Synthesis of functional phosphates [P(C2F5) 3F2X]- from the phosphorane adduct [P(C 2F5)3F2(dmap)]

Article abstract of DOI:10.1021/ic500857b

Weakly coordinating anions (WCAs) are of great academic as well as industrial interest. To advance the fluoroalkyl phosphate anion [P(C ₂F₅)₃F₃]^-, which is ideally suited for technical applications, f

Full text of DOI:10.1021/ic500857b

Article
pubs.acs.org/IC
Synthesis of Functional Phosphates [P(C2F5)3F2X]− from the
Phosphorane Adduct [P(C2F5)3F2(dmap)]
Julia Bader,† Nikolai Ignat’ev,‡ and Berthold Hoge*,†
†Center for Molecular Materials, Anorganische Chemie II, Universitat Bielefeld, Universitatsstraße 25, D-33615 Bielefeld, Germany
̈
̈
‡PM-ABE, Merck KGaA, Frankfurter Strasse 250, D-64293 Darmstadt, Germany
S
* Supporting Information
ABSTRACT: Weakly coordinating anions (WCAs) are of great academic as well as industrial interest. To advance the fluoroalkyl
phosphate anion [P(C2F5)3F3]−, which is ideally suited for technical applications, functional substituents X are attached to the Lewis acid
(C2F5)3PF2. In keeping with this, the reaction of (C2F5)3PF2 with 4-(dimethylamino)pyridine (DMAP) yields the corresponding adduct
[P(C2F5)3F2(dmap)]. Treatment of this adduct with Brønsted acids (HX) leads to the selective formation of the corresponding
phosphate anions [P(C2F5)3F2X]− by trapping the proton with the liberated base DMAP. In this way, OH functions can be transformed
in one step into WCAs, slightly increasing the coordination properties of the corresponding anion. An ion exchange to the corresponding
[PPh4] salts results in solids, whereas the corresponding imidazolium salts are obtained as room-temperature ionic liquids.
A modification of the FAP anion could be achieved by the
addition of functional substituents X to the phosphorane moiety
(C2F5)3PF2. It is conceivable that the chemical properties of the
resulting weakly coordinating anions can be controlled by the
nature of X and ideally tuned to a desired application.
The selective synthesis of such functionalized phosphates
proved to be quite difficult and strongly depends on the chosen
reaction conditions. Thus, the preparation of difluorohydroxotris-
(pentafluoroethyl)phosphate, [P(C2F5)3F2OH]−, by the direct
reaction of (C2F5)3PF2 with an aqueous solution of a hydroxide
salt, requires the strict adherance to several conditions like
temperature, concentration and solvent.12 Our previous inves-
tigations have shown that a direct synthesis of an alkoxyphosphate
[P(C2F5)3F2OR]− (R = alkyl, aryl) is not possible, either, by the
reaction of (C2F5)3PF2 with ethanol nor by the reaction with alkali
metal alcoholates.
INTRODUCTION
■
Weakly coordinating anions1 are required for the application in
ionic liquids, as lithium ion or proton conducting materials, and
for the stabilization of reactive or unstable cations. Thereby,
[PF6]− is one of the most commonly used anions. It is employed as
Li[PF6] in electrolytes for lithium ion batteries2 as well as in
combination with organic cations like imidazolium derivatives as
ionic liquid.3,4 Disadvantageously, the PF bond is sensitive toward
hydrolysis. The coordination of a proton to a fluorine atom
weakens the PF bond, facilitating elimination of HF and the
subsequent reaction of PF5 with water.5,6 To circumvent this
obstacle, perfluoroalkyl substituents are introduced to the phosphate
anion to enhance the stability toward hydrolysis. Fluoroperfluor-
oalkyl phosphate derivatives have been known for about 40 years.7
The technical product (C2F5)3PF2, which is produced by
means of electrochemical fluorination of trialkylphosphanes,8
reacts with LiF to the corresponding salt Li[P(C2F5)3F3] (LiFAP)
(FAP = fluoroalkyl phosphate). LiFAP is hydrolytically much
more stable than Li[PF6] and exhibits an electrochemical stability
up to 5 V versus Li/Li+.9 Additionally, the FAP anion is ideally
suited for the application in ionic liquids. For this purpose,
(C2F5)3PF2 is converted selectively in an aqueous HF solution to
the corresponding phosphoric acid [H(OH2)n][P(C2F5)3F3],10
which serves as a starting material for the synthesis of a broad
variety of ionic liquids. Salts with imidazolium derivatives as
cations, for example, are hydrophobic. The water uptake is up to
10 times lower than that of comparable hexafluorophosphates, and
also the viscosity is significantly reduced.11
Received: April 11, 2014
© XXXX American Chemical Society
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Scheme 1. Synthetic Strategy for Functionalized Difluorotris(pentafluoroethyl)phosphates [P(C2F5)3F2X]−
Scheme 2. Synthesis of [P(C2F5)3F2(dmap)]
which occurs in the meridional form I/III as well as in the facial
form II (cf. Figure 1).10
Therefore, the development of a new protocol that enables a
selective synthesis of [P(C2F5)3F2X]− derivatives is highly
desirable. One possible synthetic strategy is based on adducts of
the phosphorane (C2F5)3PF2 with basic molecules. Subse-
quently, the base could abstract the proton from Brønsted acids
(HX), affording the selective formation of functionalized
derivatives [P(C2F5)3F2X]− (see Scheme 1).
Muetterties et al. described adducts of pentafluorophosphor-
ane with ethers, sulfoxides, and amines,13 and Sheldrick
succeeded in 1973 in the first structural characterization of a
pyridine adduct. The solid-state structure of [PF5(py)] exhibits
an octahedrally coordinated phosphorus atom.14
The 19F NMR spectrum of [P(C2F5)3F2(dmap)] reveals only
one resonance for the fluorine atoms FA bound directly to the
phosphorus atom, which agrees with the meridional conformer
I as well as the facial conformer II. The chemical shift of the
fluorine atoms FA at δ(19F) = −99.4 supports a trans config-
uration of the fluorine atoms and therefore isomer I, which is
also present in the solid state.
