) ¼ 77 Hz], dF gem : ꢀ163.9 [ddd, 3J(FF) ¼ 144
Hz, 3J(FH) ¼ 6 Hz, 2J(PF) ¼ 8 Hz], dH vinyl : 7.59 [ddd,
3J(PH) ¼ 12 Hz, 3J(FH) ¼ 77 Hz, 3J(FH) ¼ 6 Hz],
2
2
d
C b-vinyl : 159.5 [dddd, J(PC) ¼ 33.4 Hz, J(CF) ¼ 43.6 Hz,
1J(CF) ¼ 283.0, 337.9 Hz].
ꢀ3
=
=
Z-PPh2(CF CFBu), 5. PPh2(CF CF2) (0.5 g, 1.88 ꢂ 10
mol) was dissolved in 100 cm3 of ether and cooled to
ꢀ90 ꢁC, whereupon n-BuLi (1.5 cm3, 3.00 ꢂ 10ꢀ3 mol) was
added dropwise, resulting in a colour change from yellow to
brown. After allowing the solution to warm to ꢀ60 ꢁC, ice/
water (100 cm3) was added and the mixture left to stand until
all the ice had melted; the organic soluble material was then
extracted into diethyl ether (4 ꢂ 50 cm3). Removal of the sol-
vent yielded a brown oil that was purified by column chroma-
tography (eluent 1:1 hexane–toluene) to afford 5 as a brown oil
(0.470 g, 82%). (Found: C, 71.0; H, 6.5; F, 12.1%. C18H19F2P
requires C, 71.0; H, 6.3; F, 12.5%). n/cmꢀ1 (neat): 3056 (C–H
dH
:
7.51 [m, br], 7.40 [m, br], dC
: 126.8
ipso
aromatic
[d, 1J(PC) ¼ 81 Hz], dC meta : 126.9 [d, 3J(PC) ¼ 7 Hz],
d
C para : 127.6 [s], dC ortho : 131.7 [d, 2J(PC) ¼ 20 Hz], dC b-vinyl
:
149.7 [ddd, 1J(CF) ¼ 253 Hz, 2J(CF) ¼ 61 Hz, 2J(PC) ¼ 19
Hz], dC a-vinyl : 152.7 [ddd, 1J(CF) ¼ 293 Hz, 2J(CF) ¼ 44
1
Hz, J(PC) ¼ 38 Hz].
=
=
Reaction of PPh2(CCl CF2) with LiAlH4. PPh2(CCl CF2)
(1.0 g, 3.54 ꢂ 10ꢀ3 mol) was reacted with LiAlH4 (0.54 g,
0.014 mol) using the same method outlined above for
=
PPh2(CF CF2) to yield a mixture of the following species.
=
Major products: E-PPh2(CCl CFH), 7 (see following reaction
for details); Ph2PH (see above). Minor products:
2
=
arom), 2964, 2928, 2874 (C–H alkyl), 1670 (C C), 1132, 1091
:
(C–F). dP : ꢀ27.1 [dd, 3J(PF) ¼ 89 Hz, 2J(PF) ¼ 5 Hz], dF cis
ꢀ132.7 [ddt, 3J(FF) ¼ 141 Hz, 3J(PF) ¼ 89 Hz, 3J(FHa) ¼ 23
PPh2(CCl CH2): dP ꢀ32.8 [s], dH trans 6.6 [dd, J(HH) ¼ 2.4
=
Hz], dF gem : ꢀ159.1 [dtd, 3J(FF) ¼ 141 Hz, 4J(FHa) ¼ 10 Hz,
Hz, 3J(PH) ¼ 11 Hz], dH
6.4 [dd, 2J(HH) ¼ 2.4 Hz,
cis
2J(PF) ¼ 5 Hz], dH
Ha : 2.5 [ddt, 3J(FHa) ¼ 23 Hz,
3J(PH) ¼ 28 Hz]; Z-PPh2(CCl CFH): dP ꢀ4.3 [d,
=
butyl
4J(FHa) ¼ 10 Hz, 3J(HaHb) ¼ 7.5 Hz], dHb
:
1.6 [tt,
1.4 [tq,
: 1.0 [t,
3J(PF) ¼ 24 Hz], dF
ꢀ99.6 [dd, 3J(PF) ¼ 24 Hz,
trans
3J(HaHb) ¼ 7.5 Hz, 3J(HbHc) ¼ 7.5 Hz], dHc
:
2J(HF) ¼ 80 Hz]; E-PPh2(CH CFH): dP ꢀ26.9 [d,
=
3J(HbHc) ¼ 7.5 Hz, 3J(HcHd) ¼ 7.5 Hz], dHd
3J(PF) ¼ 17 Hz], dF ꢀ95.2 [ddd, 3J(HF) ¼ 21 Hz,
3J(HcHd) ¼ 7.5 Hz], dCd : 14.0 [s], dCc : 22.4 [s], dCa : 27.4
2J(HF) ¼ 86 Hz, 3J(PF) ¼ 17 Hz], dH
6.90 [ddd,
cis
2
3
2
3
[dd, J(CF) ¼ 23 Hz, J(CF) ¼ 2 Hz], dCb : 28.1 [s], dC meta
:
3J(HH) ¼ 11.7 Hz, J(HF) ¼ 86 Hz, J(PH) ¼ 6 Hz], dH gem
3
128.9 [d, J(PC) ¼ 6.6 Hz], dC para : 129.4 [s], dC ortho : 133.8
[d, 2J(PC) ¼ 19.4 Hz], dC a-vinyl : 149.1 [ddd, 1J(PC) ¼ 51.2
Hz, 2J(CF) ¼ 42.5 Hz, 1J(CF) ¼ 287.0 Hz], dC b-vinyl : 164.9
[ddd, 2J(PC) ¼ 19.3 Hz, 2J(CF) ¼ 46.4 Hz, 1J(CF) ¼ 251.1 Hz].
