Perfluorinated phosphine and hybrid P-O ligands for Pd catalysed C-C bond forming reactions in solution and on Teflon supports

Article abstract of DOI:10.1039/c9ra04863d

The synthesis of two types of phosphine ligands that feature perfluorinated ponytails is reported. A bidentate (RfCH₂CH₂)₂PCH₂CH₂P(CH₂CH₂Rf)₂ (Rf = CF₃(CF

Full text of DOI:10.1039/c9ra04863d

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PAPER
Perfluorinated phosphine and hybrid P–O ligands
for Pd catalysed C–C bond forming reactions in
solution and on Teflon supports†
Cite this: RSC Adv., 2019, 9, 28936
Farzana Begum, Muhammad Ikram, Brendan Twamley and Robert J. Baker *a
ab
ac
a
The synthesis of two types of phosphine ligands that feature perfluorinated ponytails is reported. A bidentate
(
RfCH
opening
spectroscopically characterised. The electronic effects of the fluorous chains have been elucidated from
2
CH
2
)
2
PCH
2
CH
2
P(CH
2
CH
2
Rf)
2
(Rf ¼ CF
3
(CF
2
)
n
; n ¼ 5, 7) and an alkoxyphosphine made by ring
a
fluorous epoxide, RfCH
2
CH(OH)CH
2
PR (Rf CF (CF ), have been prepared and
2
¼
3
2 7
)
1
1
either the
JPt–P or JP–Se coupling constants in Pt(II) or phosphine selenide compounds. Whilst the
bidentate phosphines do not give stable or active Pd catalysts, the hybrid ligand does allow Susuki, Heck
and Sonogashira catalysis to be demonstrated with low catalyst loadings and good turnovers. Whilst
a fluorous extraction methodology does not give good performance, the ligand can be adsorbed onto
Teflon tape and for the Suzuki cross coupling reaction the catalytic system can be run 6 times before
activity drops and this has been traced to oxidation of the ligand. Additionally the crystal structure of the
hybrid phosphine oxide is reported and the non-covalent interactions discussed.
Received 27th June 2019
Accepted 8th September 2019
DOI: 10.1039/c9ra04863d
rsc.li/rsc-advances
modications of phosphines decorated with uorous ponytails of
varying lengths have since been reported, with a wide scope in
Introduction
6
Immobilisation of homogeneous catalysts is an attractive meth- catalytic reactions. The uses of uorous ponytails are not limited to
7
odology for generating recoverable and recyclable catalysts and phosphines and a range of ligand types have been prepared. An
1
many methods have been exploited. The principle advantage is elegant use of the preferential solubility of uorous phosphines in
2
catalyst recoverability and recycling, especially where expensive uorous solvents has been using the concept of phase transfer
metals are used. As an example, N-heterocyclic carbenes, which are activation by the modication of Grubbs II catalyst [(NHC)Ru(]
prevalent in homogeneous catalysis, have been extensively studied CHR)(PRf
3
)Cl
2
]. The initiation step involves dissociation of the
3
and a plethora of immobilisation techniques reported. An inter- phosphine to form the vacant coordination site so when run under
esting methodology has been in the use of uorous groups as the biphasic conditions the phosphine is “removed” from the reaction
solubility in organic solvents can be tuned by control of the solvent and cannot re-coordinate, thus the overall rate of reaction
8
number of uorous groups or the choice of uorous or organic can be increased. We have shown that using a uorous alkoxide as
solvent. This is due to the ‘thermomorphic’ behaviour of mixed a quenching agent we can recycle catalysts for the ring opening of
9
solvent systems where at certain temperatures the uorous and caprolactone. However, by introducing the electron withdrawing
organic solvents are miscible, but phase separation occurs upon peruorinated ponytails, the electronic parameters of the phos-
4
changing the temperature. Therefore if the metal complex can phines can be signicantly affected. Methods to combat this have
6,10
11
have signicant solubility in the uorous phase then homogenous included the use of aryl spacers or methylene groups that can
catalysis and catalyst separation can be controlled by simply attenuate this electronic impact. As an illustrative example, the
changing the temperature. The rst example of this was reported n(C^O) stretching frequency in Vaska's type complexes
by Horv ´a th in the synthesis of a peruorinated triphenylphos- [IrCl(CO)(PR ) ] can be compared with electron poor (P(OPh) )
3
2
3
ꢀ
1
5
phine rhodium complex in hydroformylation reactions, and many (n(C^O ¼ 2003 cm )) or electron rich (PCy
) (n(C^O ¼
3
ꢀ1
12
1
931 cm )) traditional phosphines for catalysis and Rf
3
P (Rf ¼
ꢀ
1
11b
CH
2
CH
2
(CF
2
)
5
CF
3
); (n(C^O ¼ 1976 cm )).
a
School of Chemistry, University of Dublin Trinity College, Dublin 2, Ireland. E-mail:
The major drawbacks of these methodologies are that the u-
bakerrj@tcd.ie
orous solvents and ponytails are not environmentally friendly and
can persist in the environment causing long term adverse effects.
Secondly, the syntheses of the uorous ligands are typically
b
13
Department of Chemistry, Mirpur University of Science and Technology, Mirpur AJK,
Pakistan
c
Department of Chemistry, Abdul Wali Khan University, Mardan, Pakistan
prohibitively expensive for large scale applications and sometimes
†
Electronic supplementary information (ESI) available. CCDC 1912783. For ESI
and crystallographic data in CIF or other electronic format see DOI:
0.1039/c9ra04863d
14
multi-step synthesis using experimentally difficult conditions, or
15
formed in poor yields, although new synthetic pathways
1
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1
6
19
somewhat reduce this effect. Finally, as the uorous chains are peruoromethylcyclohexane was measured using a F NMR
4
increased the solubility in all solvents tends to decrease, meaning spectroscopic methodology at 4 : 96 for 1 and 2 : 98 for 2; when
characterisation becomes difficult. Light uorous (i.e. <40% uo- n ¼ 9 a solid precipitated out of the reaction mixture and proved
rine) chemistry has been used to circumvent some of these to be insoluble in all organic and uorous solvents, even at
17
issues, most notably the use of uorous silica for phase separa- elevated temperatures. In contrast, the reactions with 1,2-
tion. These reagents are expensive and subsequent washing steps biphosphinobenzene were extremely sluggish and very low
may degrade the catalyst, but several interesting applications have yielding (d
P
¼ ꢀ31 ppm) so further reactivity studies were not
18
been reported. A medium uorous approach (i.e. 40–60% uo- conducted.
rine) has been utilised successfully, but typically use protic solvents
such as water, which is incompatible with some organometallic
19
catalysts; however judicious use of uorinated solvents can alle-
20
viate this problem. Given the observation that the temperature
can control the solubility of the uorinated ligands in both uo-
rous and organic solvent, the elimination of the expensive and
environmentally unfriendly uorinated solvent can be achieved by
thermomorphic control for liquid/solid phase separation i.e. the
(
1)
To understand the changes in the electronic effect of the
ligand we sought to synthesise [(PP)PtCl ] as the magnitude of
the JPt–P coupling constant has been used to evaluate the s-
donor ability of phosphines, specically where a decrease in the
coupling constant can be related to a decrease in the s-donation
uorinated catalyst will dissolve in suitably chosen organic
2
1
solvents at high temperatures but will precipitate upon lowering of
21
the temperature. An emerging solution has been to use uorous
supports such as Teon or Gore-Tex whereby the uorous catalyst
is presumably adsorbed onto the surface and provides an efficient
27
from the phosphorus. Thus, an NMR tube was charged with one
22
vehicle for catalyst delivery and recovery, although catalyst
leaching can still be of concern. The sorption process is not well
understood, but we have shown that measurable, though rather
equivalent of 1 and one equivalent of [(COD)PtCl
2
] in the
amphiphilic solvent 1,3-triuoromethylbenzene and heated to
0 C for 1 h. This afforded a shi in the P{ H} NMR spectrum
ꢁ
3
1
1
5
23
1
weak, non-covalent C–F/F–C interactions could be involved.
from d ¼ ꢀ26 ppm to d ¼ +49 ppm with Pt satellites ( J
¼
P
P
Pt–P
Herein we report on two synthetic pathways for the formation of
phosphines and expand the idea of supporting these uorinated
ligands onto PTFE tape, commonly used in the laboratory, and
their use in homogeneous catalysis, particularly targeted at the
recovery and reuse of the expensive uorous ligands in C–C cross
coupling reactions, that avoids issues of catalyst decomposition
and/or leaching. This “ligand-on-Teon” has been characterised by
thermal methods.