[P(C2F5)3F2(dmap)] crystallizes in the monoclinic space
group P21/c with four formula units per unit cell.16 The
asymmetric unit is represented by one [P(C2F5)3F2(dmap)]
unit. The plane of the pyridine ring is nearly parallel with the
F1−P1−F2 vector. In contrast, the plane of the pyridine ring in
[PF5(py)] is rotated by about 45° with respect to comparable
F−P−F vectors, which was explained by intermolecular F−H
contacts.14 The length of the coordinative N−P bond is, at
190.9 pm, comparable to that observed for [PF5(py)] (189.8 pm)
and is significantly shorter than the sum of the van der Waals radii
of 350 pm.17 The bond lengths and angles of the DMAP
substituent match those of free DMAP (cf. Figure 2).
RESULTS AND DISCUSSION
■
In analogy to PF5, which forms a solid pyridine adduct
(mp 179−182 °C),13 the reaction of (C2F5)3PF2 with 4-(dimethyl-
amino)pyridine (DMAP) in diethyl ether selectively leads to
the adduct [P(C2F5)3F2(dmap)] (cf. Scheme 2) as a colorless
solid in a yield of 97%.15 The product can be handled in air for
a short time and melts at 150−153 °C.
The addition of a nucleophile X− to (C2F5)3PF2 generally
may yield three different stereoisomers [P(C2F5)3F2X]−. Two
isomers are distinguishable by NMR spectroscopy (cf. Figure 1).
Figure 1. Possible stereoisomers for [P(C2F5)3F2X]− derivatives.
Figure 2. Molecular structure and numbering scheme of [P-
(C2F5)3F2(dmap)] in the solid state. H atoms are omitted for clarity.
50% probability amplitude displacement ellipsoids are shown. Selected
bond lengths [pm] and angles [deg]: P1−F1 162.3(1), P1−F2
162.5(1), P1−N1 190.9(1), P1−C1 197.5(2), P1−C3 198.1(2), P1−
C5 197.2(2); F1−P1−F2 179.5(1), C1−P1−C5 171.1(1).
Form III exhibits two chemically inequivalent fluorine atoms FA
and FB, whereas in isomers I and II both phosphorus-bound
fluorine atoms are equivalent.
Isomers I and II, where the pentafluoroethyl groups are
oriented meridionally (I) and facially (II), cannot be
discriminated that easily. The chemical shift of the fluorine
atoms FA in the 19F NMR spectrum, however, provides
important structural information. The fluorine atoms FA in I
display chemical shifts in the range of δ(19F) = −80 to −110,
whereas the resonances for the chemically equivalent fluorine
atoms FA in conformer II are usually observed at a significantly
lower field. A known example for this argument is [P(C2F5)3F3]−,
(C4F9)3PF2 reacts with DMAP in diethyl ether to give the
desired adduct [P(C4F9)3F2(dmap)]. Our attempt to isolate the
adduct simply by removing the solvent in vacuum was not
successful. The compound [P(C4F9)3F2(dmap)] decomposes
and trifluorotris(nonafluorobutyl)phosphate, [P(C4F9)3F3]−, is
formed among other side products.
B
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(C2F5)2PF3 reacts with DMAP, but [P(C2F5)2F4]− is formed
as a side product. The desired product [P(C2F5)2F3(dmap)]
could be detected by NMR spectroscopic methods with a
conversion of 40%. The resonance of [P(C2F5)2F3(dmap)] in
the 31P NMR spectrum is detected in the expected range and
exhibits a JP,FA coupling constant of 940 Hz as well as a JP,FB
coupling constant of 996 Hz. The coupling to the fluorine
atoms of the CF2 units results in a quintet. For the fluorine
atoms of the pentafluoroethyl groups, in the CF3 range as well
as in the CF2 range, only one resonance is detected in the 19F
NMR spectrum. On the basis of the chemical equivalence of
the pentafluoroethyl groups, it is not possible to distinguish
between the two structures depicted in Figure 3 by NMR
spectroscopy.
the phosphorus atom (FA), only one resonance appears in the
19F NMR spectrum. Because of the chemical shift of δ(19F) =
−86.6, a meridional configuration with regard to the
pentafluoroethyl groups is postulated. This structure could be
proven by a single-crystal structure analysis.
1
1
The compound crystallizes in the triclinic space group
P1 with two formula units per unit cell (cf. Figure 4).16 One
̅
Figure 4. Molecular structure and numbering scheme of the
[P(C2F5)3F2OH]− ion as its [PPh4]+ salt. 50% probability amplitude
displacement ellipsoids are shown. Selected bond lengths [pm] and
angles [deg]: P1−F1 163.0(2), P1−F2 162.9(2), P1−O1 164.7(3),
P1−C1 195.9(4), P1−C3 197.8(4); F1−P1−F2 176.4(1), O1−P1−
C5 175.1(2).
Figure 3. Possible isomers of [P(C2F5)2F3(dmap)].
The chemical shift of the fluorine atoms FB in the 19F NMR
spectrum at δ = −83.1 is in favor of a trans conformation and
therefore supports isomer I.
The adduct [P(C2F5)3F2(dmap)] was synthesized as a
precursor for various [P(C2F5)3F2X]− derivatives via the
reaction with Brønsted acids HX.15
[PPh4][P(C2F5)3F2OH] unit represents the asymmetric unit.
The general molecular structure of the anion resembles that of
[P(C2F5)3F2(dmap)]. The proton of the hydroxy function
(H1) is directed at a fluorine atom of the difluoromethylene
unit of a neighboring anion. The H1−O1−P1−F2 dihedral
angle of 22.4° is a consequence of weak intermolecular contact.
Quantum chemical calculations at the B3LYP/6-311G+(2d,p)18
level of theory favor a Cs symmetrical conformation and therefore
a H1−O1−P1−F2 dihedral angle of 0°. In general, the structural
parameters are described well by quantum chemical calculations.