6.11
[dd,
=
3J(HH) ¼ 11.7
Hz,
3J(HF) ¼ 21
Hz];
13
3
PPh2(CH CF2): dP ꢀ33.3 [d, J(PF) ¼ 45 Hz]
ꢀ3
=
=
E-PPh2(CCl CFH), 7. PPh2(CCl CF2) (1.02 g, 3.61 ꢂ 10
mol) was dissolved in THF (50 cm3) and LiAlH(OBut)3 (1.83 g,
7.20 ꢂ 10ꢀ3 mol) added. Following workup, as for 6 above,
resulted in isolation of 7 as a pale yellow oil, after purification
by column chromatography (eluent 1:1 hexane–toluene) (0.591
g, 62%). (Found: C, 63.4; H, 4.3; Cl, 14.8%. C14H11ClFP
requires C, 62.5; H, 4.2; Cl, 13.4%). dP : ꢀ14.5
[d, 3J(PF) ¼ 84 Hz], dF : ꢀ106.5 [dd, 3J(PF) ¼ 84 Hz,
=
=
Reaction of PPh2(CF CF2) with LiAlH4. PPh2(CF CF2)
(2.0 g, 7.52 ꢂ 10ꢀ3 mol) was dissolved in diethyl ether (50
cm3) and cooled to ꢀ80 ꢁC, whereupon freshly powdered
LiAlH4 (1.14 g, 0.030 mol) was added, the resulting solution
being allowed to return to room temperature overnight. Dry
hexane (100 cm3) was added and the solution filtered to yield
a pale yellow filtrate that was dried over MgSO4 , re-filtered
and the solvent removed in vacuo to yield a mixture of the
2J(FH) ¼ 82 Hz], dH
:
7.35 [dd, 3J(PH) ¼ 12 Hz,
vinyl
2J(FH) ¼ 82 Hz], dH aromatic : 7.51 to 7.40 [m, br], dC
:
ipso
following species. Major products: Z-PPh2(CF CFH), 6
(see following reaction for details); Ph2PH: dP ꢀ39.0
54
127.0 [d, 1J(PC) ¼ 79 Hz], dC meta : 126.9 [d, 3J(PC) ¼ 7.7
=
2
Hz], dC para : 127.7 [s], dC ortho : 131.8 [d, J(PC) ¼ 20.3 Hz],
1
3
1
[dq, J(PH) ¼ 218 Hz, J(PH) ¼ 7 Hz], dH 5.37 [d, J(PH) ¼
dC b-vinyl : 155.0 [dd, 1J(CF) ¼ 275 Hz, 2J(PC) ¼ 19 Hz],
2
1
=
218 Hz]. Minor products: PPh2(CF CH2):
dP ꢀ9.5
d
C a-vinyl : 119.0 [dd, J(CF) ¼ 26 Hz, J(PC) ¼ 55 Hz].
[d, 2J(PF) ¼ 40.4 Hz], dF ꢀ96.2 [ddd, 3J(HF) ¼ 20.4, 50.9 Hz,
2J(PF) ¼ 40.4 Hz], dH
5.45 [ddd, 2J(HH) ¼ 2.6 Hz,
OPR3 À x(CF CF2)x (x = 1, R = Et, 8; R = iPr, 9; R = Ph,
trans
=
3J(HH) ¼ 20.4 Hz, 3J(PH) ¼ 23.4 Hz], dH
5.03 [ddd,
cis
=
10; x = 2, R = Ph, 11). The synthesis of OPEt2(CF CF2) (8)
2J(HH) ¼ 2.6 Hz, 3J(HF) ¼ 50.9 Hz, 3J(PH) ¼ 6.4 Hz];
=
is typical. PEt2(CF CF2) (0.178 g, 0.001 mol) was dissolved
E-PPh2(CF CFH): dP ꢀ19.9 [dd, 2J(PF) ¼ 10.5 Hz,
=
in THF (5 cm3) and an excess of 27% w/w H2O2 (10.5 cm3)
was added at 0 ꢁC (ice bath). The mixture was stirred for 20
to 30 min and the progress of the reaction checked by
31P{1H} NMR spectroscopy. Water (15 cm3) and chloroform
(20 cm3) were added to the reaction mixture and
3J(PF) ¼ 32.9 Hz], dF
ꢀ134.3 [ddd, 3J(FF) ¼ 19 Hz,
trans
3J(PF) ¼ 33 Hz, 2J(HF) ¼ 74 Hz], dF
ꢀ141.3 [ddd,
gem
3J(PF) ¼ 10.5 Hz, 3J(FF) ¼ 19 Hz, 3J(HF) ¼ 17 Hz], dH cis
6.86 [ddd, 2J(HF) ¼ 74 Hz, 3J(HF) ¼ 17 Hz, 3J(PH) ¼ 4
Hz]; Z-PPh2(CH CFH): dP ꢀ9.8 [d, 3J(PF) ¼ 58.6 Hz], dF
=
=
OPEt2(CF CF2) was extracted into the organic phase, which
was dried with MgSO4 . After filtration the solvent was
removed to yield 8 as a clear liquid.
