Novel electrochemical pathway to fluoroalkyl phosphines and phosphine oxides

Article abstract of DOI:10.1016/j.jfluchem.2013.04.009

Novel versatile electrocatalytic route for obtaining fluoroalkylated phosphines and phosphine oxides from white phosphorous or diphenylchlorophosphine is discussed. This process occurs under electrochemical generation of nickel complexes in low oxidation

Full text of DOI:10.1016/j.jfluchem.2013.04.009

Accepted Manuscript
Title: Novel Electrochemical Pathway to Fluoroalkyl
Phosphines and Phosphine Oxides
Author: Dmitry Y. Mikhaylov Tatyana V. Gryaznova Yulia B.
Dudkina Fedor M. Polyancev Shamil K. Latypov Oleg G.
Sinyashin Yulia H. Budnikova
PII:
S0022-1139(13)00167-X
DOI:
Reference:
http://dx.doi.org/doi:10.1016/j.jfluchem.2013.04.009
FLUOR 8099
To appear in:
FLUOR
Received date:
Revised date:
Accepted date:
4-2-2013
23-4-2013
27-4-2013
Please cite this article as: D.Y. Mikhaylov, T.V. Gryaznova, Y.B. Dudkina, F.M.
Polyancev, S.K. Latypov, O.G. Sinyashin, Y.H. Budnikova, Novel Electrochemical
Pathway to Fluoroalkyl Phosphines and Phosphine Oxides, Journal of Fluorine
Chemistry (2013), http://dx.doi.org/10.1016/j.jfluchem.2013.04.009
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*Graphical Abstract - Pictogram
Page 1 of 15

*Graphical Abstract - Synopsis
The electrochemical joint reduction of fluoroalkyl iodides in presence of 2,2’-bipyridine nickel
dibromide with white phosphorous or diphenylchlorophosphine leads effectively to fluoroalkyl
phosphines in mild conditions.
Page 2 of 15

*Highlights (for review)
 Organofluorine phosphines are obtained from white phosphorous under electrocatalysis
 The procedure is applicable for partly fluorinated and fully fluorinated phosphines
 Electrocatalytic coupling with diphenylchlorophosphine leads to fluorinated product
 Electrochemically generated bypiridine nickel (0) complex serves as catalyst
 Available fluoroalkyl iodides are used as the fluoroalkyl sources
Page 3 of 15

*Manuscript
Novel Electrochemical Pathway to Fluoroalkyl Phosphines and Phosphine Oxides
Dmitry Y. Mikhaylov, Tatyana V. Gryaznova, Yulia B. Dudkina, Fedor M. Polyancev, Shamil K.
Latypov, Oleg G. Sinyashin and Yulia H. Budnikova*
A.E.Arbuzov Institute of Organic and Physical Chemistry Kazan Scientific Center of Russian
Academy of Sciences, 8 Arbuzov str., 420088, Kazan, Russian Federation
Tel.: +7-843-279-53-35, Fax: +7-843-273-22-53
E-mail: yulia@iopc.ru
Abstract
Novel versatile electrocatalytic route for obtaining fluoroalkylated phosphines and phosphine
oxides from white phosphorous or diphenylchlorophosphine is discussed. This process occurs
under electrochemical generation of nickel complexes in low oxidation state during undivided
electrolysis of organofluorine iodides and phosphorous-containing substrate in mild conditions
without supporting electrolyte.
Keywords: Electrocatalysis, white phosphorus, nickel complex, fluoroalkyl halides, fluorinated
phosphines
1. Introduction
Among organofluorine compounds, those containing perfluoroalkyl groups (RF) have
became especially important; thus, it is required to develop new approaches to introducing these
particular groups. Perfluoroalkylsubstituted phosphines have lately drawn much attention due to
their potential applications as ligands in organometallic chemistry [1-8] particularly in fluorous
biphase catalysis [9]. Phosphines functionalized with perfluorinated chains are known for their
thermomorphic properties with a significant increase in solubility observed on raising the
temperature [10-11]. Lastly, fluorine substitution has been successfully employed in phosphorus
chemistry to increase bioabsorption and metabolic stability of biologically important compounds.
After a pioneer work of Emeleus and Hazeldine [12] reporting the first synthesis of
tris(trifluoromethyl)phosphine in 1953 some efforts in the field of perfluoroalkylphosphines have
been made. In 1999 Lagow and coworkers reported direct elemental fluorination of
trialkylphosphines in the solution phase reactor [13], Caffyn et al perfomed the synthesis of
tris(perfluoroalkyl)phosphines by the reaction of triphenylphosphite with Ruppert’s reagent
(RFSiMe3)
[14].
Alternative
synthetic
procedure
for
synthesis
of
diphenyl(perfluoroalkyl)phosphines was based on the reaction of trimethylsilylphosphines with
Page 4 of 15