The P−O distance of 164.7 pm represents a classical single
bond.19
An acetato ligand is introduced by the reaction of [P(C2F5)3F2-
(dmap)] with acetic acid (HOAc) or acetic anhydride. In the case
of acetic acid, the product [HDMAP][P(C2F5)3F2OAc] is isolated
as a colorless solid in a yield of 93% and fully characterized
by multinuclear NMR spectroscopy. The reaction with acetic
anhydride, yielding [P(C2F5)3F2OAc]− and concluding the
formation of the amide [AcDMAP]+, shows that the acidic
hydrogen atom in HX is not necessarily required for this reaction.
To generate the hydroxophosphate ion [P(C2F5)3F2OH]−,
[P(C2F5)3F2(dmap)] is dissolved in diethyl ether and treated
with an excess of water. NMR monitoring discloses the
selective formation of [HDMAP][P(C2F5)3F2OH]. Attempts
to isolate the salt by removing the solvent in vacuum were not
successful.
After a cation exchange with [PPh4]Cl and the subsequent
aqueous workup, the hydroxophosphate salt [PPh4]-
[P(C2F5)3F2OH] was isolated as a colorless solid (mp 139 °C)
in 94% yield.
The 1JP,F coupling constant decreases significantly going from
[P(C2F5)3F2(dmap)] to [P(C2F5)3F2OH]− from J = 986 to 846
1
Hz. In the H NMR spectrum, the OH proton gives rise to a
The precursor [P(C2F5)3F2(dmap)] is reacted with phenol,
yielding the corresponding phenolatophosphate [HDMAP]-
[P(C2F5)3F2OPh] as a room-temperature ionic liquid.
signal at 5.1 ppm; in deuterated tetrahydrofuran (THF-d8),
acetone-d6, and CDCl3, only a triplet splitting due to a JH,F
3
coupling of J = 14 Hz is observed. In CD3CN, however, an
additional doublet splitting due to the 2JH,P coupling of J = 3 Hz
is detected, which is supported by the phosphorus decoupled
1H NMR experiment. For the fluorine atoms bonded directly to
The treatment of [P(C2F5)3F2(dmap)] with 0.5 equivalents
of hydroquinone in diethyl ether furnishes [HDMAP]2[{P-
(C2F5)3F2O}2C6H4] as a colorless solid. Results of an elemental
analysis as well as an electrospray ionization (ESI) mass
C
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spectrum (negative scan mode) confirm the formation of the
doubly charged diphosphate anion [{P(C2F5)3F2O}2C6H4]2−.
Figure 5. Molecular structure and numbering scheme of [HDMAP]-
[P(C2F5)3F2OEt)]. All carbon bonded hydrogen atoms are omitted for
clarity. 50% probability amplitude displacement ellipsoids are shown.
Selected bond lengths [pm] and angles [deg]: P1−F1 164.2(2), P1−
F2 162.9(2), P1−O1 166.2(2), P1−C1 195.7(3), P1−C3 198.4(3);
F1−P1−F2 175.8(1), F1−P1−C3 83.7(1), O1−P1−C3 169.8(1).
For [HDMAP][P(C2F5)3F2OPh] as well as for [HDMAP]2-
[{P(C2F5)3F2O}2C6H4], only one resonance is detected spectros-
copically by NMR for the fluorine atoms directly bound to the
phosphorus atom. The chemical shift of around δ(19F) = −86
favors a meridional configuration with regard to the pentafluor-
oethyl groups, which is confirmed for some [P(C2F5)3F2X]
derivatives (X = OH, DMAP, OEt) by single-crystal structure
analyses.
Our knowledge of alkoxypentafluorophosphates is scarce.
Riesel and Kant reported in 1985 the synthesis of
ethoxypentafluorophosphate [PF5OEt]−, which was obtained
by the reaction of PCl5 with HF and ethanol in the presence of
triethylamine.20
trifluoroethanol. The product [HDMAP][P(C2F5)3F2OCH2CF3]
was isolated in a yield of 95% after removing the solvent in
vacuum (mp 91−93 °C).
The ligation of the trifluoroethoxy group to the (C2F5)3PF2
3
moiety is evident by the observation of a JP,H coupling of
1
J = 4 Hz in the H NMR spectrum.
The reaction of [P(C2F5)3F2(dmap)] with ethanol in diethyl
ether selectively leads to the corresponding ethoxyphosphate
[HDMAP][P(C2F5)3F2OEt]. The product is isolated in a 100%
yield as a colorless solid by removing the solvent in vacuum
(mp 75−78 °C).
After a cation exchange of both [HDMAP][P(C2F5)3F2OEt]
and [HDMAP][P(C2F5)3F2OCH2CF3] by means of 1-butyl-
2,3-dimethylimidazolium chloride ([BMMIm]Cl), the pro-
ducts [BMMIm][P(C2F5)3F2OEt] and [BMMIm][P(C2F5)3-
F2OCH2CF3] were obtained in yields of 87−91% as ionic
liquids with melting points below room temperature. Their
properties were investigated by differential scanning calorimetry
(DSC) analysis. Both compounds exhibit a glass transition at
about −57 °C. The decomposition points differ significantly.
While the ethoxy derivative decomposes already at 120 °C,
[BMMIm][P(C2F5)3F2OCH2CF3] is stable up to 212 °C.
To synthesize a difluorotris(pentafluoroethyl)phosphate with
an additional functional group, [P(C2F5)3F2(dmap)] was
dissolved in diethyl ether and treated with an excess of 1,2-
ethanediol. In parallel to the desired formation of [HDMAP]-
[P(C2F5)3F2OC2H4OH], a ring closure under liberation of
C2F5H could not be excluded a priori. Under the chosen
reaction conditions, this side reaction could not be observed.
The product [HDMAP][P(C2F5)3F2OC2H4OH] was obtained
in a 89% yield as a colorless solid. It decomposes at 91 °C.