3
2
3
ꢀ125.3 [ddd, J(HF) ¼ 18 Hz, J(HF) ¼ 70 Hz, J(PF) ¼ 56
Hz]; PhPH2 : dP ꢀ121.0 [tt, 1J(PH) ¼ 199 Hz, 3J(PH) ¼ 7
55
=
=
Hz]; PPh2(CH CF2) (see reaction of PPh2(CCl CF2) with
8. (0.077 g, 41%). (Found: C, 37.0; H, 5.4; F, 28.7%.
C6H10F3PO requires C, 38.7 H, 5.4; F, 30.6%). dP : 45.8
[dd, 3J(PF2) ¼ 10 Hz, 2J(PF3) ¼ 45 Hz], dF1 trans : ꢀ81.8
[dd, 2J(F1F2) ¼ 45 Hz, 3J(F1F3) ¼ 30 Hz], dF2 cis : ꢀ106.7
[ddd, 2J(F1F2) ¼ 45 Hz, 3J(F2F3) ¼ 119 Hz, 3J(PF2) ¼ 10 Hz],
=
LiAlH4); PPh2(CH CH2): dP ꢀ11.4 [s]
ꢀ3
=
=
Z-PPh2(CF CFH), 6. PPh2(CF CF2) (0.95 g, 3.57 ꢂ 10
mol) was dissolved in THF (50 cm3) and freshly powdered
LiAlH(OBut)3 (1.81 g, 7.14 ꢂ 10ꢀ3 mol) was added at ambient
temperature; the mixture was stirred overnight. The reaction
was quenched with water and the product extracted with
40–60ꢁ petroleum ether (2 ꢂ 20 cm3), dried over MgSO4 ,
re-filtered and solvent removed in vacuo to yield 6 as a pale
3
3
d
F3 gem : ꢀ192.3 [ddd, J(F1F3) ¼ 30 Hz, J(F2F3) ¼ 119 Hz,
2J(PF3) ¼ 45 Hz]. n/cmꢀ1 (neat): 1738 (C C), 1318 ( CF2
= =
=
asym), 1165 ( C–F), 1069 ( CF2 sym).
=
9. (0.119 g, 55%). (Found: C, 45.2; H, 6.8; F, 26.2%.
C8H14F3PO requires C, 44.9; H, 6.5; F, 26.6%). dP 53.4
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
834
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 8 2 8 – 8 3 7

View Article Online
[dd, 3J(PF2) ¼ 10 Hz, 2J(PF3) ¼ 34 Hz], dF1
ꢀ80.3
SePR3 À x(CF CF2)x (x = 1, R = Et, 16; R = iPr, 17;
R = Ph, 18; x = 2, R = Ph, 19). Perfluorovinyl phosphine
=
trans
[dd, 2J(F1F2) ¼ 43 Hz, 3J(F1F3) ¼ 30 Hz], dF2 cis : ꢀ105.7
[ddd, 2J(F1F2) ¼ 43 Hz, 3J(F2F3) ¼ 119 Hz, 3J(PF2) ¼ 10 Hz],
selenides were synthesised by a similar method as the sulfidꢀes3
3
3
i
=
d
F3 gem : ꢀ189.5 [ddd, J(F1F3) ¼ 30 Hz, J(F2F3) ¼ 119 Hz,
12 to 15. For example, PPr2(CF CF2) (0.85 g, 4.30 ꢂ 10
2J(PF3) ¼ 34 Hz]. n/cmꢀ1 (neat): 1732 (C C), 1314 ( CF2
mol) was refluxed with selenium (0.455 g, 5.70 ꢂ 10ꢀ3 mol) in
20 cm3 toluene for 3 h. After this period the excess selenium
was filtered off and the solvent removed to yield 17 as a brown
liquid.
=
=
=
asym), 1204 (P O), 1156 ( C–F), 1063 ( CF2 sym).
=
=
10. (0.183 g, 65%). (Found: C, 59.5; H, 3.5; F, 19.9%.
C14H10F3PO requires C, 59.6; H, 3.5; F, 20.2%). dP : 19.8
[ddd, 3J(PF1) ¼ 6 Hz, 3J(PF2) ¼ 11 Hz, 2J(PF3) ¼ 49 Hz],
dF1 trans : ꢀ79.9 [ddd, 3J(PF1) ¼ 6 Hz, 2J(F1F2) ¼ 38 Hz,
3J(F1F3) ¼ 28 Hz], dF2 cis : ꢀ101.4 [ddd, 2J(F1F2) ¼ 38 Hz,
16. (0.418 g, 39%). dP : 33.4 [dd, 1J(SeP) ¼ 730 Hz,
3J(PF2) ¼ 10 Hz, 2J(PF3) ¼ 34 Hz,], dF1
:
ꢀ79.9
trans
[dd, 2J(F1F2) ¼ 38 Hz, 3J(F1F3) ¼ 32 Hz], dF2 cis : ꢀ99.8
3
3J(F2F3) ¼ 120 Hz, J(PF2) ¼ 11 Hz], dF3 gem : ꢀ186.6 [ddd,
[ddd, 2J(F1F2) ¼ 38 Hz, 3J(F2F3) ¼ 123 Hz, 3J(PF2) ¼ 10 Hz],
3J(F1F3) ¼ 28 Hz, 3J(F2F3) ¼ 120 Hz, 2J(PF3) ¼ 49 Hz].