3
[
487 Hz). This can be compared to 3523 Hz for the electron rich
28
(dmpe)PtCl
PCH CH P(CF CF ) PtCl ]
2 2 2 3 2 2
2
]
or 3362 Hz for the electron poor [(CF
3
CF
2 2
) -
29
indicating that the methylene
spacers do attenuate the electron withdrawing nature of the u-
orous groups to a degree, and in line with numerous other
experimental studies. Interestingly, over an hour, a black
precipitate formed and the P{ H} NMR spectrum showed
several peaks in addition to free ligand, and we were unable to
obtain analytically pure material for further analysis. One was
identied as the phosphine oxide (3), by the deliberate oxidation
11
3
1
1
Results and discussion
of the ligand (d
P
¼ 31.6 ppm), was only soluble in uorinated
We will rst describe the synthesis of the ligands, followed by solvents (peruorinated hexane or 1,3-triuoromethylbenzene).
their use as traditional homogeneous catalysts under biphasic This suggests that the metal complexes of this ligand are
susceptible to decomposition and in line with data from some
other uorous phosphine palladium compounds.
conditions, before describing the characterisation on Teon
and nally the catalysis using the ligand-on-Teon approach.
25,30
Synthesis and characterisation of uorous P–O ligands. For
the synthesis of P–O ligands we decided to utilise the ring
opening of a commercially available uorous epoxide using
Synthesis and characterisation of uorous phosphine ligands
The synthesis of the phosphine and P–O ligands with uorous
ponytails was achieved in good yields using two methodologies.
Synthesis and characterisation of bidentate phosphine
ligands. We were inspired by the reported synthesis of the
a phosphide nucleophile, favouring the nucleophilic attack at the
2
N
least hindered carbon, via an S
type reaction and would control
the regioselectivity (Scheme 2). This type of reactivity has been
31
used to form several hydroxylated phosphine ligands, but offers
bidentate
P(CH (CH
CF
PCH
uoroalkyl
CH Rf
, (1, m ¼ 2, Rf ¼ (CF
, n ¼ 5, 7, 9) and the pincer phosphine 1,3-C
phosphine
(RfCH
or m ¼ 5, Rf
2
CH
2 2
) -
a different synthetic strategy for placement of the uorous group
far away from the phosphine so the electronic effects on the
phosphorus centre can be controlled using the R groups. This
24
2
)
m
2
2
2
)
2
2 5 3
) CF ;
2
5
¼
(CF
(CH
2
)
n
3
6
-
26
H
4
2
2
CH
2
Rf
2
)
2
(Rf ¼ (CF
2
)
n
CF
3
, n ¼ 5, 7). In terms of
allows comparatively electron rich phosphines to be prepared.
t
catalysis, only ligand 1 has been applied in the Rh catalysed
hydroformylation of hexene in scCO . We repeated the
synthesis of (RfCH CH ) P(CH ) P(CH CH Rf) (eqn (1)) and
Preliminary investigations show that when [ Bu
2
P]Li is added
3
1
2
to the uorous epoxide, followed by quenching with water,
P
1
2
2 2
2 2
2
2
2
{ H} NMR spectroscopy showed a single peak at d ¼ 19.3 ppm
P
3
1
31
1
the reaction can be conveniently followed by P and P{ H}
that can be assigned to the expected ring opened product.
NMR spectroscopy; all intermediates have been identied
However when the smaller [Ph P]Li was used, two peaks were
2
(Fig. S8†). The partition coefficient between toluene and
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observed at d
P
¼ ꢀ27.1 and ꢀ15.5 ppm indicating that the
nucleophile ring opened at both positions; this has been
previously observed in non-uorous epoxides. To regain
31
control of regioselectivity, we increased the size of the nucleo-
n
phile by reacting the phosphine–borane adducts with BuLi and
3
2
31
the epoxide. Under these conditions only one peak in the
P
1
{
¼
2 3
H} NMR spectrum was observed in all Li[R P$BH ] adducts (R
i
t
Ph, d
P
¼ 12.8 ppm; R ¼ Pr, d
P
¼ 32.5 ppm; R ¼ Bu, d ¼ 40.6
P
ppm), indicating a regioselective ring opening. All spectroscopic
1
13
1
31
1
7
data ( H, C{ H}, P{ H}, Li NMR and IR spectrosocopy)
support the formulation of the ring opened salts 5–7 (ESI†).
Deprotection of the borane by reuxing with TMEDA followed
by quenching with degassed water gave ligands 11–13 in good
yield; the order of the quenching and deprotection did not
make a difference to the isolated yield but could not be done
simultaneously as by-products from quenching the tmedaBH
complex complicated purication. This reaction can be
3
33
3
1
1
11
conveniently followed by P{ H} and B NMR spectroscopy
3
1
1
and the shi in the P{ H} NMR spectra are accompanied by
1
the loss of the J
7.4 ppm; 13, d
NMR spectrum ascribed to the TMEDA$BH
31P–11
coupling (11, d ¼ 19.3 ppm; 12, d ¼
B
P
P
11 1
2
P
¼ ꢀ22.6 ppm) and resonances in the B{ H}
33b
3
complex.
All
other NMR spectroscopy conrm the formulations (ESI†).
Importantly for catalysis, the partition coefficient between per-
1
9
Scheme 1 Synthesis of P–O ligands (Rf ¼ CF
3 2 7
(CF ) ).

uoromethylcyclohexane and toluene were measured using
F
4
NMR spectroscopy for 11–13 and the results were all around
5 : 45 indicating that there is little preferential solubility in
uorous phases, as anticipated from the inclusion of the
5

ꢀ
P (C(13)–H(13A)/O(1) ¼ 3.351(5) A, Fig. 2(b)); the increased
acidity of these protons have been shown computationally
hydroxy and alkyl groups.
23
previously. To explore and quantify the uorous based non-
The phosphines are sensitive to oxygen, and the corre-
sponding phosphine oxide can be readily prepared and isolated
by simply exposing the phosphine to air (Scheme 1). In order to
understand the electronic changes that occur in these three
ligands, the phosphines 11–13 were reacted with elemental Se
39
covalent interactions, Hirshfeld surface can be conveniently
used and close interactions are labelled in Fig. 2(c) as red spots.
4
0
Fig. 2(c) highlights the C–F/H–C interactions (dC(10)/F(5)
sp2
¼
ꢀ
˚
3
.449(5) A and dC(5)/F(14) ¼ 3.107(5) A) and numerous C–F/F–C
˚
interactions ranging from 2.744(4) to 2.934(4) A (sum of the van
and the phosphine selenide 17–19 isolated and characterised by
41
1
der Waals radii ¼ 2.92 A˚ ).
multinuclear NMR spectroscopy (Scheme 1). The J
coupling
P–Se
ꢁ
Bifurcated three-point interactions (F/F/F ¼ 54.43 ) are also
present holding chains together. Finally, the Hirschfeld surfaces
can give quantitative information and the H/F close contacts
account for 30.0%, while the F/F ¼ 24.9% and H/H only 22.2%.
constants have been used to give electronic information on the
3
4
1
phosphorus and the coupling constants are JP–Se ¼ 674 Hz for
1
1
1
7, JP–Se ¼ 688 Hz for 18 and JP–Se ¼ 705 Hz for 19, in line with
the expected trends i.e. the lower the coupling constant the
more electron rich the phosphine. Moreover we can compare
1
35
i
1
Catalytic studies in solution
the shi from R P]Se (R ¼ Ph, J
¼ 736 Hz; R ¼ Pr, J
3
P–Se
P–Se
36
t
1
36
¼
686; R ¼ Bu, J
¼ 687 Hz) or Ph PEt model compounds
P–Se
2
To assess the use of the uorous phosphines 11–13 in catalysis
we chose to explore their Pd complexes in the Heck, Suzuki and
1
(
JP–Se ¼ 725 Hz); these data show that the phosphines are not
signicantly affected by the uorous ponytails.