By NMR spectroscopy, only one resonance at δ(19F) =
−94.5 is detected for the fluorine atoms FA bound directly to
the phosphorus atom. This is in accordance with a trans
orientation of the fluorine atoms at the phosphorus atom.
The product crystallizes in the monoclinic space group P21/n
with four formula units per unit cell.16 The proton H1 at the
nitrogen atom of the pyridine ring is aligned with the oxygen
atom O1 of the ethoxy group (cf. Figure 5) with an O−N
distance of 312.9 pm, which is consistent with the sum of the
van der Waals radii of 310 pm.17 This shows that the
introduction of an oxygen-bound functional group increases the
coordination properties of the anion. The C5−P−F1 angle of
83.7° is significantly compressed by a strong interaction of the
fluorine atom F1 with the electron lone pairs of the oxygen
atom.
Summary of NMR Spectroscopic Data. The chemical
shift of [P(C2F5)3F2X]− derivatives in the 31P NMR spectrum
ranges from δ(31P) = −145 to −155 with a characteristic
coupling pattern. The signal is split into a triplet due to the 1JP,F
coupling to the fluorine atoms directly bound to the
phosphorus atom. Thereby coupling constants range from
846 Hz for [P(C2F5)3F2OH]− to 986 Hz for [P(C2F5)3-
F2(dmap)]. An additional quintet-of-triplets splitting results
To investigate the influence of electron-withdrawing
substituents on the physical properties of the corresponding
phosphate anion, [P(C2F5)3F2(dmap)] was treated with
2
from the JP,F coupling to the fluorine atoms of the CF2 units,
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throughout all preparative procedures. Nonvolatile compounds were
handled in a dry N2 atmosphere using Schlenk techniques.
NMR spectra were recorded at room temperature with a Bruker
Avance II 300 spectrometer (1H: 300.13 MHz; 13C: 75.47 MHz; 19F:
282.40 MHz; 31P: 111.92 MHz) with positive shifts being downfield
from the external standards [85% orthophosphoric acid (31P), CCl3F
(19F), and tetramethylsilane (1H, 13C)].
which are in cis and trans positions relative to the functional
substituent X.
The 19F NMR spectra of difluorotris(pentafluoroethyl)-
phosphate derivatives can be divided generally into three
regions (cf. Table 1). (A) Both resonances of the cis- and trans-
Melting points were determined by using an HWS Mainz 2000
apparatus. C, H, and N analyses were carried out with a HEKAtech
Euro EA 3000 apparatus. Electron ionization (EI) (20 eV) and ESI
mass spectra were recorded with a Finnigan MAT 900 S spectrometer.
The moisture content of ionic liquids was measured by a Karl
Fischer titration (831 KF-Coulometer, Metrohm), and the content of
chloride and fluoride ions was measured by ion chromatography (830
Metrohm). The thermal stability (DSC) of ionic liquids was measured
using a Netzsch DSC 204.
Table 1. Selected NMR Spectroscopic Data for
[P(C2F5)3F2X] Derivatives with Increasing Coupling
1
Constant J(PFA)
Data collection for X-ray structure determination of [P(C2F5)3-
F2(dmap)], [PPh4][P(C2F5)3F2OH], and [HDMAP][P(C2F5)3-
F2OEt] was performed on a STOE IPDS II diffractometer using
graphite-monochromated Mo Kα radiation (71.073 pm). The data
were corrected for Lorentz and polarization effects. A numerical
absorption correction based on crystal-shape optimization was applied
for all data (X-Shape 2.01, Crystal Optimisation for Numerical
Absorption Correction, STOE & Cie GmbH, Darmstadt, 2001). The
programs used herein are Stoe’s X-Area (X-Area 1.16, STOE & Cie
GmbH Darmstadt, 2003), including X-RED and X-Shape for data
reduction and numerical absorption correction (X-RED32 1.03, Stoe
Data Reduction Program, Stoe & Cie GmbH, Darmstadt, 2002), and
X-Step32 program (X-STEP32 1.06f, Stoe & Cie GmbH, Darmstadt,
2000), including SHELXS-97 (G. M. Sheldrick, SHELXS-97,
positioned CF3 units are detected around −80 ppm and
assigned to the respective C2F5 groups on the basis of their
integrals of 2:1. (B) The signals of the CF2 units are observed
in a range from −110 to −125 ppm and assigned on the basis
University of Gottingen, 1998) and SHELXL-97 (G. M. Sheldrick,
̈
2
of their integrals as well as their JP,F coupling constants.
SHELXL-97, University of Gottingen, 1997) for structure solution and
̈
However, on the basis of the chemical shift or the coupling
pattern alone, no statement can be made about the respective
substituent X. (C) Characteristic of the substituent X is the
chemical shift of the fluorine atoms bound directly to the
refinement. All hydrogen atoms were placed in idealized positions
using a riding model. The last refinement cycles included atomic positions
for all atoms, anisotropic thermal parameters for all non-hydrogen atoms,
and isotropic thermal parameters for all hydrogen atoms.
1
Synthesis of [P(C2F5)3F2(dmap)]. (C2F5)3PF2 (12.2 g, 28.6 mmol)
was added slowly to a suspension of 4-dimethylaminopyridine (2.8 g,
22.9 mmol) in diethyl ether (100 mL). After stirring for 15 min, all
volatile compounds were removed in vacuo. A colorless solid remained
phosphorus atom as well as the corresponding JP,F coupling
constant. Trans positioned fluorine atoms exhibit a chemical
shift in a range of −80 to −100 ppm for the discussed neutral
and negatively charged [P(C2F5)3F2X] derivatives.