d
F3 gem : ꢀ182.9 [ddd, J(F1F3) ¼ 32 Hz, J(F2F3) ¼ 123 Hz,
3
3
n/cmꢀ1 (CH2Cl2): 1734 (C C), 1323 ( CF2 asym), 1173
2J(PF3) ¼ 34 Hz]. n/cmꢀ1 (neat): 1736 (C C), 1316 ( CF2
=
=
= =
=
( C–F), 1072 ( CF2 sym).
=
=
asym), 1144 ( C–F), 1065 ( CF2 sym).
=
11. Complete conversion to the phosphine oxide was not
obtained, data characteristic of 11 is given below. dP : 8.4
[ttt, 3J(PF1) ¼ 10 Hz, 3J(PF2) ¼ 11 Hz, 2J(PF3) ¼ 56 Hz],
dF1 trans : ꢀ77.3 [ddd, 3J(PF1) ¼ 10 Hz, 2J(F1F2) ¼ 31 Hz,
3J(F1F3) ¼ 30 Hz], dF2 cis : ꢀ99.4 [ddd, 2J(F1F2) ¼ 31 Hz,
17. (0.536 g, 45%). (Found: C, 39.6; H, 5.9; F, 6.7%.
C8H14F3PSe requires C, 34.7; H, 5.1; F, 11.2%). dP : 55.9
[dd, 1J(SeP) ¼ 766 Hz, 3J(PF2) ¼ 10 Hz, 2J(PF3) ¼ 24 Hz,],
dF1 trans : ꢀ79.7 [dd, 2J(F1F2) ¼ 33 Hz, 3J(F1F3) ¼ 32 Hz],
dF2 cis : ꢀ98.5 [ddd, 4J(SeF) ¼ 28 Hz, 2J(F1F2) ¼ 33 Hz,
3
3J(F2F3) ¼ 121 Hz, 3J(PF2) ¼ 11 Hz], dF3
:
ꢀ192.4
3J(F2F3) ¼ 124 Hz, J(PF2) ¼ 10 Hz], dF3 gem : ꢀ179.6 [ddd,
gem
[ddd, 3J(F1F3) ¼ 30 Hz, 3J(F2F3) ¼ 121 Hz, 2J(PF3) ¼ 56 Hz].
3J(F1F3) ¼ 32 Hz, 3J(F2F3) ¼ 124 Hz, 2J(PF3) ¼ 24 Hz].
n/cmꢀ1 (CH2Cl2): 1734 (C C), 1333 ( CF2 asym), 1200
n/cmꢀ1 (neat): 1732 (C C), 1316 ( CF2 asym), 1144
=
=
=
=
=
(P O), 1181 ( C–F), 1071 ( CF2 sym).
=
=
=
=
=
( C–F), 1059 ( CF2 sym), 550 (P Se).
18. (0.835 g, 56%). (Found: C, 48.0; H, 2.7; F, 8.1%.
C14H10F3PSe requires C, 48.7; H, 2.9; F, 9.0%). dP : 22.2
[ddd, 1J(SeP) ¼ 785 Hz, 3J(PF1) ¼ 3 Hz, 3J(PF2) ¼ 12 Hz,
2J(PF3) ¼ 46 Hz,], dF1 trans : ꢀ80.4 [ddd, 2J(F1F2) ¼ 33 Hz,
3J(F1F3) ¼ 30 Hz, 3J(PF1) ¼ 3 Hz], dF2 cis : ꢀ96.3 [ddd,
4J(SeF) ¼ 18 Hz, 2J(F1F2) ¼ 33 Hz, 3J(F2F3) ¼ 123 Hz,
3J(PF2) ¼ 12 Hz], dF3 gem : ꢀ176.6 [ddd, 3J(SeF) ¼ 3 Hz,
3J(F1F3) ¼ 30 Hz, 3J(F2F3) ¼ 123 Hz, 2J(PF3) ¼ 46 Hz].
SPR3 À x(CF CF2)x (x = 1, R ¼ Et, 12; R = iPr, 13;
=
R = Ph, 14; x = 2, R = Ph, 15). Perfluorovinyl phosphine sul-
fides were synthesised by refluxing the phosphine with a large
excess of sulfur, the synthesisꢀ3of 14 being typical.
=
PPh2(CF CF2) (0.710 g, 2.67 ꢂ 10 mol) was dissolved in
toluene (15 cm3) and an excess of sulfur (0.193 g, 6 ꢂ 10ꢀ3
mol) was added. The solution was refluxed for 18 h, with addi-
tional 0.2 g portions of sulfur added every 3 h. After the reac-
tion was judged to have gone to completion (31P{1H} NMR
spectroscopy), the solvent was removed and the residue puri-
fied by column chromatography using 50:50 toluene–ether as
eluent. The solvent was removed to give 14 as a yellow oil.