We were able to grow single crystals of 16 from slow evapo-
ration of DCM and the structure is shown in Fig. 1 (metric
parameters are collated in Tables S1 and S2†).
The structure conrms the regioselectivity of the ring opening
and the metric parameters are unexceptional. For example the
ꢀ
P]O ¼ 1.486(3) A is comparable to the P]O bond length of
ꢀ
37
1
.4871(15) A in the hemihydrate of triphenylphosphine,
ꢀ
(Ph
3
P]O)(H
2
O)0.5 or to the P]O bond length of 1.494(2) A in
38
2
Ph MeP]O which features no hydrogen bonding. However, the
packing and non-covalent interactions (Fig. 2) warrant comment.
There are strong intermolecular O–H/O]P interactions (O(1)/
Fig. 1 Molecular structure of 16 with atomic displacement parameters
ꢀ
O(2) ¼ 2.698(4) A, Fig. 2(a)) and a longer intramolecular C–H/O– shown at 50% probability.
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Scheme 2 Summary of catalytic experiments from ligands 11–13 with
results reported in Table 1.
Sonogashira reaction required 2 mol% of the catalyst and the
yields were low, with long reaction times.
Moreover, in the Heck reaction we observe only the E
isomer by NMR spectroscopy. Because of the electron rich
t
nature of the Bu substituted phosphine, we were able to also
use bromobenzene in the Suzuki cross coupling reaction,
Fig. 2 Non-covalent bonding patterns in 1: hydrogen bonding (a)
normal to the a-axis showing the connectivity along layers; (b) normal albeit in reduced yield (yield ¼ 23%; TON ¼ 2300) and only
to the b-axis showing the connectivity between layers; (c) Hershfield
traces of product formed with chlorobenzene (yield ¼ <5%).
analysis showing the F/F (red lines) and H/F (green lines)
interactions.
For context, a number of uorous phosphines have been
developed for cross coupling reactions and our yields are
similar to those observed for the complexes [PdCl
2
(n-C10
or per-
uoroarylated SCS pincer palladium complex for the heck
-
1
6c
45
F
21PPh
2
)]
or
a
peruoroalkylated PCP
Sonogashira C–C coupling reactions. These important reactions
4
6

42
have been extensively studied and uorous ligands examined,
reaction that could be recycled by uorous solid-phase
extraction. However, Gladysz and co-workers have shown
that in peruoroalkylated SCS pincer compounds of Pd, the
thus providing a benchmark. The Heck reaction is typically used
43
as a testbed for new catalytic systems, but all intimate a highly
reactive undercoordinated Pd(0) that is intrinsically unstable
outside the catalytic cycle and the formation of Pd nanoparticles
4
7
catalyst is actually Pd nanoparticles. We do not compare to
4
8
4
the state of the art NHC based catalysts where TON of 10 –
1
44
can also effectively catalyse these reactions. These can present
challenges for effective recycling protocols.
6
0 are obtained using very low catalyst loadings. To illus-
trate the concept of electron richness further, the Suzuki
The uorous bidentate phosphines 1 and 2 give immediate
precipitation of a black powder upon addition of any source of
1
reaction was followed by H NMR spectroscopy using ligand
1
1
1 and 12 (ligand 13 gave overlapping peaks in the H NMR
3
1
1
Pd(II), or Pd(0) and P{ H} NMR analysis of the mixture showed
numerous peaks indicating decomposition of the Pd ligand
complex. No further catalytic studies were conducted with this
ligand, although we note that it can form catalytically compe- Table 1 Summary of catalysis results shown in Scheme 2
24
tent rhodium complexes for hydroformylation. Conversely,
reaction of ligands 11–13 with palladium sources afforded
active catalysts for Heck, Suzuki and Sonogashira C–C coupling
reactions (Scheme 2) using 0.5–1 mol% of the catalyst and the
results are summarised in Table 1. The purpose of this study
was not to fully optimise conditions nor demonstrate scope of
the reaction, but as a proof of principle that the reactions work
so that the ligand-on-Teon approach can be then tested and
compared. Therefore the yields of the reaction, whilst high,
have not been optimised. However, we note that the
ꢀ1
Reaction
Suzuki
Ligand
Yield (%)
TON
TOF (h )
11
95
91
75
81
72
68
48
36
25
9500
9100
7500
8100
7157
6713
2460
1772
1423
1187
1137
937
1012
894
839
151
111
89
12
13
11
Heck
1
1
2
3
Sonogashira
11
12
13
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spectrum that proved impossible to deconvolute) and the
conversion to biphenyl measured over time (Fig. 3). It is clear
that the most electron rich phosphine enhances the rate of
the reaction. Also apparent is that there is no initiation step
within the timeframe of our measurements.
Some recycling studies were carried out in solution by
quenching the reaction and then extracting the ligand in uo-
rinated solvents. Whilst we did recover some of the ligand, the
NMR studies showed this was as the oxide and, given the rather
low partition coefficients, in variable yields. This approach
clearly does not hold any benet for an efficient catalyst recy-
cling strategy.
Supported ligands on Teon
Fig. 4 TGA of phosphine ligands 11–13 adsorbed onto Teflon tape.
We next turned our attention to supporting the ligands 11–13
on Teon tape. The P–O ligands were dissolved in acetone and
a piece of Teon tape of ca. 1 cm length added and this was
stirred for 10 minutes. Removal of the Teon tape and drying Ligand-on-Teon studies
under a stream of N gas afforded a brownish coloured
2
The next step in our study was to observe if the ligand-on-Teon
approach could be used as a recycling study. Our initial attempts
with the Pd catalyst did not generate reproducible results, and
NMR studies showed that the ligand–metal complex was present
in solution as well as on the Teon tape, in line with the partition
coefficients measured for the ligand. However, it is well known
that in homogeneous catalysis the price of the ligand is orders of
magnitude more than the precious metal, so recycling the
ligand may give signicant cost savings as well as negating the
issue of metal leaching during multiple recycles. Moreover, the
generally high molecular weights of the ligands mean that rela-
tively large amounts of catalysts are needed to obtain high reac-
tion rates and/or selectivity. We used a model reaction to examine
the recyclability of the ligand that gave the most active catalyst (11
in this experiment), the coupling of iodobenzene with phenyl-
boronic acid to form biphenyl and Fig. 5 reports the isolated
3
1
1
material (ESI†). P{ H} NMR analysis of the solution revealed
no ligand present. This reaction was also followed in an NMR
tube and, without adjusting any instrument parameters, the
intensity of the ligand peak deceases to ca 5% in just a few
minutes. IR spectroscopy of the Teon tape was not informa-
tive, but TGA (Fig. 4) shows the presence of the ligands which
ꢁ
ꢁ
are lost at ca 300 C; Teon decomposes at 600 C. Qualita-
tively, 13 appears to sorp more than the other two ligands. It is
worth noting that the surface of Teon is undened as the
porosity and chemical permeability has been previously
51
4
9
50
studied, especially for uses as phase vanishing reactions.