1
(12.1 g, 97%), mp 150−153 °C. H NMR (300.1 MHz, CDCl3): δ =
3
3.2 (s, 6H, CH3), 6.7 (d, JH,H = 7 Hz, 1H), 8.4 (m, 1H) ppm;
CONCLUSIONS
13C{1H} NMR (75.5 MHz, CDCl3): δ = 38.6 (s, CH3), 105.9 (s, C1),
138.9 (s, C2), 156.1 (s, C3) ppm; 13C{19F} NMR (75.5 MHz,
CDCl3): δ = 116.7 (m, CF2), 118.2 (m, CF3) ppm; 19F NMR (282.4
MHz, CDCl3): δ = −80.4 (m, trans-CF3), −81.6 (m, cis-CF3), −99.4
(d, 1JP,F = 986 Hz, PF2), −111.5 (m, cis-CF2), −115.3 (d, m, 2JP,F = 95
Hz, trans-CF2) ppm; 31P NMR (111.9 MHz, CDCl3): δ = −144.5 (t,
■
To develop the chemistry of weakly coordinating anions
derived from [P(C2F5)3F3]−, which is ideally suited for an
application as ionic liquid, functional substituents X (X = OH,
OAlkyl, OAryl, OAcyl) were attached to the phosphorane
moiety (C2F5)3PF2. The reaction of the Lewis acid (C2F5)3PF2
with DMAP quantitatively afforded the corresponding adduct
[P(C2F5)3F2(dmap)]. This adduct offers an access to the
corresponding phosphate anions [P(C2F5)3F2X]− when treated
with Brønsted acids (HX). The proton was trapped by the
liberated base DMAP. This allows the one-step introduction of
a OH substitution into WCAs. Bifunctional diols can be
substituted selectively once or twice, depending on the
stoichiometry employed. The corresponding [PPh4] salts are
isolated as solids, whereas the corresponding imidazolium salts
were obtained as room-temperature ionic liquids. [P(C2F5)3F2X]−
derivatives with partially fluorinated substituents exhibit an
increased thermal stability with regard to their nonfluorinated
counterparts.
1
2
2
quin, t, JP,F = 986 Hz, JP,Fcis = 107 Hz, JP,Ftrans = 97 Hz) ppm.
Elemental analysis (%) calcd: N 5.11, C 28.48, H 1.84; found: N 4.91,
C 28.63, H 1.67. Mass spectrum (EI, 20 eV) {m/z (%) [assignment]}:
407 (12) [M].+, 307 (50) [M-C2F5]+, 207 (15) [M-2 C2F5]+, 122
(100) [C7H10N2]+, 69 (6) [CF3]+.
Synthesis of [PPh4][P(C2F5)3F2OH]. [P(C2F5)3F2(dmap)] (0.96 g,
1.75 mmol) was dissolved in diethyl ether and treated with an excess of
water. After stirring for 30 min, [PPh4]Cl (0.66 g, 1.75 mmol), dissolved
in water (2 mL), was added and stirred for 20 min. The organic phase
was separated and extracted three times with water. The organic phase
was freed from solvent in vacuo. A colorless solid remained (1.29 g,
94%), mp 139 °C. 1H NMR (300.1 MHz, CD3CN): δ = 5.1 (t, d, 3JF,H
=
2
14 Hz, JP,H = 3 Hz, 1 H, POH), 7.8−8.1 (m, 20 H, CHarom.) ppm;
13C{1H} NMR (75.5 MHz, CD3CN): δ = 118.5 (d, 1JP,C = 90 Hz, C1),
2
3
130.3 (d, JP,C = 13 Hz, C2), 134.7 (d, JP,C = 10 Hz, C3), 135.4 (d,
4JP,C = 3 Hz, C4) ppm; 13C{19F} NMR (75.5 MHz, CD3CN): δ = 119.1
(m, CF2), 120.7 (m, CF3) ppm; 19F NMR (282.4 MHz, CD3CN): δ =
EXPERIMENTAL SECTION
■
1
(C2F5)3PF2 and (C4F9)3PF2 were provided by the Merck KGaA
company, Darmstadt, Germany. (C2F5)2PF3 was prepared according to
the protocol described in the patent application.21 All other chemicals
were obtained from commercial sources and used without further
purification. Standard high-vacuum techniques were employed
−80.1 (m, trans-CF3), −81.2 (m, cis-CF3), −86.6 (d, JP,F = 846 Hz,
2
PF2), −114.1 (d, JP,F = 86 Hz, CF2) ppm; 31P NMR (111.9 MHz,
1
CD3CN): δ = 23.2 (s, [PPh4]+), −148.3 (t, sept, J(PF) = 845 Hz,
2JP,F = 86 Hz) ppm. Elemental analysis (%) calcd: C 46.05, H
2.71; found: C 46.40, H 2.79. ESI mass spectrum in the negative
E
dx.doi.org/10.1021/ic500857b | Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
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range (neg.) {m/z (%) [assignment]}: 443.2 (100) [M]−, 323.2 (41)
[P(C2F5)2F2O]−.
(2.8 g, 95%), mp 91−93 °C. 1H NMR (300.1 MHz, CD3CN): δ = 3.2
(s, 6 H, CH3), 4.4 (quar, d, 3JF,H = 9 Hz, 3JP,H = 4 Hz, 2 H, OCH2CF3),
3
3
Synthesis of [HDMAP][P(C2F5)3F2OAc]. A sample of [P(C2F5)3-
F2(dmap)] (0.52 g, 0.96 mmol) was treated in dichloromethane with
acetic acid (HOAc; 0.19 g, 3.17 mmol) and stirred at room
temperature for 3 h. After removing volatile compounds in vacuo, a
colorless solid remained (0.54 g, 93%). 1H NMR (300.1 MHz,
CD3CN): δ = 1.9 (s, 3 H, OC(O)CH3), 3.2 (s, 6 H, N(CH3)2), 6.9 (d,
3JH,H = 7 Hz, 1 H, H1), 7.9 (d, 3JH,H = 7 Hz, 1 H, H2) ppm; 13C{1H}
NMR (75.5 MHz, CD3CN): δ = 23.3 (s, OC(O)CH3), 39.6 (s,
6.8 (d, JH,H = 7 Hz, 2 H, H1), 8.0 (d, JH,H = 7 Hz, 2 H, H2) ppm;
13C{1H} NMR (75.5 MHz, CD3CN): δ = 39.6 (s, N(CH3)2), 64.1 (m,
OCH2CF3), 106.9 (s, C1), 138.9 (s, C2), 157.7 (s, C3) ppm; 13C{19F}
NMR (75.5 MHz, CD3CN): δ = 118.8 (m, CF2), 120.4 (m, CF3),
124.5 (m, OCH2CF3) ppm; 19F NMR (282.4 MHz, CD3CN): δ =
−75.4 (s, OCH2CF3), −79.6 (m, trans-CF3), −80.8 (m, cis-CF3),
−93.8 (d, m, JP,F = 883 Hz, PF2), −112.2 (d, m, JP,F = 88 Hz, CF2)
ppm; 31P NMR (111.9 MHz, CD3CN): δ = −149.9 (t, sept, 1JP,F = 886
Hz, 2JP,F = 88 Hz) ppm. Elemental analysis (%) calcd: N 4.32, C 27.79,
H 2.02; found: N 4.47, C 28.10, H 1.64. ESI mass spectrum in the
negative range (neg.) {m/z (%) [assignment]}: 1088.9 (13) [KM2]−,
525.2 (100) [M]−.