12. (0.208 g, 38%). dP : 47.2 [dd, 3J(PF2) ¼ 10 Hz,
2J(PF3) ¼ 37 Hz], dF1 trans : ꢀ80.0 [dd, 2J(F1F2) ¼ 39 Hz,
3J(F1F3) ¼ 32 Hz], dF2 cis : ꢀ101.3 [ddd, 2J(F1F2) ¼ 39 Hz,
n/cmꢀ1 (neat): 1726 (C C), 1317 ( CF2 asym), 1144
=
=
=
=
( C–F), 1058 ( CF2 sym), 582 (P Se).
=
19. Complete conversion of starting material was not achieved
even after extended periods of reaction. dP : 4.5 [ttt,
1J(SeP) ¼ 848 Hz, 3J(PF1) ¼ 5 Hz, 3J(PF2) ¼ 13 Hz,
2J(PF3) ¼ 47 Hz,], dF1 trans : ꢀ78.6 [ddd, 2J(F1F2) ¼ 33 Hz,
3J(F1F3) ¼ 32 Hz, 3J(PF1) ¼ 5 Hz], dF2 cis : ꢀ96.9 [ddd,
2J(F1F2) ¼ 33 Hz, 3J(F2F3) ¼ 124 Hz, 3J(PF2) ¼ 13 Hz],
3
3
d
F3 gem : ꢀ181.2 [ddd, J(F1F3) ¼ 33 Hz, J(F2F3) ¼ 124 Hz,
2J(PF3) ¼ 47 Hz]. n/cmꢀ1 (neat): 1741 (C C), 1312 ( CF2
= =
3
3J(F2F3) ¼ 123 Hz, J(PF2) ¼ 10 Hz], dF3 gem : ꢀ184.4 [ddd,
=
asym), 1159 ( C–F), 1048 ( CF2 sym), 599 (P Se).
=
=
3J(F1F3) ¼ 32 Hz, 3J(F2F3) ¼ 123 Hz, 2J(PF3) ¼ 37 Hz].
n/cmꢀ1 (neat): 1737 (C C), 1318 ( CF2 asym), 1150
=
=
=
=
=
( C–F), 1065 ( CF2 sym), 592 (P S).
13. (0.290 g, 47%), mp 32 ꢁC. (Found: C, 41.3; H, 7.1; P, 13.2;
S, 13.3%. C8H14F3PS requires C, 41.7; H, 6.1; P, 13.5; S,
13.9%). dP : 63.6 [dd, 3J(PF2) ¼ 10 Hz, 2J(PF3) ¼ 28 Hz],
dF1 trans : ꢀ79.1 [dd, 2J(F1F2) ¼ 37 Hz, 3J(F1F3) ¼ 32 Hz],
dF2 cis : ꢀ101.4 [ddd, 2J(F1F2) ¼ 37 Hz, 3J(F2F3) ¼ 122 Hz,
3J(PF2) ¼ 10 Hz], dF3 gem : ꢀ181.4 [ddd, 3J(F1F3) ¼ 32 Hz,
3J(F2F3) ¼ 122 Hz, 2J(PF3) ¼ 28 Hz]. n/cmꢀ1 (nujol): 1730
F2PR3 À x(CF CF2)x (x = 1, R = Et, 20; R = iPr, 21;
=
R = Cy,
22;
=
R = Ph,
23;
x = 2,
R = Ph,
24),
=
F2PPh2(CF CFH), 25, and F2PPh2(CCl CFH), 26. All reac-
tions were performed on a NMR tube scale in a dry box with
addition of XeF2 , in portions, to one equivalent of the phos-
phine dissolved in CDCl3 . The reactions were exothermic with
evolution of xenon gas. The products were identified using 19
and 31P{1H} NMR spectroscopy.
F
=
=
=
=
(C C), 1318 ( CF2 asym), 1146 ( C–F), 1061 ( CF2 sym),
20. dP : ꢀ23.6 [tddd, 3J(PF1) ¼ 13 Hz, 3J(PF2) ¼ 12 Hz,
2J(PF3) ¼ 77 Hz, 1J(PF4) ¼ 654 Hz], dF1 trans : ꢀ81.3 [dddt,
3J(PF1) ¼ 13 Hz, 2J(F1F2) ¼ 32 Hz, 3J(F1F3) ¼ 37 Hz,
4J(F1F4) ¼ 7 Hz], dF2 cis : ꢀ97.4 [dtdd, 3J(PF2) ¼ 12 Hz,
2J(F1F2) ¼ 32 Hz, 3J(F2F3) ¼ 113 Hz, 4J(F2F4) ¼ 39 Hz],
dF3 gem : ꢀ180.4 [dddt, 2J(PF3) ¼ 77 Hz, 3J(F1F3) ¼ 37 Hz,
=
600 (P S).
14. (0.390 g, 49%). (Found: C, 56.2; H, 3.5; P, 10.2; S, 10.9%.