corresponding perfluoroalkyl iodides [15]. Recently published comprehensive review on
fluoroalkyl-containing phosphines has only short column devoted to direct synthesis of RFI with
elemental phosphorus and majority of methods have obvious drawbacks [16]. Partially
fluorinated phosphines with “fluorous ponyltails” (-(CH2)n-RF) recently have gained much
attention [9]. First report on the synthesis of P(CH2CH2(CF2)5CF3)3 published in 1985 was based
on utilizing PCl3 and IZnCH2CH2RF6 [17]. Further developments in this field were made by
using Grignard reagents [18] of fluoroalkyl halides. Gladysz and co-workers reported procedure
from gaseous PH3, fluorinated olefins and radical initiators [19]. The synthesis of (RF)3P by
means of reduction of the difuorophosphoranes (RF)3PF2 with the NaBH4 is known [20-21].
Apparently, this method is not suitable for long-chain Rf phosphines, as only experiments with
phosphoranes of C2 and C4 and their products were described in the patent. Although the higher
perfluoroalkyl derivatives were included in the general patent formula, the authors specify that
the C1-C4 derivatives are preferred. Initial perfluoroalkyl phosphoranes are produced by
electrochemical fluorination of corresponding trialkylphosphines (49-74%) or phosphine oxides
(24-46% yield) in anhydrous hydrogen fluoride, and as can be expected, the yield of
tris(perfuoroalkyl)difuorophosphoranes diminishes with increasing number of CH2 groups in the
aliphatic chain of the starting trialkylphosphine due to adverse degradation processes [22-24].
Although growing interest in a last few decades resulted in number of publications on the
synthesis of tertiary fluoroalkylphosphines the convenient route for obtaining these compounds
is a question of a great demand.
The interest in the direct synthesis of organophosphorus compounds from elemental
phosphorus, escaping the traditional stages of its chlorination, stems from the increasing needs to
reorient the chemical technology towards the strategic target of combining increased ecological
safety with low-waste production. In this context, a replacement of the current process for the
preparation of organophosphorus compounds using phosphorus chloride and oxychloride is of
paramount importance. We previously described the convenient electrochemical pathway to
triarylphosphines from white phosphorous [25-30]. However, this approach was unsuccessful in
case of alkylphosphines. Furthermore, just recently we developed the electrocatalytic
fluoroalkylation of olefins with readily available fluoroalkyl halides as a source of
organofluorine moieties [31-33]. The scope of the current contribution is to obtain
organofluorine phosphines and phosphine oxides from white phosphorus or
diphenylchlorophosphine by means of the electrosynthesis mediated by highly reactive nickel
species.
2. Results and Discussion
Page 5 of 15