1
2
N(CH3)2), 107.1 (s, C1), 138.6 (s, C2), 157.7 (s, C3), 166.3 (d, 2JP,C
=
18 Hz, OC(O)CH3) ppm; 13C{19F} NMR (75.5 MHz, CD3CN): δ =
116.7 (m, CF2), 120.0 (m, CF3) ppm; 19F NMR (282.4 MHz,
CD3CN): δ = −80.2 (m, trans-CF3), −81.8 (m, cis-CF3), −86.9 (d, m,
2
1JP,F = 923 Hz, PF2), −115.3 (d, m, JP,F = 85 Hz, trans-CF2), −116.0
Synthesis of [BMMIm][P(C2F5)3F2OEt]. [HDMAP][P(C2F5)3F2OEt]
(5.3 g, 9 mmol) was dissolved in dichloromethane (50 mL) and
treated with 1-butyl-2,3-dimethylimidazolium chloride (1.7 g, 9 mmol)
dissolved in dichloromethane (5 mL). After stirring for 2 h, the organic
phase was separated and extracted three times with water. Volatile
compounds of the organic phase were removed in vacuo. A colorless
liquid remained (4.9 g, 87%). 1H NMR (300.1 MHz, CD3CN): δ = 0.9
(d, m, 2JP,F = 103 Hz, cis-CF2) ppm; 31P NMR (111.9 MHz, CD3CN):
1
2
2
δ = −146.3 (t, quin, t, JP,F = 915 Hz, JP,Fcis = 103 Hz, JP,Ftrans
=
84 Hz) ppm.
Synthesis of [HDMAP][P(C2F5)3F2OPh]. [P(C2F5)3F2(dmap)]
(0.52 g, 0.95 mmol) was dissolved in diethyl ether and treated with
phenol (0.13 g, 1.34 mmol). After stirring for 12 h, two phases had
formed. The solvent was removed in vacuo, and a colorless liquid
remained. 1H NMR (300.1 MHz, CD3CN): δ = 3.4 (s, 6 H, CH3), 6.7
(d, 3JH,H = 7 Hz, 2 H, H1), 7.1 (m, 5H, OC6H5), 8.3 (d, 3JH,H = 7 Hz, 2
H, H2) ppm; 13C{1H} NMR (75.5 MHz, CD3CN): δ = 39.7 (s, CH3),
106.9 (s, C1), 115.2 (s, C5), 120.4 (s, C6/7), 128.9 (s, C6/7), 138.8
(s, C2), 157.0 (s, C4), 157.6 (s, C3) ppm; 13C{19F} NMR (75.5 MHz,
CD3CN): δ = 118.1 (m, CF2), 119.7 (m, CF3) ppm; 19F NMR (282.4
MHz, CD3CN): δ = −79.4 (m, trans-CF3), −80.5 (m, cis-CF3), −85.5
3
3
(t, JH,H = 7 Hz, 3 H, H9/13), 1.0 (t, JH,H = 7 Hz, 3 H, H13/9), 1.3
(sext, 3JH,H = 8 Hz, 2 H, H8), 1.7 (quin, 3JH,H = 7 Hz, 2 H, H7), 2.5 (s,
3 H, H11), 3.7 (s, 3 H, H10), 3.9 (m, 4 H, H6/H12), 7.2 (m, 2 H,
H4/H5) ppm; 13C{1H} NMR (75.5 MHz, CD3CN): δ = 9.0 (s, C11),
12.7 (s, C9), 16.0 (s, C13), 19.1 (s, C8), 31.2 (s, C7), 34.7 (s, C10),
48.0 (s, C6), 61.8 (s, C12), 120.8 (s, C4/5), 122.2 (s, C5/4), 144.3 (s,
C2) ppm; 19F NMR (282.4 MHz, CD3CN): δ = −80.1 (m, trans-CF3),
1
1
2
−81.3 (m, cis-CF3), −93.9 (d, m, JP,F = 870 Hz, PF2), −113.3 (d, m,
(d, m, JP,F = 896 Hz, PF2), −111.5 (d, m, JP,F = 97 Hz, cis-CF2),
2
2JP,F = 84 Hz, trans-CF2), −116.9 (d, m, JP,F = 86 Hz, cis-CF2) ppm;
−112.7 (d, m, 2 JP,F = 79 Hz, trans-CF2) ppm; 31P NMR (111.9 MHz,
1
31P NMR (111.9 MHz, CD3CN): δ = −149.5 (t, sept, JP,F = 866 Hz,
1
2
CD3CN): δ = −147.5 (t, quin, t, JP,F = 893 Hz, JP,Fcis = 98 Hz,
2JP,Ftrans = 84 Hz) ppm.
2JP,F = 84 Hz) ppm.