C14H10F3PS requires C, 56.4; H, 3.4; P, 10.4; S, 10.7%). dP :
32.5 [ddd, 3J(PF1) ¼ 4 Hz, 3J(PF2) ¼ 12 Hz, 2J(PF3) ¼ 46
Hz], dF1 trans : ꢀ80.3 [ddd, 3J(PF1) ¼ 4 Hz, 2J(F1F2) ¼ 34
Hz, 3J(F1F3) ¼ 30 Hz], dF2 cis : ꢀ97.4 [ddd, 2J(F1F2) ¼ 34
Hz, 3J(F2F3) ¼ 122 Hz, 3J(PF2) ¼ 12 Hz], dF3 gem : ꢀ178.0
[ddd, 3J(F1F3) ¼ 30 Hz, 3J(F2F3) ¼ 122 Hz, 2J(PF3) ¼ 46
3
3J(F2F3) ¼ 113 Hz, J(F3F4) ¼ 7 Hz]. dF4 P–F : ꢀ43.9 [dddd,
1J(PF4) ¼ 654 Hz, 4J(F1F4) ¼ 7 Hz, 4J(F2F4) ¼ 39 Hz,
3J(F3F4) ¼ 7 Hz].
Hz]. n/cmꢀ1 (neat): 1728 (C C), 1317 ( CF2 asym), 1106
=
=
21. dP : ꢀ19.6 [tddd, 3J(PF1) ¼ 13 Hz, 3J(PF2) ¼ 12 Hz,
2J(PF3) ¼ 72 Hz, 1J(PF4) ¼ 690 Hz], dF1 trans : ꢀ80.7 [dddt,
3J(PF1) ¼ 13 Hz, 2J(F1F2) ¼ 28 Hz, 3J(F1F3) ¼ 39 Hz,
4J(F1F4) ¼ 9 Hz], dF2 cis : ꢀ95.5 [dtdd, 3J(PF2) ¼ 12 Hz,
2J(F1F2) ¼ 28 Hz, 3J(F2F3) ¼ 111 Hz, 4J(F2F4) ¼ 45 Hz],
dF3 gem : ꢀ176.7 [dddt, 2J(PF3) ¼ 72 Hz, 3J(F1F3) ¼ 39 Hz,
=
( C–F), 1060 ( CF2 sym), 645 (P S).
=
=
=
15. Conversion of PPh(CF CF2)2 was incomplete. dP : 17.4
[ttt, 3J(PF1) ¼ 6 Hz, 3J(PF2) ¼ 13 Hz, 2J(PF3) ¼ 50 Hz],
dF1 trans : ꢀ77.7 [ddd, 3J(PF1) ¼ 6 Hz, 2J(F1F2) ¼ 31 Hz,
3J(F1F3) ¼ 31 Hz], dF2 cis : ꢀ97.4 [ddd, 2J(F1F2) ¼ 31 Hz,
3J(F2F3) ¼ 122 Hz, J(PF2) ¼ 13 Hz], dF3 gem : ꢀ183.0 [ddd,
3
3
2
3
3J(F1F3) ¼ 31 Hz, J(F2F3) ¼ 122 Hz, J(PF3) ¼ 50 Hz].
3J(F2F3) ¼ 111 Hz, J(F3F4) ¼ 9 Hz]. dF4 P–F : ꢀ62.1 [dddd,
T h i s j o u r n a l i s Q T h e R o y a l S o c i e t y o f C h e m i s t r y a n d t h e
C e n t r e N a t i o n a l d e l a R e c h e r c h e S c i e n t i f i q u e 2 0 0 4
N e w . J . C h e m . , 2 0 0 4 , 2 8 , 8 2 8 – 8 3 7
835

View Article Online
1J(PF4) ¼ 690 Hz, 4J(F1F4) ¼ 9 Hz, 4J(F2F4) ¼ 45 Hz,
3J(F3F4) ¼ 9 Hz].
References
22. dP : ꢀ25.6 [tddd, 3J(PF1) ¼ 13 Hz, 3J(PF2) ¼ 12 Hz,
2J(PF3) ¼ 71 Hz, 1J(PF4) ¼ 684 Hz], dF1 trans : ꢀ79.8 [dddt,
3J(PF1) ¼ 13 Hz, 2J(F1F2) ¼ 28 Hz, 3J(F1F3) ¼ 39 Hz,
4J(F1F4) ¼ 10 Hz], dF2 cis : ꢀ95.3 [dtdd, 3J(PF2) ¼ 12 Hz,
2J(F1F2) ¼ 28 Hz, 3J(F2F3) ¼ 110 Hz, 4J(F2F4) ¼ 45 Hz],
dF3 gem : ꢀ176.7 [dddt, 2J(PF3) ¼ 71 Hz, 3J(F1F3) ¼ 39 Hz,
1
D. M. Roddick and R. C. Schnabel, in Inorganic Chemistry:
Towards the 21st Century, ACS Symposium Series 555, ed.
J. S. Thrasher, ACS, Washington, D.C., 1994, ch. 27; W. Levason,
in The Chemistry of Organophosphorus Compounds, ed.