Whether our compounds are surface sorped or entrained
inside the pores was not thoroughly investigated in this study,
but the high temperatures of ligand loss from the TGA
experiments and the much enhanced stability to air, points to
an entrainment process; we are investigating this adsorption
process in more detail and will report in due course. In
passing, we also note that though the stirrer bars we used were
PTFE coated, and could act as similar sources for sorption, the
Teon did not noticeably discolour in any of our experiments.
yields and TON of biphenyl. In this case, the ligand was not
19
present in the solution at the end of the reaction, as judged by
F
31
1
and P{ H} NMR spectroscopy (including a uorous standard)
and can be recycled multiple times before activity appreciably
31
1
drops off. The presence of 14 was then observed by P{ H} NMR
spectroscopy, pointing to an oxidative decomposition pathway.
Fig. 3 Plot of the % conversion of biphenyl using ligands 11 and 12, as Fig. 5 Recycling study of the coupling of iodobenzene and phenyl-
monitored by NMR spectroscopy. boronic acid using ligand-on-Teflon method.
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5
7
4
the corresponding dialkylchlorophosphines with NaBH .
Conclusions
58
59
Pd dba , [PdCl (MeCN) ] were made via literature procedures.
2
3
2
2
n
The synthesis and applicability of two electronically different The concentration of BuLi was veried via a Gilman double
phosphine ligands with uorous ponytails in a variety of C–C titration before use. All other chemicals and solvents were ob-
bond forming reactions have been shown. Whilst a uoroalkyl tained from commercial sources and used as received. The
2 2 2 2 2 2 2 2
phosphine (RfCH CH ) PCH CH P(CH CH Rf)
does not give syntheses of 14–19 and catalytic studies can be found in the ESI.†
catalytically competent palladium complexes, a b-hydrox-
yphosphine with the uorous chain further away from the
phosphine centre does. The catalysis can be run with low
loadings and reasonable turnovers, but because of the hydroxy
group cannot be recycled with conventional uorous solvent
recovery methods. However, we have shown that the ligands can
be sorped onto Teon tape and used for the Suzuki cross
coupling reaction of simple substrates with 6 recycles before
activity starts to drop off. The ligand on Teon approach add to
the growing numbers of reactions that can be catalysed by u-
orous immobilisation, but further optimisation could include
precise catalyst loading as this approach does not require
metals on the tape and the downside of metal leaching is
avoided. More generally, this work also shows that ligand effects
in recycling strategies are very important to consider.
Synthesis of 3 and 4
To solid (Rf) PCH CH P(Rf) was added 2.5 equivalents of H O
2 2
2
2
2
2
(30 wt% solution in water) under a nitrogen atmosphere. The
mixture was stirred for 3 hours and then the excess peroxide
decomposed by heating to 90 C under an ambient atmosphere
until all the water had been evaporated. The residue was
extracted into 1,4-bis(triuoromethyl) benzene and dried over
ꢁ
MgSO . Removal of the solvent afforded a white microcrystal-
4
line air stable powder.
ꢁ
1
3
: yield 78%; mp: 134–138 C; H NMR (FC-72): d ¼ 1.08 (m,
H
19
6
H, CH
2
) 1.29 (m, 6H, CH
2
), 3.14 (m, 4H, CH
2
CH
2
); F NMR
CH ),
4
(
ꢀ
FC-72): d
118.7 (CF
NMR (FC-72): d
F
¼ ꢀ84.5 (t, JFF ¼ 15 Hz, CF
3
), ꢀ103.1 (m CF
2
1
2
3
1
2
), ꢀ119.2 (CF
2
), ꢀ120.9 (CF
2
), ꢀ122.5 (CF
2
); P{ H}
ꢀ1
P
¼ 31.6 (s); IR (cm ): 2949 (w), 1530 (w), 1444
(
w), 1364 (w), 1234 (s), 1184 (s), 1141 (s), 1122 (m), 1068 (m),
Experimental
General
1
017 (w), 996 (w), 943 (w), 928 (w), 847 (w), 770 (w), 721 (m), 708
+
(m), 645 (m), 566 (w), 529 (m); ms (EI): 1511.7 [40%, M ].
ꢁ
1
4
: yield 45%; mp: 162–168 C; H NMR (FC-72): d ¼ 1.10 (m,
1
13
1
31
1
77
1
7
H
H, C{ H}, P{ H}, Se{ H} and Li NMR spectra were
19
6
H, CH
2
) 1.32 (m, 6H, CH
2
), 3.18 (m, 4H, CH
¼ ꢀ84.7 (t, JFF ¼ 14 Hz, CF ), ꢀ102.7 (m CF
), ꢀ119.1 (CF ), ꢀ120.7 (CF
NMR (FC-72): d
¼ 32.8 (s); IR (cm ): 2949 (w), 1444 (w), 1370
w), 1332 (w), 1197 (s), 1184 (s), 1115 (s), 1081 (m), 959 (m), 932
w), 872 (w), 737 (m), 705 (m), 652 (m), 558 (w), 528 (m);
2
CH
2
); F NMR
recorded on a Bruker AV400 spectrometer operating at 400.23
MHz, 155.54 MHz, 161.98 MHz 76.33 MHz and 156 MHz
respectively, and were referenced to the residual H and
4
(FC-72): d
F
3
2
CH ),
2
); P{ H}
2
3
1
1
ꢀ
118.4 (CF
2
2
2
), ꢀ122.5 (CF
1
13
C
ꢀ
1
P
resonances of the solvent used or external H PO , Me Se or LiCl.
3
4
2
(
(
IR spectra were recorded on a PerkinElmer Spectrum One
spectrometer with attenuated total reectance (ATR) accessory.
All thermogravimetric analysis were measured on the Perki-
nElmer Pyris 1 TGA heating at 10 C per minute in a nitrogen
atmosphere. Data for 11 were collected on a Bruker D8 Quest
ꢁ
Synthesis of 5–7
PHBH
3
ꢁ
R
2
3
(2.82 mmol) in hexane (5 cm ) was cooled to ꢀ78 C
n
3
˚
ECO using Mo Ka (l ¼ 0.71073 A). The sample was mounted on and BuLi (1.45 cm of a 2.37 M solution in hexane, 3.1 mm) was
a MiTeGen microloop and data collected at 100(2) K using an added dropwise with stirring. Aer warming to room tempera-
Oxford Instruments Cryostream low temperature device. Bruker ture 3-(peruorooctyl)-1,2-propenoxide (0.78 ml, 2.8 mm) was
52
APEX soware was used to collect and reduce data and added dropwise and stirred overnight. The solvent was removed
determine the space group. The structure was solved using under vacuum to give a yellowish-brown oil.
5
3
ꢀ1
direct methods (XT) and rened with least squares minimi-
5: IR n (cm ); 2958 (w, CH), 2390 (s, BH), 1432, 1364 (w, CH),
54
55
zation (XL) in Olex2. Absorption corrections were applied 1232, 1194, 1143, 1122 (s, CF), 1061, 1075 (s, CF), 1074 (s, CO);
56
1
3
using SADABS. Crystal data, details of data collection and
renement are given in Table S1.† The hydrogen H2a on O was 6CH
H NMR (400 MHz, C
6
D
6
): d
H
¼ 1.07 (18H, d, JH–P ¼ 12.5 Hz,
1
2
2
3
), 1.47 (3H, d, JB–H ¼ 2.43 Hz, BH
3
), 1.75 (1H, m, JP–H
¼
1
3
located on the difference map and rened with restraints 77.14 Hz, JP–H ¼ 15.24 Hz, JH–H ¼ 10.41, CH
2
P), 1.84 (1H, m,
2
2
1
3
(
DFIX). The uorine atoms are prolate and were modelled with
restraints to minimize this (ISOR). CCDC 1912783 contains the
supplementary crystallographic data for this paper.