Synthesis of [HDMAP]2[{P(C2F5)3F2O}2C6H4]. [P(C2F5)3F2(dmap)]
(1.11 g, 2.0 mmol) was dissolved in diethyl ether and treated with
hydroquinone (0.11 g, 1.0 mmol). After stirring for 4 h, volatile
compounds were removed in vacuo. A colorless solid remained
(0.85 g, 78%). 1H NMR (300.1 MHz, CD3CN): δ = 3.1 (s, 6 H, CH3),
Synthesis of [BMMIm][P(C2F5)3F2OCH2CF3]. [HDMAP]-
[P(C2F5)3F2OCH2CF3] (4.7 g, 7.3 mmol) was dissolved in dichloro-
methane (50 mL) and treated with 1-butyl-2,3-dimethylimidazolium
chloride (1.4 g, 7.4 mmol) dissolved in dichloromethane (3 mL). After
stirring for 1 h, the organic phase was separated and extracted three
times with water. Volatile compounds of the organic phase were
removed in vacuo. A colorless liquid remained (4.5 g, 91%). 1H NMR
3
3
6.8 (m, 4 H, H4/5), 6.8 (d, JH,H = 8 Hz, 2 H, H2), 7.9 (d, JH,H = 8
Hz, 2 H, H2) ppm; 19F NMR (282.4 MHz, CD3CN): δ = −80.4 (m,
1
3
trans-CF3), −81.6 (m, cis-CF3), −86.9 (d, m, JP,F = 881 Hz, PF2),
(300.1 MHz, CD3CN): δ = 0.9 (t, JH,H = 7 Hz, 3 H, H9), 1.3 (sext,
2
2
3JH,H = 8 Hz, 2 H, H8), 1.7 (quin, 3JH,H = 7 Hz, 2 H, H7), 2.5 (s, 3 H,
−112.9 (d, m, JP,F = 98 Hz, cis-CF2), −113.9 (d, m, JP,F = 80 Hz,
trans-CF2) ppm; 31P NMR (111.9 MHz, CD3CN): δ = −148.0 (t,
quin, t, JP,F = 882 Hz, JP,Fcis = 96 Hz, JP,Ftrans = 78 Hz) ppm.
Elemental analysis (%) calcd: N 4.67, C 32.07, H 1.51; found: N 4.73,
C 32.40, H 2.26.
3
H11), 3.7 (s, 3 H, H10), 4.0 (t, JH,H = 7 Hz, 2 H, H6), 4.4 (m, 2 H,
1
2
2
H12), 7.2 (m, 2 H, H4/H5) ppm; 13C{1H} NMR (75.5 MHz,
CD3CN): δ = 9.0 (s, C11), 12.7 (s, C9), 19.1 (s, C8), 31.2 (s, C7),
34.7 (s, C10), 48.0 (s, C6), 64.2 (m, C12), 120.8 (s, C4/5), 122.3 (s,
C5/4), 124.5 (m, C13), 144.8 (s, C2) ppm; 19F NMR (282.4 MHz,
CD3CN): δ = −75.9 (s, 3F, −OCH2CF3), −80.3 (m, 3F, trans-CF3),
−81.7 (m, 6F, cis-CF3), −94.5 (d, m, 1JP,F = 884 Hz, 2F, PF2), −113.4
(m, 6F, cis-, trans-CF2) ppm; 31P NMR (111.9 MHz, CD3CN): δ =
Synthesis of [HDMAP][P(C2F5)3F2OEt]. Ethanol (10.6 g, 230 mmol),
dissolved in diethyl ether (100 mL), was treated with [P(C2F5)3F2-
(dmap)] (12.5 g, 23 mmol) and stirred for 30 min. Volatile compounds
were removed overnight in vacuo. A colorless solid remained (13.6 g,
1
100%), mp 75−78 °C. H NMR (300.1 MHz, CD3CN): δ = 1.1 (t, d,
1
2
3JH,H = 7 Hz, 4JP,H = 1 Hz, 3 H, OCH2CH3), 3.2 (s, 6 H, CH3), 4.0 (m,
3JP,H = 7 Hz, 3JH,H = 7 Hz, 2 H, OCH2CH3), 5.3 (s, 1 H, NH+), 6.8 (d,
−149.9 (t, sept, JP,F = 885 Hz, JP,F = 85 Hz) ppm.
Synthesis of [HDMAP][P(C2F5)3F2OC2H4OH]. A sample of
[P(C2F5)3F2(dmap)] (0.60 g, 1.1 mmol) was dissolved in diethyl
ether and treated with ethanediol (0.10 g, 1.6 mmol). After stirring for
24 h, volatile compounds were removed in vacuo. A colorless solid
remained (0.61 g, 89%), mp 88 °C (decomposition: 91 °C). 1H NMR
(300.1 MHz, CD3CN): δ = 3.2 (s, 6H, CH3), 3.5 (t, 3JH,H = 4 Hz, 2 H,
3
3JH,H = 7 Hz, 2 H, H1), 8.0 (d, JH,H = 7 Hz, 2 H, H2) ppm; 13C{1H}
NMR (75.5 MHz, CD3CN): δ = 16.0 (d, 3JC,P = 10 Hz, OCH2CH3), 39.6
(s, N(CH3)2), 61.8 (m, OCH2CH3), 107.1 (s, C1), 138.5 (s, C2), 157.0
(s, C4), 157.9 (s, C3) ppm; 13C{19F} NMR (75.5 MHz, CD3CN): δ =
118.8 (m, CF2), 122.5 (m, CF3) ppm; 19F NMR (282.4 MHz, CD3CN):
δ = −80.6 (m, trans-CF3), −81.8 (m, cis-CF3), −94.5 (d, m, 1JP,F = 869
3
3
3
H5), 4.0 (d, t, JP,H = 4 Hz, JH,H = 4 Hz, 2 H, H4), 6.8 (d, JH,H = 8
Hz, 2 H, H1), 8.0 (d, JH,H = 8 Hz, 2 H, H2) ppm; 13C{1H} NMR
(75.5 MHz, CD3CN): δ = 39.6 (s, N(CH3)2), 62.1 (d, JP,C = 9 Hz,
3
Hz, PF2), −113.5 (d, m, 2JP,F = 83 Hz, trans-CF2), −114.4 (d, m, 2 JP,F
=
2
86 Hz, cis-CF2) ppm; 31P NMR (111.9 MHz, CD3CN): δ = −149.4 (t,
sept, 1JP,F = 869 Hz, 2JP,F = 88 Hz) ppm. Elemental analysis (%) calcd: N
4.71, C 30.32, H 2.71; found: N 4.74, C 30.32, H 2.69. ESI mass spectrum
in the negative range (neg.) {m/z (%) [assignment]}: 965.0 (9)
[NaM2]−, 471.2 (100) [M]−, 445.1 (21) [P(C2F5)3F3]−.