F. R. Hartley, Wiley, New York, 1990, vol. 1, ch. 15.
2
3
E. Zbiral, in Organophosphorus Reagents in Organic Synthesis, ed.
J. I. G. Cadogan, Academic Press, New York, 1979, p. 223.
F. W. Bennet, G. R. A. Brandt, H. J. Emeleus and R. N.
3
3J(F2F3) ¼ 110 Hz, J(F3F4) ¼ 9 Hz]. dF4 P–F : ꢀ60.3 [dddd,
´
Haszeldine, J. Chem. Soc., 1953, 1565; A. B. Burg, W. Mahler,
A. J. Bilbo, C. P. Haber and D. L. Herring, J. Am. Chem. Soc.,
1957, 79, 247.
1J(PF4) ¼ 684 Hz, 4J(F1F4) ¼ 10 Hz, 4J(F2F4) ¼ 45 Hz,
3J(F3F4) ¼ 9 Hz].
23. dP : ꢀ62.8 [tddd, 3J(PF1) ¼ 17 Hz, 3J(PF2) ¼ 13 Hz,
2J(PF3) ¼ 78 Hz, 1J(PF4) ¼ 707 Hz], dF1 trans : ꢀ80.1 [dddt,
3J(PF1) ¼ 17 Hz, 2J(F1F2) ¼ 29 Hz, 3J(F1F3) ¼ 33 Hz,
4J(F1F4) ¼ 8 Hz], dF2 cis : ꢀ95.7 [dtdd, 3J(PF2) ¼ 13 Hz,
2J(F1F2) ¼ 29 Hz, 3J(F2F3) ¼ 112 Hz, 4J(F2F4) ¼ 41 Hz],
dF3 gem : ꢀ178.2 [dddt, 2J(PF3) ¼ 78 Hz, 3J(F1F3) ¼ 33 Hz,
4
5
6
7
8
M. Fild, O. Glemser and G. Cristoph, Angew. Chem., Int. Ed.
Engl., 1964, 3, 801.
L. A. Wall, R. E. Donadio and W. J. Pummer, J. Am. Chem. Soc.,
1960, 82, 4846.
M. F. Ernst and D. M. Roddick, Inorg. Chem., 1989, 28,
1624.
R. G. Peters, B. L. Bennett, R. C. Schnabel and D. M. Roddick,
Inorg. Chem., 1997, 36, 5962.
See, for example: L. Maier, D. Seyferth, F. G. A. Stone and E. G.
Rochow, J. Am. Chem. Soc., 1957, 79, 5884; M. S. Holt, J. H.
Nelson and N. W. Alcock, Inorg. Chem., 1986, 25, 2288; L. P.
Barthel-Rosa, V. J. Catalano and J. H. Nelson, J. Chem. Soc.,
Chem. Commun., 1995, 1629; L. P. Barthel-Rosa, V. J. Catalano,
K. Maitra and J. H. Nelson, Organometallics, 1996, 15, 3924.
I. L. Knunyants, R. N. Sterlin, R. D. Yatsenko and L. N. Pinkina,
Isv. Akad. Nauk. SSSR. Otd. Khim. Nauk., 1960, 1991.
3
3J(F2F3) ¼ 112 Hz, J(F3F4) ¼ 7 Hz]. dF4 P–F : ꢀ50.1 [dddd,
1J(PF4) ¼ 707 Hz, 4J(F1F4) ¼ 8 Hz, 4J(F2F4) ¼ 41 Hz,
3J(F3F4) ¼ 7 Hz].
24. dP : ꢀ66.6 [tttt, 3J(PF1) ¼ 18 Hz, 3J(PF2) ¼ 15 Hz,
2J(PF3) ¼ 88 Hz, 1J(PF4) ¼ 739 Hz], dF1 trans : ꢀ75.5 [dddt,
3J(PF1) ¼ 18 Hz, 2J(F1F2) ¼ 18 Hz, 3J(F1F3) ¼ 39 Hz,
4J(F1F4) ¼ 9 Hz], dF2 cis : ꢀ92.7 [dtdd, 3J(PF2) ¼ 15 Hz,
2J(F1F2) ¼ 18 Hz, 3J(F2F3) ¼ 112 Hz, 4J(F2F4) ¼ 46 Hz],
dF3 gem : ꢀ180.6 [dddt, 2J(PF3) ¼ 88 Hz, 3J(F1F3) ¼ 39 Hz,
3J(F2F3) ¼ 112 Hz, 3J(F3F4) ¼ 6 Hz]. dF4 P–F : ꢀ56.5 [dttt,
1J(PF4) ¼ 739 Hz, 4J(F1F4) ¼ 9 Hz, 4J(F2F4) ¼ 46 Hz,
3J(F3F4) ¼ 6 Hz].
9
10 I. L. Knunyants, E. J. Perova and V. V. Tuleneva, Dokl. Akad.
Nauk. SSSR., 1959, 121, 576.
11 A. H. Cowley and M. W. Taylor, J. Am. Chem. Soc., 1969, 91,
1929.
12 H. G. Horn, R. Kontges, H. C. Marsmann and F. Kolkmann,
Z. Naturforsch., B: Anorg. Chem. Org. Chem., 1978, 33, 1422.
13 J. Ichikawa, H. Jyono, S. Yonemaru, T. Okauchi and T. Minami,
J. Fluorine Chem., 1999, 97, 109.
14 K. K. Banger, R. P. Banham, A. K. Brisdon, W. I. Cross, G.
Damant, S. Parsons, R. G. Pritchard and A. Sousa-Pedares,
J. Chem. Soc., Dalton Trans., 1999, 427.
15 J. Burdon, P. L. Coe, I. B. Haslock and R. L. Powell, Chem.
Commun., 1996, 49.