We demonstrate herein the possibility to prepare compounds with P-C bonds directly
from white phosphorus and organofluorine halides under the action of electrochemically
generated complexes of nickel in low oxidation state or organofluorine -complexes, obtained
on their basis. For this purpose, electrochemical reduction of solutions of fluoroalkyl iodides in
DMF in the presence of tetraphosphorus emulsion and (bpy)NiBr2 complex as a catalyst were
performed (Scheme 1).
Scheme 1. Electroreductive preparation of fluoroalkyl derivatives of white phosphorous.
The reaction proceeds in undivided electrochemical cell equipped with Pt-cathode and sacrificial
Zn-anode without any supporting electrolyte. Electroconductivity was provided by NiBr2bpy at
the beginning of the reaction, and in the initial stage of the process was fair and quickly became
very good after dissolving the zinc anode. Tertiary phosphines are observed in all cases as major
products in reaction mixture by 31P NMR (more than 90%). Ep reduction for NiBr2bpy is -1.50V,
for С6F13I -1.76V and C6H4F9I -1.80V (GC, DMF, ref.Ag/AgNO3) respectively.
The oxidation of phosphine to phosphine oxide probably proceeds under the action of
oxygen trace and at the product isolation stage because no special precautions were taken and
nickel compounds are known to promote this reaction.[34-35] It is shown previously that the
autocatalytic transformation of phosphines to phosphine oxides under tine influence of Ni°
complexes and molecular oxygen at room temperature takes place. To avoid this reaction,
syntheses should be carried out in the absence of oxygen at all stages using the so-called argon
line and at below -5 °C.
However, we targeted to show the proof-in-principle of organofluorine addition to white
phosphorous and it was decided to further oxidize the phosphine to phosphine oxides, which are
easy to handle. Whereas compounds 1 and 3 are new, 2 [13,14] and 4 [17,23] were previously
reported. The important aspect is that the electrolyses were performed without any supporting
electrolyte which simplifies the product isolation and makes this method more convenient. It
should be noted that in absence of nickel catalyst and in presence of supporting electrolyte the
phosphines can be observed by 31P NMR spectra, however the yields are poor and there are
Page 6 of 15

various undesired side products. In this case, 31P NMR spectrum shows phosphines (less than
10%), phosphine oxides, phosphonium salts and therefore electrosynthesis proceeds
nonselectively. The structure of product 3 was fully characterized by variety of NMR correlation
methods. Starting from phosphorus the molecule structure up to C3 carbon can be directly
established by 2D 1Н-31P HMBC and 1H-13C HSQC/HMBC, connectivities (Fig. 1).
Unfortunately due to large quantity of vicinal fluorine atoms with strong spin-spin couplings to
more remote fluorine bearing carbons (C4-C6) their intensities are dramatically diminished and
13
therefore no signals were assigned in C NMR spectra for these carbons (ESI). Proton-fluorine
and fluorine-fluorine correlation NMR experiments were particularly helpful in this case and
allowed to us follow along the perfluorinated chain and thus establish the whole molecule
structure. This conclusion in additionally supported by agreement of the calculated (GIAO
B3LYP/6-31G(d)//B3LYP/6-31G(d), (see supporting information)) versus experimental 19F
1
chemical shifts (R2 = 0.96). Moreover, comparison of experimental H CSs with calculated for
two main conformers of 3 (“disk” and “pyramid” like) let us suggest that this molecule in
solution prefer the “disk”-like structure (Fig. 1).
Figure 1. Principal 1Н-31P/13C HMBC, 1H-19F HETCOR and 19F-19F COSY connectivity’s for
compound 3 (top). Main conformation of 3 (bottom).
We suppose that white phosphorus can be involved in the reaction with perfluoroalkyl
under conditions of cyclic regeneration of metallocomplex catalyst at the electrode. By analogy
with the white phosphorus functionalization process by Grignard reagents, it is proposed that a
key stage of the reaction consists in the interaction of organonickel compound, [RFNiIIXLn], with
white phosphorus according to the following sequence (Scheme 2). In course of the reaction
several processes may occur. First of all, the tetraphosphorous molecule reacts with
Page 7 of 15