C4), 67.8 (s, C5), 106.8 (s, C1), 138.6 (s, C2), 157.6 (s, C3) ppm;
13C{19F} NMR (75.5 MHz, CD3CN): δ = 116.7 (m, CF2), 120.6 (m,
CF3), 124.5 (m, OCH2CF3) ppm; 19F NMR (282.4 MHz, CD3CN):
δ = −79.3 (m, trans-CF3), −80.4 (m, cis-CF3), −93.2 (d, m, 1JP,F = 873
1
Hz, PF2), −112.6 (d, m, JP,F = 83 Hz, CF2) ppm; 31P NMR (111.9
Synthesis of [HDMAP][P(C2F5)3F2OCH2CF3]. [P(C2F5)3-
F2(dmap)] (2.5 g, 4.5 mmol) was dissolved in diethyl ether and
treated with trifluoroethanol (0.9 g, 9.0 mmol). After stirring for 12 h,
volatile compounds were removed in vacuo. A colorless solid remained
1
2
MHz, CD3CN): δ = −149.2 (t, sept, JP,F = 871 Hz, JP,F = 86 Hz)
ppm. Elemental analysis (%) calcd: N 4.59, C 29.52, H 2.64; found: N
4.62, C 29.54, H 2.28.
F
dx.doi.org/10.1021/ic500857b | Inorg. Chem. XXXX, XXX, XXX−XXX

Inorganic Chemistry
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F(000) = 784; 16951 reflections up to θ = 27.4° collected, 6886
independent reflections, thereof 4005 with I > 2σ(I), 453 parameters.
R values: R1 = 0.061 for refl. with I > 2σ(I), wR2 = 0.189 for all data.
Data for [HDMAP][P(C2F5)3F2OEt]: colorless crystal, Mr = 594.27,
monoclinic, space group P21/n, a = 7.945(1) Å, b = 15.662(2) Å, c =
17.246(3) Å, β = 95.19(1)°, V = 2137.2(6) Å3, Z = 4, F(000) = 1184;
19 082 reflections up to θ = 27.0° collected, 4653 independent
reflections, thereof 2458 with I > 2σ(I), 332 parameters. R values: R1 =
0.036 for refl. with I > 2σ(I), wR2 = 0.073 for all data. Additional
crystallographic data are available in the Supporting Information.
(17) Holleman, A. F.; Wiberg, E. Lehrbuch der Anorganischen Chemie;
Walter de Gruyter: Berlin, Germany, 1995, 101. Aufl., 1838 ff.
(18) Gaussian 03, Revision C.02; Gaussian, Inc.: Wallingford, CT,
2004. Complete citation is given in Supporting Information.
(19) Corbridge, D. E. C. PhosphorusAn Outline of Its Chemistry, 5th
ed.; Elsevier: Amsterdam; New York, 1995, pp 54−58.
ASSOCIATED CONTENT
* Supporting Information
■
S
Results of DFT calculations. This material is available free of
charge via the Internet at http://pubs.acs.org. CCDC 971886
([PPh4][P(C2F5)3F2OH]), CCDC 971887 ([P(C2F5)3-
F2(dmap)]), and CCDC 971888 ([HDMAP][P(C2F5)3F2OEt])
contain the supplementary crystallographic data for this paper.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif.
AUTHOR INFORMATION
Corresponding Author
*E-mail: b.hoge@uni-bielefeld.de.
Notes
■
(20) Riesel, L.; Kant, M. Z. Anorg. Allg. Chem. 1985, 530, 207−212.
Riesel, L.; Kant, M. Z. Anorg. Allg. Chem. 1985, 531, 73−81.
(21) Ignatyev, N.; Welz-Biermann, U.; Schmidt, M.; Kucheryna, A.;
Willner, H. WO 2005/049628 A1, Merck Patent GmbH, Darmstadt,
Germany.
The authors declare no competing financial interest.
REFERENCES
■
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U.; Kucheryna, A.; Sartori, P.; Willner, H. WO 03/002579, Merck
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041431 A1, Merck Patent GmbH, Darmstadt, Germany. (b) Bader, J.;
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(16) Data for [P(C2F5)3F2(dmap)]: colorless crystal, Mr = 548.20,
monoclinic, space group P21/c, a = 9.852(1) Å, b = 16.814(1) Å, c =
11.826(1) Å, β = 110.31(1)°, V = 1837.2(3) Å3, Z = 4, F(000) = 1080;
28 196 reflections up to θ = 29.7° collected, 5148 independent
reflections, thereof 4009 with I > 2σ(I), 302 parameters. R values: R1 =
0.037 for refl. with I > 2σ(I), wR2 = 0.103 for all data. Data for
[PPh4][P(C2F5)3F2OH]: colorless crystal, Mr = 782.41, triclinic, space
group P1, a = 10.654(2) Å, b = 12.364(2) Å, c = 13.811(2) Å, α =
̅
63.56(1)°, β = 73.57(1)°, γ = 77.74(1)°, V = 1554.5(5) Å3, Z = 2,
G
dx.doi.org/10.1021/ic500857b | Inorg. Chem. XXXX, XXX, XXX−XXX