16 K. K. Banger, A. K. Brisdon and A. Gupta, Chem. Commun.,
1997, 139.
17 See, for example: K. D. Berlin and G. B. Butler, J. Org. Chem.,
1961, 26, 2537; R. Rabinowitz and J. Pellon, J. Org. Chem., 1961,
26, 4623; D. J. Peterson, J. Org. Chem., 1966, 31, 950.
18 N. A. Barnes, A. K. Brisdon, M. J. Ellis and R. G. Pritchard,
J. Fluorine Chem., 2001, 112, 35.
25. dP : ꢀ61.0 [tdd, 3J(PF1) ¼ 5 Hz, 2J(PF2) ¼ 100 Hz,
1J(PF3) ¼ 697 Hz], dF1 cis : ꢀ154.8 [dtdd, 3J(PF1) ¼ 5 Hz,
3J(F1F2) ¼ 131 Hz, 4J(F1F3) ¼ 31 Hz, 2J(HF2) ¼ 74 Hz],
dF2 gem : ꢀ168.8 [dddt, 2J(PF2) ¼ 100 Hz, 3J(F1F2) ¼ 131
3
3
Hz, J(F2F3) ¼ 6 Hz, J(HF3) ¼ 7 Hz]. dF3 P–F : ꢀ48.9 [dddd,
4
3
1J(PF3) ¼ 697 Hz, J(F1F3) ¼ 31 Hz, J(F2F3) ¼ 6 Hz].
26. dP : ꢀ49.3 [td, 3J(PF1) ¼ 26 Hz, 1J(PF2) ¼ 703 Hz], dF1 cis
:
ꢀ154.8 [ddt, 3J(PF1) ¼ 26 Hz, 4J(F1F2) ¼ 8 Hz, 2J(HF2) ¼ 79
1
4
Hz], dF2 P–F : ꢀ39.4 [dd, J(PF2) ¼ 703 Hz, J(F1F2) ¼ 8 Hz].
=
OPPh2(CFBrCF2Br), 27. OPPh2(CF CF2) (0.235 g,
8.33 ꢂ 10ꢀ4 mol) was dissolved in chloroform (10 cm3) and a
solution of bromine in CHCl3 (2.12 cm3, 0.417 mol dmꢀ3
,
8.84 ꢂ 10ꢀ4 mol) was added. The solution was refluxed for
48 h, after which time the deep red solution had lightened to
yellow. The solution was concentrated in vacuo to yield
OPPh2(CFBrCF2Br), 27, as a yellow-brown oil. (0.350 g,
95%). (Found: C, 38.4; H, 2.6; P, 6.8%. C14H10F3Br2PO
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2
requires C, 38.0; H, 2.3; P, 7.0%). dP : 27.3 [dd, J(PFa) ¼ 61
3
0
Hz, J(PFb ) ¼ 3 Hz], dFa
:
ꢀ132.4 [ddd, (CFBrCF2Br),
2J(PFa) ¼ 61 Hz, 3J(FaFb) ¼ 23 Hz, J(FaFb ) ¼ 18 Hz],
3
0
dFb
:
ꢀ50.6 [dd, (CFBrCF2Br), 3J(FaFb) ¼ 23 Hz,
2
0
0
:
J(FbFb ) ¼ 170 Hz], dFb
ꢀ53.0 [ddd, (CFBrCF2Br),
3
3
2
0
0
0
J(PFb ) ¼ 3 Hz, J(FaFb ) ¼ 18 Hz, J(FbFb ) ¼ 170 Hz],
2
2
0
d
Ca : 104.4 [dddd, (CFBrCF2Br), J(CFb) ¼ J(CFb ) ¼ 32.8
Hz, 1J(CP) ¼ 63.7 Hz, 1J(CFa) ¼ 283.9 Hz], dCb : 120.5 [dddd,
(CFBrCF2Br), 2J(CP) ¼ 5.8 Hz, 2J(CFa) ¼ 32.8 Hz,
1
1
0
J(CFb) ¼ J(CFb ) ¼ 313.9 Hz], dC
:
127.5 [d,
ipso
1J(PC) ¼ 69.5 Hz], dC meta : 129.2 [dd, 3J(PC) ¼ 12.6 Hz,
5J(CF) ¼ 1.9 Hz], dC para : 132.7 [d, 4J(PC) ¼ 8.7 Hz], dC ortho
:
4
28 A. D. Beveridge, H. C. Clark and J. T. Kwon, Can. J. Chem.,
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Tetrahedron, 1996, 52, 37.
133.9 [dd,
2
J(PC) ¼ 7.7 Hz, J(CF) ¼ 2.9 Hz].
Acknowledgements
30 L. Xue, L. Lu, S. D. Pedersen, Q. Liu, R. M. Narake and D. J.
Burton, J. Org. Chem., 1997, 62, 1064.
We thank Ineos Fluor for providing samples of HFC-134a and
acknowledge the use of the EPSRC’s Chemical Database Ser-
vice at Daresbury. We also wish to thank the EPSRC for sup-
port of the UMIST NMR spectroscopy service (GR/L52246)
and FT-IR/Raman spectrometer (GR/M30135).
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