JP–H ¼ 69.2 Hz, J
¼ 15.4, J
¼ 10.3, CH P), 2.23 (1H, m,
H–H
H–H
3
2
1
JH–F ¼ 15.0 Hz, J
¼ 15.0 Hz, J
¼ 6.2 Hz, CH CF ), 2.59
H–H
H–H
2
2
2
1
3
(1H, m,
J
H–F ¼ 15.0 Hz,
J
H–H ¼ 15.0 Hz,
J
H–H ¼ 6.2 Hz,
1
3
1
All manipulations were carried out using standard Schlenk CH
2
CF
2
), 4.73 (1H, q, CHOH); C{ H} NMR (100 MHz, C
6
D
6
): d
C
3
1
and glove box techniques under an atmosphere of a high purity ¼ 27.95 (d, JC–P ¼ 3 Hz, CH
3
), 31.53 (d, JC–P ¼ 30.5 Hz, P–CH
2
),
1
2
dry argon. THF and Hexane was distilled over potassium, C
and toluene over sodium whilst DCM, acetonitrile, CDCl and all CF
uorous solvents and catalyst precursors were distilled over CaH CF
D
6 6
38.75 (d, JC–P ¼ 31.1 Hz, CCH
3
1
), 45.10 (m, JC–F ¼ 22.8 Hz,
2
3
2
CH
CF
2
), 63.5 (CHOH), 105 (m, JC–F ¼ 270 Hz, JC–F ¼ 32.9 Hz,
1
2
1

2
2
3
), 110 (tt, JC–F ¼ 270 Hz, JC–F ¼ 32.9, CF
2
), 113 (tt, JC–F
¼
¼
¼
2
1
2
and degassed immediately prior to use. The Teon® tape (PTFE 257 Hz, JC–F ¼ 32.9 Hz, 4CF ), 115 (tt, J
¼ 288 Hz, J
2
C–F
C–F
1
2
thread seal tape BS 7786: 1995 Grade L) was obtained from 32.9 Hz, CF CH ), 118.5 (tt, 118.7,
J
C–F
¼ 257 Hz,
J
2
2
C–F
1
9
commercial sources. 1 and 2 were made by the literature proce- 32.9 Hz, CF
dure. The phosphine boranes were prepared by the reduction of ꢀ112.90 (CF
2
CF
3
); F NMR (376 MHz, C
6
D
6
): d
F
¼ ꢀ81.85(CF
3
),
),
24
2
), ꢀ122.30(CF
2
), ꢀ123.16 (CF
2
), ꢀ123.73 (CF
2
This journal is © The Royal Society of Chemistry 2019
RSC Adv., 2019, 9, 28936–28945 | 28941

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RSC Advances
Paper
7
11
3
2
ꢀ
126.79 (CF
2
); Li NMR (156 MHz, C
6
D
6
): dLi ¼ 1.07; B NMR 15.24 Hz, JH–H ¼ 10.41, CH
2
P), 1.84 (1H, m, JP–H ¼ 69.2 Hz,
1
1
1
3
1
(
128 MHz, C D ): d ¼ ꢀ42.92 (m, J
¼ 2.43 Hz, J
¼ 60
JH–H ¼ 15.4, J
¼ 10.3, CH P), 2.01 (3H, d, J
¼ 2.43 Hz,
6
6
B
B–H
B–P
H–H
2
B–H
3
1
1
1
2
1
3
Hz); P{ H} NMR (162 MHz, C D ): d ¼ 40.61 (d, J ¼ 60 Hz). BH ), 2.22 (1H, m, J
¼ 15.0 Hz, J
¼ 15.0 Hz, J
¼
6
6
P
P–B
3
H–F
H–H
H–H
ꢀ
1
2
1
6
: IR n (cm ); 2966 (w, CH), 2377 (s, BH), 1465, 1370 (w, CH), 6.2 Hz, CH CF ), 2.53 (1H, m, J
¼ 15.0 Hz, J
¼ 15.0 Hz,
2
2
H–F
H–H
3
1
238, 1201, 1145, 1114 (s, CF), 1065, 1047 (s, CF), 1036 (s, CO);
H NMR (400 MHz, C
J
H–H ¼ 6.2 Hz, CH
2 2
CF ), 4.02 (1H, s, CHOH), 4.63 (1H, q,
1
3
13
1
3
6
D
6
): d
H
¼ 0.77 (12H, d, JH–P ¼ 12.5 Hz, CHOH); C{ H} NMR (100 MHz, C
6
D
6
): d
C
¼ 27.34 (d, JC–P
¼
2
3
1
1
(CH
3
)), 0.90 (2H, m, JH–P ¼ 69.5 Hz, JH–H ¼ 10.5 Hz, CHCH
3
), 3 Hz, CH
3
), 29.51 (d, JC–P ¼ 30.5 Hz, PCH
2
), 32.43 (d, JC–P
¼
1
2
2
1
.35 (3H, d, JB–H ¼ 2.45 Hz, BH
3
), 1.37 (1H, m, JP–H ¼ 75.5 Hz, 31.1 Hz, CCH
3
), 45.68 (m,
J
C–F ¼ 22.8 Hz, CF
2
CH
2
), 63.02
1
3
2
1
2
J
H–H ¼ 15.24 Hz, JH–H ¼ 10.41, CH
2
P), 1.44 (1H, m, JP–H
¼
¼
(CHOH), 105 (m, JC–F ¼ 270 Hz, JC–F ¼ 32.9 Hz, CF
2
CF
3
), 110
1
3
2
1
2
1
2
68.2 Hz, J
¼ 15.1, J
¼ 10.2, CH P), 2.01 (1H, m, J
(tt, J ¼ 270 Hz, J ¼ 32.9, CF ), 113 (tt, J ¼ 257 Hz, J
H–H
H–H
3
2
H–F
C–F
C–F
2
C–F
C–F
1
1 2
1
5.0 Hz, J
¼ 15.0 Hz, J
¼ 6.2 Hz, CH CF ), 2.37 (1H, m, ¼ 32.9 Hz, CF ), 115 (tt, J ¼ 288 Hz, J ¼ 32.9 Hz, CF CH ),
H–H
H–H
2
2
2
C–F
C–F
2
2
19
2
1
3
1
2
JH–F ¼ 15.0 Hz, J
¼ 15.0 Hz, J
¼ 6.2 Hz, CH CF ), 4.43 118.5 (tt, 118.7, J
¼ 257 Hz, J
¼ 32.9 Hz, CF CF );
F
),
B
¼
H–H
1
H–H
2
2
C–F
C–F
2
3
1
3
3
(
1H, q, CHOH); C{ H} NMR (100 MHz, C
6
D
6
): d
C
¼ 16.5 (d, JC– NMR (376 MHz, C
6
D
6
): d
), ꢀ122.96 (CF
), 57.70 NMR (128 MHz, C ): d
F
¼ ꢀ81.39 (CF
3
), ꢀ112.75 (CF
2
1
1
11
P
¼ 3 Hz, CH
3
), 22.1 (d, JC–P ¼ 30.5 Hz, P–CH
2
), 28.1 (d, JC–P
¼
ꢀ122.07 (CF
2
2
), ꢀ123.56 (CF
2
), ꢀ126.69 (CF
2
);
2
1
1
3
1.1 Hz, CCH
3
), 45.66 (m,
J
C–F ¼ 22.8 Hz, CF
2
CH
2
6
D
6
B
¼ ꢀ43.36 (m, JB–H ¼ 2.43 Hz, JB–P
1
2
31
1
1
(
(
¼
CHOH), 108 (m, JC–F ¼ 270 Hz, JC–F ¼ 32.9 Hz, CF
2
CF
3
), 112 60 Hz); P{ H} NMR (162 MHz, C
6
D
6
): d
P
¼ 40.20 (d, JP–B ¼ 60
1
2
1
2
+
tt, JC–F ¼ 270 Hz, JC–F ¼ 32.9, CF
2
), 115 (tt, JC–F ¼ 257 Hz, JC–F Hz); MS (MALDI ) m/z: found for C19
27
H F17OPB 636.1736
1
2
32.9 Hz, 4CF ), 116 (tt,
J
¼ 288 Hz,
J
C–F
¼ 32.9 Hz, calculated 636.16211.