organofluorine sigma-complex of nickel similarly as for aryl-nickel complexes [28-29,35].
Another one is abovementioned Grignard-type functionalization. Moreover, the anode material is
also important due to the possible formation of the corresponding intermediate metal phosphides
with various reactivity and due to the favorable transmetallation at several stages. A variety of
intermediates with P-RF bond are formed during the synthesis. However the main feature is that
the total process selectively yields to the full disclosure of all P-P bonds and result to the final
product with three P-C bonds.
Scheme 2. Proposed reaction sequence.
The process scheme is given in general terms on the basis of detailed mechanism studies of
the of activation and transformation of white phosphorus in systems containing Ni(0)L generated
electrochemically, alkyl (or aryl) halide, sacrificial anode (Zn, Mg, Al), highly reactive -
organonickel complexes in electrocatalytic processes, described earlier [29,30,36-38]. In order to
confirm the white phosphorus pathway, the organonickel compound RNiXL formation and the
functionalization of white phosphorus by this nickel complex were separated. The mechanism of
P4 funсtionalization is still not completely understood. Interestingly, the electrolysis of
perfluoroalkyl halide in the presence of white phosphorus and zinc anode (in the absence of
nickel complex catalyst) yields no desired fluoroalkyl phosphines or their oxides. So,
intermediate organozink, RFZnI, obtained by RFX reduction in the presence of Zn2+ in these
conditions does not allow to break the P-P bonds of white phosphorus or its oligomers
selectively. The most part of the white phosphorus is polymerized in low reactive insoluble
structures with a high content of phosphorus. Electrolysis in the divided electrolytic cell with the
absence of zinc ion generated from the anode does not produce the desired products also.
Earlier we described nickel-catalyzed electrochemical coupling between mono- or di-
chlorophenylphosphines and aryl or heteroaryl halides [39]. Aiming to expand the scope of the
proposed method we decided to alter the source of phosphorous and therefore examined the
electrocatalytic fluoroalkylation with diphenylchlorophosphine (Scheme 3).
Page 8 of 15

Scheme 3. Electrocatalytic fluoroakylation of diphenylchlorophosphine.
The structure of compound 7 was unequivocally established directly starting from one
“end” of molecular up to another “end” through variety NMR connectivity’s (1Н-13C HMBC,
1
19
1
1
1Н-31P HMBC, H-19F HETCOR, F-19F COSY, H-19F HETCOR and finally Н-13C HMBC).
Moreover good correlation of the calculated (GIAO B3LYP/6-31G(d)//B3LYP/6-31G(d), (see
supporting information)) versus experimental 19F chemical shifts (R2 = 0.98) additionally
supports the above conclusion on the structure.
Compounds 6 and 8 were previously obtained by Rossi et al. upon reaction of Ph2P- ions
and RFI in HMPA, DMPU or liquid ammonia and under photochemical irradiation [40].
However, the yields of diphenyl(perfluorohexyl)phosphine 6 were low and authors do not
provide 31P NMR data for diphenyl(perfluorohexyl)phosphine.
3. Conclusions
Hereby we report one-step versatile and convenient method for obtaining organofluorine
derivatives of phosphorous, directly from white phosphorus or diphenylchlorophosphine with
good yields. Electrochemically generated nickel (0) complex with 2,2’-bipyridine serves as
catalyst. The procedure is applicable either for partly fluorinated as well as fully fluorinated
phosphines and phosphine oxides. Moreover, it was possible to avoid the use of hazardous PH3,
air and moisture sensitive organometallic reagents, complicated reactors, high temperatures and
pressure. The ability to perform the reaction without any supporting electrolyte greatly
simplifies the workup procedure. Further efforts are forwarded to discover the mechanistic
details of these intriguing reactions.
4. Experimental
Page 9 of 15

