Difluorotriorganylphosphoranes for the Synthesis of Fluorophosphonium and Bismuthonium Salts

Article abstract of DOI:10.1002/ejic.201600539

Fluoride ion affinities (FIA), provided by DFT calculations, are exceedingly useful for the design of new Lewis acids with defined reactivities. Herein, we report the synthesis, characterization and reactivity of new difluoro(perfluoroorganyl)phosphoranes, which readily abstract fluoride ions from difluoro(triorganyl)phosphoranes. Highly reactive fluorobismuthonium cations and the [Ph₃Bi(NCCH₃)₂]²⁺cation are accessible through the treatment of difluoro(triorganyl)bismuth(V) compounds with the Lewis acidic phosphoranes discussed here.

Full text of DOI:10.1002/ejic.201600539

DOI: 10.1002/ejic.201600539
Full Paper
Fluorinated Phosphoranes
Difluorotriorganylphosphoranes for the Synthesis of
Fluorophosphonium and Bismuthonium Salts
Sven Solyntjes,[a] Beate Neumann,[a] Hans-Georg Stammler,[a] Nikolai Ignat'ev,[b] and
Berthold Hoge*[a]
Abstract: Fluoride ion affinities (FIA), provided by DFT calcula- fluoro(triorganyl)phosphoranes. Highly reactive fluorobismuth-
tions, are exceedingly useful for the design of new Lewis acids onium cations and the [Ph3Bi(NCCH3)2]2+ cation are accessible
with defined reactivities. Herein, we report the synthesis, char- through the treatment of difluoro(triorganyl)bismuth(V) com-
acterization and reactivity of new difluoro(perfluoroorgan- pounds with the Lewis acidic phosphoranes discussed here.
yl)phosphoranes, which readily abstract fluoride ions from di-
Introduction
phan et al. recently broadened the number of electrophilic
phosphorus(V) cations (EPCs)[15,16] and reported the crystal
structure of the triorganylfluorophosphonium salt [Ph(C6F5)2-
PF][F{Al(C6F5)3}2].[17] Some of these species are effective cata-
lysts in hydrodefluorination,[17] hydrosilylation and hydrodeoxy-
genation processes.[15,18] The remarkable Lewis acidity of these
fluorophosphonium compounds is most certainly caused by the
presence of electron-withdrawing perfluoroorganic substitu-
ents (here C6F5)[17] or cationic imidazolium[19] and pyridinium[20]
groups.
Since Thorpe reported the synthesis of PF5 from PCl5 and
AsF3,[1] a multitude of hexacoordinate Lewis acid/Lewis base
complexes with PF5 have been reported.[2] PF5 possesses a high
fluoride ion affinity[3,4] and forms the stable, weakly coordinat-
ing [PF6]– anion. Weakly coordinating anions (WCAs)[5,6] are use-
ful compounds, in particular for applications in ionic liquids
(ILs),[7] for the stabilization of reactive cations[8] or as conduct-
ing salts in lithium ion batteries (Li[PF6]).[9]
The replacement of fluoride ligands at the phosphorus(V)
centre of PF5 by other groups should affect the Lewis acidity.
Thus, the introduction of three electron-withdrawing penta-
fluoroethyl groups in the equatorial positions of PF5 leads to
difluorotris(pentafluoroethyl)phosphorane, (C2F5)3PF2, an easy
to handle, strong Lewis acid that possesses a high catalytic ac-
tivity in organic reactions.[10,11] DFT calculations and experimen-
tal results point to a higher fluoride ion affinity for (C2F5)3PF2
than for PF5 and a higher stability of the corresponding anion
[(C2F5)3PF3]– towards water in comparison to [PF6]–.[12]
Gabbaï et al. investigated the synergistic effect between in-
tramolecular phosphonium and borane-based Lewis acids. This
motif was also expanded to the heavier antimony(V) homo-
logues. These compounds show an exceptionally high affinity
to fluoride ions, for example, and can be used as sensitive sen-
sors for fluoride ions and other small, nucleophilic anions.[21]
A few years ago, we launched a broad DFT-based program
on the different electron-withdrawing effects of various per-
fluoroaryl groups.[22] With this knowledge, we are able to de-
sign new fluorophosphoranes with well-defined fluoride ac-
ceptor capabilities. For this purpose, the fluoride ion affinity
(FIA), obtained by DFT calculations, was selected as a reliable
indicator for the Lewis acidity.[3,4,6]
On the other hand, the incorporation of electron-releasing
substituents such as n-butyl or isopropyl groups efficiently di-
minishes the fluoride ion affinity of the difluorophosphoranes
R3PF2 (R = nBu, iPr), and these species are fluoride ion do-
nors.[13] The fluorophosphonium salts [RnPF4–n][EFm] (n ≠ 0, E =
Another way to improve the Lewis acidity within the de-
B, m = 4; E = P, As, m = 6) can be formed through the transfer scribed [Ar3PF]+ motif could be the change of the central atom.