2
C–F
1
2
19
ꢀ1
CF CH ), 118 (tt, J
¼ 257 Hz, J
¼ 32.9 Hz, CF CF );
F
9: IR n (cm ); 3495 (s, OH), 2963 (w, CH), 2403 (s, BH), 1471,
2
2
C–F
C–F
2
3
NMR (376 MHz, C D ): d ¼ ꢀ81.45 (CF ), ꢀ112.73 (CF ), 1427, 1371, 1352, 1332 (w, CH), 1239, 1196, 1128, 1107 (s, CF),
6
6
F
3
2
7
1
ꢀ
122.30 (CF
2
), ꢀ123.08 (CF
2
), ꢀ123.71 (CF
2
), ꢀ126.52 (CF
2
); Li 1075, 1047 (s, CF), 1029 (s, CO); H NMR (400 MHz, C
6
D
6
): d
H
¼
1
1
3
2
NMR (156 MHz, C
6
D
6
): dLi ¼ 0.98; B NMR (128 MHz, C
6
D
6
): d
B
1.24 (12H, d, JH–P ¼ 12.5 Hz, CH
3
), 1.26 (2H, m, JH–P ¼ 69.5 Hz,
1
1
31
1
3
1
¼
ꢀ43.23 (m, JB–H ¼ 2.43 Hz, JB–P ¼ 60 Hz); P{ H} NMR (162
J
H–H ¼ 10.5 Hz, CHCH
3
), 1.40 (3H, t, JB–H ¼ 2.45 Hz, BH
3
), 2.08
1
+
2
1
3
MHz, C
6
D
6
): d
P
¼ 32.50 (d, JP–B ¼ 60 Hz). MS(ES ) m/z: found for (1H, m, JP–H ¼ 75.5 Hz, JH–H ¼ 15.24 Hz, JH–H ¼ 10.41, CH
2
P),
P),
+
2
1
3
C
17
F
17
H
23LiOBP: 615.1450 [M + H ], calculated 615.1468.
2.20 (1H, m, JP–H ¼ 68.2 Hz, JH–H ¼ 15.1, JH–H ¼ 10.2, CH
2
ꢀ
1
2
1
3
7
: IR n (cm ); 2955 (w, CH), 2382 (s, BH), 1669 (s, C]C, Ar), 2.44 (1H, m, J
¼ 15.0 Hz, J
¼ 15.0 Hz, J
¼ 6.2 Hz,
H–F
H–H
H–H
2
1
3
1
469, 1394 (w, CH), 1238, 1202, 1148, 1114 (s, CF), 1022 (s, CO); CH CF ), 2.64 (1H, m, J
¼ 15.0 Hz, J
¼ 15.0 Hz, J
¼
2
2
H–F
H–H
H–H
1
1
13
1
H NMR (400 MHz, C D ): d ¼ 1.71 (3H, d, J
¼ 2.43 Hz, 6.2 Hz, CH CF ), 4.43 (s, OH), 4.41 (1H, q, CHOH); C{ H} NMR
6
6
H
B–H
2
2
2
1
3
3
1
BH
3
), 2.31 (1H, m, JP–H ¼ 77.14 Hz, JH–H ¼ 15.24 Hz, JH–H
¼
¼
(100 MHz, C
6
D
6
): d
C
¼ 17.06 (d, JC–P ¼ 3 Hz, CH
3
), 19.06 (d, JC–P
), 36.13 (d, JC–P ¼ 31.1 Hz, CCH
2
1
3
1
1
1
0.41, CH
0.3, CH
6.2 Hz, CH
2
P), 2.60 (1H, m, JP–H ¼ 69.2 Hz, JH–H ¼ 15.4, JH–H
¼ 30.5 Hz, P–CH
2
3
), 45.49 (m,
1
2
1
3
2
1
2
P), 3.66 ( H, m, JH–F ¼ 15.0 Hz, JH–H ¼ 15.0 Hz, JH–H
J
J
C–F ¼ 22.8 Hz, CF
2
CH
CF
2
), 60.88 (CHOH), 108 (m, JC–F ¼ 270 Hz,
2
1
2
1
2
¼
2
CF
2
), 4.58 (1H, m, JH–F ¼ 15.0 Hz, JH–H ¼ 15.0 Hz,
C–F ¼ 32.9 Hz, CF
2
3
), 111 (tt, JC–F ¼ 270 Hz, JC–F ¼ 32.9,
3
4
1
2
1
J
H–H ¼ 6.2 Hz, CH
2
CF
2
), 4.87 (1H, q, CHOH), 7.54 (2H, m, JH–P CF
2
), 114 (tt, JC–F ¼ 257 Hz, JC–F ¼ 32.9 Hz, CF
2
), 115 (tt, JC–F
¼
¼
2
3
3
2
1
2
¼
1.2 Hz, J
¼ 7.5 Hz, ArH), 7.75 (4H, m, J
¼ 8.4 Hz, J
288 Hz, J
¼ 32.9 Hz, CF CH ), 119 (tt, J
¼ 257 Hz, J
H–H
H–P
H–H
C–F
2
2
C–F
C–F
1
3
1
19
¼
7.5 Hz, ArH); C{ H} NMR (100 MHz, C D ): d ¼ 34.74 (d, 32.9 Hz, CF CF ); F NMR (376 MHz, C D ): d ¼ ꢀ80.63 (CF ),
6
6
C
2
3
6
6
F
3
1
2
JC–P ¼ 30.5 Hz, P–CH ), 45.35 (m, J
¼ 22.8 Hz, CF CH ), ꢀ111.38 (CF ), ꢀ121.65 (CF ), ꢀ122.53 (CF ), ꢀ123.36 (CF ),
2
1
C–F
2
2
2
2
2
2
2
11
1
6
1.76 (CHOH), 108 (m, JC–F ¼ 270 Hz, JC–F ¼ 32.9 Hz, CF
2
CF
3
), ꢀ126.15 (CF
2
); B NMR (128 MHz, C
6
D
6
): d
B
¼ ꢀ43.74 (m, JB–H
): d
22OBP:
1
2
1
1
31
1
1
11 (tt, JC–F ¼ 270 Hz, JC–F ¼ 32.9, CF
2
), 113 (tt, JC–F ¼ 257 Hz, ¼ 2.43 Hz, JB–P ¼ 67 Hz); P{ H} NMR (162 MHz, C
6
D
F H
17
6
P
¼
2
1
2
1
+
J
C–F ¼ 32.9 Hz, CF
2
), 116 (tt, JC–F ¼ 288 Hz, JC–F ¼ 32.9 Hz, 31.96 (d, JP–B ¼ 67 Hz); MS (ES ) m/z: found for C17
1
2
+
CF
1
2
CH
2
), 119 (tt, 118.7, JC–F ¼ 257 Hz, JC–F ¼ 32.9 Hz, CF
2
CF
2
), 607.1248 [M + H ] calculated 607.1230.
1
9
ꢀ1
28.80 (m, ArC), 131.18 (m, ArC), 132.17 (m, ArC); F NMR (376
10: IR n (cm ): 3299 (s, OH) 2955 (w, CH), 2387 (s, BH), 1668
MHz, C D ): d ¼ ꢀ81.73 (CF ), ꢀ112.86 (CF ), ꢀ122.18 (CF ), (s, C]C, Ar), 1474, 1395, 1370 (w, CH), 1236, 1200, 1144, 1133
6
6
F
3
2
2
7
1
ꢀ
123.09 (CF ), ꢀ123.59 (CF ), ꢀ126.62 (CF ); Li NMR (156 (s, CF), 1022 (s, CO); H NMR (400 MHz, C D ): d ¼ 1.01 (1H,
2
2
2
6
6
H
1
1
2
1
3
MHz, C D ): d ¼ 0.88 ppm; B NMR (128 MHz, C D ): d ¼ m, J
¼ 77.14 Hz, J
15.24 Hz, J
¼ 10.41, CH P), 1.16
6
6
Li
6
6
B
P–H
H–H ¼
H–H
2
1
1
31
1
2
1
3
ꢀ
38.52 (m, JB–H ¼ 2.43 Hz, JB–P ¼ 54 Hz); P{ H} NMR (162 (1H, m, JP–H ¼ 69.2 Hz, JH–H ¼ 15.4, JH–H ¼ 10.3, CH
2
P), 1.5
1
1
2
1
MHz, C
6
D
6
): d
P
¼ 12.81 (d, JP–B ¼ 54 Hz).