4.1. General consideration
All reactions were carried out under dry argon atmosphere. All solvents employed were purified
and dried prior to use. N,N-Dimethylformamide was purified by double fractionation distillation
over melting potash. Organofluorine iodides was purchased from P&M Invest and used without
further purification. Preparative electrolyses were performed by means of the direct current
source B5-49 in thermostatically controlled cylindrical undivided 80 mL electrolyser (a three-
electrode cell). Platinum with surface area of 20 cm2 was used as a cathode, Zn-rod as an anode.
The working electrode potential was determined using reference electrode SCE. Electrolysis was
carried out at constant current. The high rate of the catalyst regeneration allows using the
constant current density of 5 mA/cm2, but the cathode potential was controlled and consistent to
nickel complex reduction. During electrolysis, the electrolyte was stirred with a magnetic stirrer.
Mass spectra were recorded in EI mode using ThermoQuest TRACE MS. (Bpy)NiBr2 was
prepared according reported procedure [41].
4.2. NMR experiments
NMR investigation was carried out in the NMR department (A.E.Arbuzov Institute of Organic
and Physical Chemistry) of the Federal Collective Spectral Analysis Center for physical and
chemical investigations of structure, properties and composition of matter and materials. NMR
experiments were carried out with Bruker spectrometers AVANCE-400 (161.9 MHz (31P),400.1
MHz (1Н), 376.5 MHz (19F), 100.6 MHz (13С)) equipped with a pulsed gradient unit capable of
producing magnetic field pulse gradients in the z-direction of 53.5Gcm-1. Chemical shifts are
1
reported in the δ (ppm) scale relative to the residual H and 13C signal of (CD3)2CO, (C6D6)
31
19
andto external 85% H3PO4 for Pand C6F6 (-164.9 ppm) for FNMR spectra. Chemical shifts
were calculated within the DFT framework using a hybrid exchange-correlation functional,
B3LYP, at the 6-31G(d) level as implemented in Gaussian 98 [33]. Full geometry optimizations
were done at the same level of theory. All data were referred to TMS (1H and 13C) and C6F6
chemical shifts that were calculated under the same conditions.
4.3. Electrosynthesis of tris(1H,1H,2H,2H-perfluorohexyl)phosphine (1).
Electrochemical cell was charged with 0.185 g (1.5 mmol, 1 eq) of P4, 0.112 g (0.3 mmol, 0.2
eq) of NiBr2bpy, 6.7 g (18 mmol, 12 eq.) of 1H,1H,2H,2H-perfluorohexyl iodide and DMF (50
ml) was added. The amounts of electricity passed through the electrolyte were 2F per one mole
of 1H,1H,2H,2H-perfluorohexyl iodide (965mA·h). After completing the electrolysis, the
reaction mixture was concentrated on rotary evaporator. The orange oily residue showed a major
1
product of P(CH2CH2(CF2)3CF3)3 by H NMR and 31P NMR. 1H NMR: (400 MHz,
Page 10 of 15

(CD3)2CO)δ= 1.72 (m, 6H), 2.24 (m, 6H) and 31P{1H} (161.94 MHz, (CD3)2CO)δ= -23.5 (s).
EIMS, m/z: 772 [M]+, 753, 653, 603, 539, 456. The residue was used without further purification
for the next step of synthesis.
4.4. Synthesis of tris(1H,1H,2H,2H-perfluorohexyl)phosphine oxide (3).
The residue after synthesis of compound 1 was transferred into 100 ml round-bottom flask and
treated with an excess of 10% hydrogen peroxide. After 2 hours the mixture was washed with
hexane (3х40 ml), the organic layer was separated, dried over MgSO4and the solvent was
removed. The oily solid residue was washed with cold diethyl either (20 ml) on a frit to give
O=P(CH2CH2(CF2)3CF3)3 as a white solid (3.02 g, 64% based on white phosphorous, 21%
1
current efficiency). H NMR (400 MHz, (CD3)2CO) δ= 2.33 (m, 6H), 2.64 (m, 6H); 31P{1H}
13
NMR (161.94 MHz, (CD3)2CO) δ= 44.02 (s). C NMR (100.6 MHz, (CD3)2CO): δ = 19.75 (d,
2JPC = 67.5 Hz, C1), 24.37 (t, 3JCF = 22.5 Hz, C2), 120 (C3). 19F NMR (376.5 MHz, (CD3)2CO): δ
= -81.98 (t, 3F, 4JFF = 9.63 Hz, CF3), -115.37 (s, 2F, at C3), -124.66 (s, 2F, at C4), -126.68 (t, 2F,
4JFF = 10.48 Hz, at C5). EIMS, m/z: 788 [M]+, 769, 669, 555, 472. Anal.calcd. for C18H12F27OP:
C, 27.43; H, 1.53; P, 3.93; found: C, 27.94; H, 1.72; P, 3.57.
4.5. Electrosynthesis of tris(perfluorohexyl)phosphine (2).
Electrochemical cell was charged with 0.185 g (1.5 mmol, 1 eq) of P4, 0.112 g (0.3 mmol,
0.2 eq) of NiBr2bpy,8.03 g (18 mmol, 12 eq.) of perfluorohexyl iodide and DMF (50 ml) was
added. The amounts of electricity passed through the electrolyte were 2F per one mole of
perfluorohexyl iodide (965mA·h). After completing the electrolysis, the reaction mixture was
concentrated on rotary evaporator. The vinous oily residue showed a major product of
19
31
19
P(CF2(CF2)4CF3)3 by F NMR and P NMR. F NMR (376.5 MHz, (CD3)2CO): δ: -81.05 (s,
CF3); -114.25 (d, 2JPF = 61.2 Hz,2F, at C1); -122.23 (s, 2F, at C2); -123.30 (s, 2F, at C3); -124.21
(s, 2F, at C4); -126.01 (s, 2F, at C5) and 31P{1H} (161.94 MHz, (CD3)2CO)δ= 26.6 (br s) [lit.13,14
27.9 (br)]. EIMS, m/z: 988 [M]+. The residue was used without further purification for the next
step of synthesis.
4.6. Synthesis of tris(perfluorohexyl)phosphine oxide (4).
The residue after synthesis of compound 2 was transferred into 100 ml round-bottom
flask and treated with an excess of 10% hydrogen peroxide. After 2 hours the mixture was
washed with hexane (3х40 ml), the organic layer was separated, dried over MgSO4and the
solvent was removed. The oily solid residue was washed with cold diethyl either (20 ml) on a frit
to give 3.36 g (56% based on white phosphorous, 18% current efficiency) O=P(C6F13)3.31P{1H}
Page 11 of 15