of a fluoride ion to a strong fluoride acceptor such as BF3, PF5,
If we examine group 15 of the periodic table and go from the
light element phosphorus to the heavy homologue bismuth,
we observe an expanding atomic radius, an enhanced metallic
character of the element and an increased Lewis acidity of the
corresponding bismuth compounds.[23,24] For example, quan-
tum mechanical calculations of the FIAs of pnictogen penta-
fluorides in the gas phase exhibit an increase of the Lewis acid-
ity in the series: PF5 < AsF5 < BiF5 < SbF5.[25]
or AsF5.[13,14]
In recent years, interest in highly Lewis acidic phosphorus(V)
cationic species has experienced a renaissance. In this area, Ste-
[a] Centrum für Molekulare Materialien, Fakultät für Chemie,
Universität Bielefeld,
Universitätsstraße 25, 33615 Bielefeld, Germany
E-mail: b.hoge@uni-bielefeld.de
https://www.uni-bielefeld.de/chemie/acii/hoge/
[b] Merck KGaA, PM-ATI,
This raises the question: are we able to realize fluorotriaryl-
bismuth(V) species [Ar3BiF]+ by the reactions of Ar3BiF2 and
strong Lewis acids?
Frankfurter Straße 250, 64293 Darmstadt, Germany
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Results and Discussion
The P–F bond lengths in [(C6F5)3PF3]– [160.9(1)–164.3(1) pm] are
slightly longer than those in [PF6]– [159(1) pm, Figure 1].[34]
For the rational design of Lewis acidic difluorophosphoranes,
we first envisaged tetrafluoropyridyl (NC5F4–) and 4-cyanotetra-
fluorophenyl (NC–C6F4–) ligands in addition to the common
pentafluorophenyl (C6F5–) substituent. The steric demands of
such units should furnish bulky phosphoranes and conse-
quently also bulky anions in which the negative charge is delo-
calized. The FIA of a Lewis acid (LA) is generally defined as
the negative reaction enthalpy released upon the binding of
a fluoride ion to form the corresponding fluoroanion [LA–F]–
[Equation (1)].[3,4,26,27]
(1)
Figure 1. Molecular crystal structure of the anion of 1; 50 % probability dis-
placement ellipsoids are shown; selected bond lengths [pm] and angles [°]:
P–F1 164.3(1), P–F2 163.7(1), P–F3 160.9(1), P–C1 189.8(1), P–C7 189.8(1),
P–C13 190.3(1); F1–P–F2 88.4(1), F1–P–F3 178.2(1), F1–P–C1 90.7(1), F1–P–
C13 90.5(1), C1–P–C7 175.4(1).
An increased FIA of the Lewis acid is usually accompanied
by a more pronounced stability of the corresponding fluoride
adduct towards degradation, hydrolysis or fluoride ion release.
The chosen difluorotris(perfluoroaryl)phosphoranes are listed in
Table 1 and can be categorized between the known Lewis acids,
which renders them as promising candidates for robust WCAs.
In the 19F NMR spectrum of 1 in chloroform, only the meridi-
onal configuration (B) is observed, as is also present in the crys-
tal in Figure 1. The fluorine atom FIII (see Figure 2) displays a
chemical shift in the range δ = –5 to –8 ppm, whereas the
resonances for the chemically equivalent fluorine atoms FII are
observed in the range δ = –39 to –42 ppm, which is characteris-
tic for such phosphates.
Table 1. Calculated FIAs of selected difluorophosphoranes and commonly
known Lewis acids.[a]
Lewis acid/fluoride complex
FIA [kJ/mol]
COF2/[OCF3]–
206 (exp.: 209)[b]
(C6F5)3PF2/[(C6F5)3PF3]–
BF3/[BF4]–
317
330
363
363
383
397
422
(NC5F4)3PF2/[(NC5F4)3PF3]–
–
PF5/[PF6
]
(NCC6F4)3PF2/[(NCC6F4)3PF3]–
(C2F5)3PF2/[(C2F5)3PF3]–
AsF5/[AsF6]–
Figure 2. Positions of the fluorine atoms in fAr3PF2 and the possible stereoiso-
mers [fAr3PF3]–.
[a] Method: DFT, B3LYP/6311G++(2d,p).[28] [b] Experimentally known value[27]
converted to kJ/mol.
Tris(tetrafluoropyridyl)phosphane[35]
was
synthesized
The synthesis[29] and molecular structure[30] of (C6F5)3PF2 are
well-known. Although metathetical methods are typically em-
ployed for the synthesis of R3PF2 compounds,[31,32] the direct
fluorination with elemental fluorine and helium as the carrier
gas[33] was preferred here [Equation (2)].
through the deprotonation of 2,3,5,6-tetrafluoropyridine with n-
butyllithium and reaction with PCl3. Direct fluorination of the
resulting phosphane in acetonitrile furnished phosphorane 2 as
an off-white solid in 89 % yield [Equation (3)].