(3H, d, JB–H ¼ 2.43 Hz, BH
3
), 1.9 (1H, m, JH–F ¼ 15.0 Hz, JH–H
3
2
¼
15.0 Hz, JH–H ¼ 6.2 Hz, CH
2
CF
2
), 2.3 (1H, m, JH–F ¼ 15.0 Hz,
1
3
J
H–H ¼ 15.0 Hz, JH–H ¼ 6.2 Hz, CH
2 2
CF ), 3.67 (1H, q, CHOH),
Synthesis of 8–10
3
2
4
.67 (1H, s, CHOH), 7.20 (6H, m, JH–P ¼ 1.2 Hz, JH–H ¼ 7.5 Hz,
3
3
13
1
Solid samples of 5, 6 or 8 were quenched with degassed water (5 ArH), 7.26 (4H, m, JH–P ¼ 8.4 Hz, JH–H ¼ 7.5 Hz, ArH); C{ H}
3
3
1
cm ) and DCM (10 cm ) added. The organic phase was sepa- NMR (100 MHz, C
D
): d
¼ 35.06 (d, JC–P ¼ 30.5 Hz, P–CH
),
2
6
6
C
2
1
rated, dried over MgSO
vacuo to yield yellow oil.
4
and ltered. The solvent removed in 46.00 (m, JC–F ¼ 22.8 Hz, CF
2
CH
CF
2
), 61.44 (CHOH), 108 (m, JC–F
2
1
2
¼ 270 Hz, JC–F ¼ 32.9 Hz, CF
2
3
), 111 (tt, JC–F ¼ 270 Hz, JC–F
ꢀ
1
1
2
8
: IR n (cm ): 3298 (s, OH) 2955 (w, CH), 2387 (s, BH), 1474, ¼ 32.9, CF
2
), 113 (tt, JC–F ¼ 257 Hz, JC–F ¼ 32.9 Hz, CF
2
), 116 (tt,
1
2
1
1
395, 1370 (w, CH), 1232, 1194, 1143, 1122 (s, CF), 1061, 1075 (s,
J
C–F ¼ 288 Hz, JC–F ¼ 32.9 Hz, CF
2
CH
2
), 118 (tt, 118.7, JC–F
3
), 129 (m, ArC), 131 (m, ArC), 132 (m,
¼
1
2
CF), 1074 (s, CO); H NMR (400 MHz, C
H–P ¼ 12.5 Hz, CH
6
D
6
): d
H
¼ 1.07 (18H, d, 257 Hz, JC–F ¼ 32.9 Hz, CF
3
2
1
19
J
3
), 1.65 (1H, m, JP–H ¼ 77.14 Hz, JH–H
¼
ArC); F NMR (376 MHz, C
6
D
6
): d
F
¼ ꢀ80.79 (CF ), ꢀ112.28
3
28942 | RSC Adv., 2019, 9, 28936–28945
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3
2
(
CF
2
), ꢀ121.77 (CF
2
), ꢀ122.74(CF
2
), ꢀ123.33 (CF
2
), ꢀ126.17 ¼ 15.24 Hz, JH–H ¼ 10.41, CH
2
P), 1.16 (1H, m, JP–H ¼ 69.2 Hz,
1
1
1
1
1
3
2
(
CF2); B NMR (128 MHz, C D ): d ¼ ꢀ39.33 (m,
J
¼
J
¼ 15.4, J
¼ 10.3, CH P), 1.90 (1H, m, J
¼ 15.0 Hz,
6
6
B
B–H
H–H
H–H
2
H–F
1
31
1
3
2
2
1
6
.43 Hz, J
1.69 (d, J
¼ 60 Hz); P{ H} NMR (162 MHz, C D ): d ¼
JH–H ¼ 15.0 Hz, J
¼ 6.2 Hz, CH CF ), 2.30 (1H, m, J
¼
B–P
6
6
P
H–H
2
2
H–F
1
ꢀ
1
3
¼ 60 Hz); MS(ES ) m/z: found for C F H OBP: 15.0 Hz, J
¼ 15.0 Hz, J
¼ 6.2 Hz, CH CF ), 3.67 (1H, q,
P–B
23 17 18
H–H
H–H
2
2
ꢀ
3 2
75.0920 [M ꢀ H ], calculated 675.0917.
CHOH), 4.67 (1H, s, CHOH), 7.20 (2H, m, JH–P ¼ 1.2 Hz, JH–H ¼
3 3
7
.5 Hz, ArH), 7.76 (4H, m, JH–P ¼ 8.4 Hz, JH–H ¼ 7.5 Hz, ArH);
1
3
1
1
C{ H}NMR (100 MHz, C
6
D
6
): d
C
¼ 36.03 (d, JC–P ¼ 30.5 Hz,
Synthesis of 11–13
2
PCH
2
1
), 44.39 (m, JC–F ¼ 22.8 Hz, CF
2 2
CH ), 61.44 (CHOH), 108
3
3
2
1
To a solution of 8–10 in DCM (5 cm ), TMEDA (2 cm ) was added (m, JC–F ¼ 270 Hz, JC–F ¼ 32.9 Hz, CF
2
CF
3
), 111 (tt, JC–F
¼
3
1
1
2
1
2
and the reaction was stirred for 3 hours and followed by P{ H} 270 Hz, JC–F ¼ 32.9, CF
), 116 (tt, JC–F ¼ 257 Hz, JC–F ¼ 32.9 Hz,
2
1
2
NMR spectroscopy until the complete deprotection had CF
), 119 (tt, JC–F ¼ 288 Hz, JC–F ¼ 32.9 Hz, CF
CH ), 120 (tt,
2 2
2
1
2
occurred. The solvents were removed in vacuo until all 118.7, JC–F ¼ 257 Hz, JC–F ¼ 32.9 Hz, CF
CF
131 (2C, m, ArC), 132 (4C, m, ArC); F NMR (376 MHz, C
1: IR n (cm ); 3495 (s, OH) 2963 (w, CH), 1471, 1427, 1392, ¼ ꢀ81.73 (CF ), ꢀ112.86 (CF ), ꢀ122.18 (CF ), ꢀ123.09 (CF
); P{ H} NMR (162 MHz, C
), 128 (6C, m, ArC),
2
3
1
9
TMEDA$BH
3
had been removed.
6
D
6
): d
F
ꢀ1
1
3
2
31
2
2
),
1
1
1
371, 1332 (w, CH), 1239, 1198, 1107 (s, CF), 1075 (s, CO); H ꢀ123.59 (CF
2
), ꢀ126.62 (CF
2
6
D
6
): d
P
3
+
NMR (400 MHz, C
1
CH
CH
6
D
6
): d
H
¼ 1.04 (18H, d, JH–P ¼ 12.5 Hz, CH
3
), ¼ ꢀ22.61; MS(ES ) m/z: found for C23
F H17OP: 663.0721 [M +
17
2
1
3
+
.66 (1H, m, JP–H ¼ 77.14 Hz, JH–H ¼ 15.24 Hz, JH–H ¼ 10.41, H ] calculated 663.0746.