NMR (161.94 MHz, (CD3)2CO) δ= 22.5(m), [lit.17,2325.6]. 19F NMR (376.5 MHz, (CD3)2CO): δ
= -81.67 (t, 3F, 4JFF = 8.7 Hz, CF3), -114.12 (d, 2F, 2JPF = 59.9 Hz, at C1), -122.31 (s, 2F, at C2), -
123.38 (s, 2F, at C3), -124.01 (s, 2F, at C4), -126.71 (2F, at C5). EIMS, m/z: 1004 [M]+.
Anal.calcd. for C18F39OP: C, 21.51; P, 3.09; found: C, 21.38; P, 3.15.
4.7. Electrosynthesis of diphenyl(6H-perfluorohexyl)phosphine (5).
Electrochemical cell was charged with 0.617 g (2.8 mmol, 1 eq) of diphenylchlorophosphine,
0.21 g (0.56 mmol, 0.2 eq) of NiBr2bpy, 1.197g (2.8 mmol, 1 eq.) of 6H-perfluorohexyl iodide
and DMF (50 ml) was added. The amounts of electricity passed through the electrolyte were 2F
per one mole of 6H-perfluorohexyl iodide (150 mA·h). After completing the electrolysis, the
reaction mixture was concentrated on rotary evaporator. The brown oily residue showed a major
product of Ph2P(C6F12H) by 1H NMR and 31P NMR. 1H NMR: (400 MHz, C6D6)δ= 5.52 (tt, 1H,
3
31
2JНF=51.6 Hz, JНF=5.32 Hz), 7.28-745 (m, 10H), 7.61-7.75 (m, 4H) and P{1H} NMR (161.94
2
MHz, C6D6) δ= 1.9 (t, JРF=83.4 Hz). EIMS, m/z: 486 [M]+, 185, 183, 108, 51. The residue was
used without further purification.
4.8. Synthesis of diphenyl(6H-perfluorohexyl)phosphine oxide (7).
The residue after synthesis of compound 5 was transferred into 100 ml round-bottom flask and
treated with an excess of 10% hydrogen peroxide. After 2 hours the mixture was washed with
hexafluorobenzene (3х30 ml), the organic layer was separated, dried over MgSO4and the solvent
was removed. The oily solid residue was washed with cold diethyl either (10 ml) on a frit to give
O=PPh2(C6F12H) as a white solid (0.98 g, 71% based on diphenylchlorophosphine, 69.8%
current efficiency). The product has minor phosphine impurity by 31P NMR (10 %) which can be
removed by column chromatography on silica gel (Et2O:CH2Cl2, 8:2).1H NMR (400 MHz, C6D6)
δ= 5.08 (tt, 1H, 2JНF=50.86 Hz, 3JНF=5.78 Hz, H6), 8.04 (m, 4H), 7.95 (m, 4H), 6.9-7.75 (m, 2H);
31P{1H} NMR (161.94 MHz, C6D6) δ= 23.4 (t, 2JРF=69.24 Hz). 13C NMR (100.6 MHz, C6D6): δ
= 108.59 (tt, 2JFC=253.62 Hz,3JFC=32.80 Hz, C6), 131.58 (s, Ph), 133.14 (d, 2JCP=9.56 Hz,Cipsoat
Ph). 19F NMR (376.5 MHz, C6D6): δ = -108.44 (dt, 3JFF = 13.17 Hz, 3JPF = 54.83 Hz, 2F at C2), -
3
2
4
118.08 (dt, JFF = 14.36 Hz, JPF = 68.56 Hz, 2F at C1), -121.50 (t, JFF = 10.73 Hz, 2F at C3), -
123.18 (s, 2F at C4), -129.40 (s, 2F at C5), -136.84 (s, 2F at C6). EIMS, m/z: 502 [M]+, 201, 200,
51. Anal.calcd. for C18H11F12OP: C, 43.05; H, 2.21; P, 6.17; found: C, 43.51; H, 2.46; P, 6.34.
4.9. Electrosynthesis of diphenyl(perfluorohexyl)phosphine (6).
Electrochemical cell was charged with 0.617
g
(2.8 mmol,
1
eq) of
diphenylchlorophosphine, 0.21 g (0.56 mmol, 0.2 eq) of NiBr2bpy, 1.25 g (2.8 mmol, 1 eq.) of
Page 12 of 15

perfluorohexyl iodide and DMF (50 ml) was added. The amounts of electricity passed through
the electrolyte were 2F per one mole of perfluorohexyl iodide (150 mA·h). After completing the
electrolysis, the reaction mixture was concentrated on rotary evaporator. The residue was washed
with a saturated ammonium chloride solution (3x50) and extracted with hexafluorobenzene
(3x50). The organic layer was separated, dried over MgSO4 and the solvent was removed. The
brown oily residue showed a major product of Ph2P(C6F13) by 1H NMR and 31P NMR. 1H NMR:
(400 MHz, C6D6)δ= 8.02 (4H, m), 7.78 (2H, m), 7.41 (4H, m) and 31P NMR {1H} (161.94
MHz,C6D6)δ= 2.83 (br.s). The residue was used without further purification.
4.10. Synthesis of diphenyl(-perfluorohexyl)phosphine oxide (8).
The residue after synthesis of compound 6 was transferred into 100 ml round-bottom flask and
treated with an excess of 10% hydrogen peroxide. After 2 hours the mixture was washed with
hexafluorobenzene (3х30 ml), the organic layer was separated, dried over MgSO4and the solvent
was removed. The oily solid residue was washed with cold diethyl either (10 ml) on a frit to give
O=PPh2(C6F13) as a white solid (1.06 g 73% based on diphenylchlorophosphine, 68.7% current
efficiency). The product was purified by column chromatography on silica gel (Et2O:CH2Cl2,
8:2).1H NMR (400 MHz, C6D6) δ= 8.04 (4H, m), 7.78 (2H, m), 7.14 (4H, m).31P{1H} NMR
2
2
(161.94 MHz, C6D6) δ= 23.78 (t JPF = 68.5 Hz) [lit.42 24.58 (t JPF = 71 Hz)].19F NMR (376.5
2
MHz, C6D6): δ = -81.70 (s, CF3), -109.71 (d, JPF = 60.12 Hz, 2F at C1), -122.22 (s, 2F at C2), -
123.88 (s, 2F at C3), -124.54 (s, 2F at C4), -126.70 (s, 2F at C5).EIMS, m/z: 520 [M]+, 501, 201,
69. Anal.calcd. for C18H10F13OP: C, 41.54; H, 1.92; P, 5.96; found: C, 41.05; H, 1. 64; P, 6.13.
Acknowledgements
We thank Russian Foundation for Basic Research (grant N 10-03-00335, 11-03-12152, 11-03-
92662, 12-03-31081) for the support of this work
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