2
1
3
2
P), 1.83 (1H, m, JP–H ¼ 69.2 Hz, JH–H ¼ 15.4, JH–H ¼ 10.3,
2
1
3
2
P), 2.25 (1H, m, JH–F ¼ 15.0 Hz, JH–H ¼ 15.0 Hz, JH–H
¼
2
1
Conflicts of interest
6
.2 Hz, CH
2
CF
2
), 2.51 (1H, m, JH–F ¼ 15.0 Hz, JH–H ¼ 15.0 Hz,
3
J
H–H ¼ 6.2 Hz, CH
2 2
CF ), 4.04 (1H, s, CHOH), 4.63 (1H, q,
There are no conicts to declare.
1
3
1
3
CHOH); C{ H} NMR (100 MHz, C D ): d ¼ 27.26 (d, J
¼
6
6
C
C–P
1
1
3
3
Hz, CH ), 31.84 (d, J
1.1 Hz, CCH
¼ 30.5 Hz, P–CH ), 38.60 (d, J
¼
3
C–P
2
C–P
2
3
), 44.39 (m,
J
C–F ¼ 22.8 Hz, CF
2
CH
2
), 62.73 Acknowledgements
1
2
(
(
CHOH), 105 (m, JC–F ¼ 270 Hz, JC–F ¼ 32.9 Hz, CF
2
CF
3
), 108
1
2
1
2
FB and MI thank the Higher Education Commission for Paki-
stan for funding.
tt, JC–F ¼ 270 Hz, JC–F ¼ 32.9, CF
2
), 113 (tt, JC–F ¼ 257 Hz, JC–F
1
2
¼
32.9 Hz, CF
2
), 116 (tt, JC–F ¼ 288 Hz, JC–F ¼ 32.9 Hz, CF
1
2 2
CH ),
); F NMR
2
19
1
18 (tt, 118.7, JC–F ¼ 257 Hz, JC–F ¼ 32.9 Hz, CF
2
CF
3
(
(
376 MHz, C ): d ), ꢀ112.38 (CF
6
D
6
F
¼ ꢀ80.78 (CF
3
2
), ꢀ121.77
Notes and references
3
1
1
CF ), ꢀ122.74 (CF ), ꢀ123.33 (CF ), ꢀ126.17 (CF ); P{ H}
2
2
2
2
ꢀ
NMR (162 MHz, C D ): d ¼ 19.32; MS(ES ) m/z: found for
1 (a) P. Barbaro and F. Liguori, Heterogenized Homogeneous
Catalysis for Fine Chemicals Production: Materials and
Processes, Springer, Heidelberg, 2010; (b) A. Kirschning,
Immobilized Catalysis: Solid Phases, Immobilization and
Applications, Springer, Berlin, 2004.
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1048.
7 (a) J.-M. Vincent, M. Contel, G. Pozzi and R. H. Fish, Coord.
Chem. Rev., 2019, 380, 584; (b) W.-B. Yi, J.-J. Ma,
L.-Q. Jiang, C. Cai and W. Zhang, J. Fluorine Chem., 2014,
157, 84.
8 (a) J. Balogh, A. R. Hlil, H.-L. Su, Z. Xi, H. S. Bazzi and
J. A. Gladysz, ChemCatChem, 2016, 8, 125; (b) Z. Xi,
H. S. Bazzi and J. A. Gladysz, Catal. Sci. Technol., 2014, 4,
4178; (c) R. Tuba, R. Correa da Costa, H. S. Bazzi and
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da Costa and J. A. Gladysz, Adv. Synth. Catal., 2007, 349,
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Commun., 2006, 2619.
6
6
P
ꢀ
C
19
F
17
H23OP: 621.1225 [M
ꢀ
H ] calculated 621.1215,
+
MS(MALDI+) m/z: found for C19
calculated 623.1372.
F
17
H
25OP: 623.1402 [M + H ]
ꢀ
1
1
2: IR n (cm ): 3495 (s, OH), 2963 (w, CH), 1471, 1427, 1371,
1
´
´
1
332 (w, CH), 1239, 1195, 1146, 1108 (s, CF), 1075 (s, CO); H
3
NMR (400 MHz, C
1
m, J
6
D
6
): d
H
¼ 1.19 (12H, d, JH–P ¼ 12.5 Hz, CH
3
),
2
3
.23 (2H, m, J
¼ 69.5 Hz, J
¼ 10.5 Hz, CHCH ), 1.87 (1H,
H–P
H–H
3
2
1
3
¼ 75.5 Hz, J
¼ 15.24 Hz, J
¼ 10.41, CH P), 2.06
P–H
H–H
H–H
3
2
2
1
(
(
1H, m, JP–H ¼ 68.2 Hz, JH–H ¼ 15.1, JH–H ¼ 10.2, CH
2
P), 2.31
3
1
3
1H, m,
J
H–F ¼ 15.0 Hz,
J
H–H ¼ 15.0 Hz,
J
H–H ¼ 6.2 Hz,
2
1
3
CH
.2 Hz, CH
100 MHz, C
2
CF
2
), 2.55 (1H, m, JH–F ¼ 15.0 Hz, JH–H ¼ 15.0 Hz, JH–H
¼
1
3
1
6
2
CF
2
), 4.38 (s, OH), 4.51 (1H, q, CHOH); C{ H}NMR
3
1
(
6
D
6
): d
C
¼ 17.05 (d, JC–P ¼ 3 Hz, CH
3
), 22.84 (d, JC–P
1
2
¼
30.5 Hz, PCH
2
), 27.98 (d, JC–P ¼ 31.1 Hz, CCH
3
), 46.32 (m, JC–
1
2
¼
22.8 Hz, CF CH ), 62.08 (CHOH), 105 (m, J ¼ 270 Hz, J
F
2
2
C–F
C–
1
2
¼
32.9 Hz, CF CF ), 107 (tt, J
¼ 270 Hz, J
¼ 32.9, CF ),
F
2
3
C–F
C–F
2
1
2
1
1
2
3
10 (tt, JC–F ¼ 257 Hz, JC–F ¼ 32.9 Hz, CF
2
), 112 (tt, JC–F
¼
¼
2
1
2
88 Hz, JC–F ¼ 32.9 Hz, CF
2
CH
2
), 115 (tt, JC–F ¼ 257 Hz, JC–F
): d
¼ ꢀ81.29 (CF
), ꢀ122.89 (CF ), ꢀ123.30 (CF
); P{ H} NMR (162 MHz, C ): d
21OP: 595.1061 [M + H ]
1
9
2.9 Hz, CF
2
CF
3
); F NMR (376 MHz, C
6
D
6
F
3
),
),
ꢀ
112.40 (CF
126.27 (CF
2
), ꢀ121.73 (CF
2
2
2
3
1
1
ꢀ
2
6
D
6
P
¼ 27.44.
+
+
MS(MALDI ) m/z: found for C17
F
17
H
calculated 595.1059.
ꢀ
1
1
3: IR n (cm ): 3361 (s, OH), 2959 (w, CH), 1638 (s, C]C, Ar),
1
1
468, 1368, (w, CH), 1238, 1202, 1145 (s, CF), 1021 (s, CO); H
2
1
NMR (400 MHz, C
6
D
6
): d
H
¼ 1.01 (1H, m, JP–H ¼ 77.14 Hz, JH–H
9 M. Ikram and R. J. Baker, J. Fluorine Chem., 2012, 139, 58.
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, 378; (c) S. K. Wolff, D. J. Grimwood, J. J. McKinnon, basis of Ph PHBH (Sigma Aldrich V295.00 for 5 g; cat no.
2
4
2
3
M. J. Turner, D. Jayatilaka and M. A. Spackman,
CrystalExplorer (Version 3.1), University of Western
Australia, 2012.
449563) and 3-(peruorooctyl)-1,2-propenoxide (uorochem
£28.00 for 5 g; cat no: 007145) prices correct 22/04/2019.
52 Bruker APEX 2 v2012.12–0, Bruker AXS Inc., Madison,
Wisconsin, USA.
4
0 (a) R. Shukla and D. Chopra, CrystEngComm, 2015, 17, 3596;
(
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59 G. K. Anderson and M. Lin, Inorg. Synth., 1990, 28, 60.
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