(3)
The 19F NMR spectrum of 2 in an acetonitrile solution exhib-
its a characteristic doublet of septets at δ = –3.8 ppm, which is
(2)
The treatment of (C6F5)3PF2 with [K([18]crown-6)]F affords assigned to the trans-oriented fluorine atoms at the phos-
1
4
the complex [K([18]crown-6)][(C6F5)3PF3] (1). Single crystals of 1 phorus atom. Coupling constants JP, F of 717 Hz and JF,F of
were obtained through the slow concentration of an aceto- 13 Hz were measured. The F atoms at the heterocycle were
nitrile solution. The compound crystallizes in the triclinic space observed at δ = –134.0 and –88.4 ppm. Single crystals of phos-
group P1¯. The X-ray diffraction analysis reveals an octahedrally phorane 2 were obtained through the slow concentration of an
coordinated phosphorus atom with a meridional arrangement acetonitrile solution. The compound crystallizes in the mono-
of the fluorine atoms bound directly to the phosphorus atom. clinic space group P21/n.
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The phosphorus atom is located in the centre of a slightly
Compound 4 crystallizes in the monoclinic space group
distorted bipyramid with two apical fluoride substituents P21/c. The molecular structure exhibits the classical trigonal-bi-
[d(P–F) = 163.3(1) and 164.2(1) pm]. The F1–P–F2 angle of pyramidal geometry about the phosphorus atom with nearly
177.3(1)° deviates slightly from linearity. Owing to the pro- identical structural parameters as those for phosphorane 2 (Fig-
nounced steric hindrance between the ortho-F atoms, the ure 5).
heterocyclic substituents adopt a propeller-blade geometry
(Figure 3).
Figure 5. Molecular crystal structure of 4; 50 % probability displacement ellip-
Figure 3. Molecular crystal structure of 2; 50 % probability displacement ellip-
soids are shown; selected bond lengths [pm] and angles [°]: P–F1 163.3(1),
P–F2 164.2(1), P–C 181.7(1)–181.9(1); F1–P–F2 177.3(1), F1–P–C1 91.4(1),
C1–P–C6 118.0(1), C1–P–C11 118.3(1), C6–P–C11 123.8(1).
soids are shown; selected bond lengths [pm] and angles [°]: P–F1 163.6(1),
P–F2 164.1(1), P–C 181.4(1)–181.9(1); F1–P–F2 178.1(1), F1–P–C1 90.1(1), C1–
P–C8 117.7(1), C1–P–C15 123.6(1), C8–P–C15 118.7(1).
Difluorotris(pentafluoroethyl)phosphorane is also included in
this study. This volatile liquid is produced in multiton quantities
by the electrochemical fluorination of (C2H5)3P (Simons proc-
ess).[10,36] A crystal suitable for X-ray diffraction analysis was ob-
tained by in situ crystallization of the liquid in a glass capillary
through the manual generation of a seed crystal at slightly be-
low the melting point, followed by slow cooling to –182 °C.
The phosphorane (C2F5)3PF2 (5) crystallizes in the triclinic space
The more common approach to triarylphosphanes with a
Grignard reaction failed, as the precursor NCC6F4H appeared to
be reluctant towards deprotonation by a Grignard reagent. The
synthesis of (NCC6F4)3P (3) was achieved by the reaction of
pyrophoric P(SiMe3)3 and NCC6F5 in dimethoxyethane for 72 h.
Subsequently, fluorination with XeF2 led to the phosphorane
(NCC6F4)3PF2 [4, Equation (4)].
group P1 with two molecules per asymmetric unit. One of these
¯
shows a disorder of two fluorine atoms and two alkyl groups.
However, only the non-disordered molecule is shown and dis-
cussed here. The molecular structure shows a trigonal-bi-
pyramidal coordination geometry about the phosphorus atom
with two apical fluoride substituents [d(P–F) = 161.3(1) and
161.4(1) pm]. The F1–P–F2 angle of 179.4(1)° is nearly linear.
Owing to packing effects, the freely rotatable pentafluoroethyl
groups are oriented parallel to the F1–P–F2 axis, one below and
two above the PC3 plane (Figure 6).
(4)
Single crystals of 3 and 4 were obtained by storing concen-
trated solutions of the products in acetonitrile at –28 °C. Phos-
phane 3 crystallizes in the monoclinic space group Cc. The trig-
onal-pyramidal geometry around the phosphorus atom is dis-
torted (Figure 4).
Figure 6. Molecular crystal structure of 5; 50 % probability displacement ellip-
soids are shown; selected bond lengths [pm] and angles [°]: P–F 161.3(1)–
161.4(1), P–C 188.5(3)–189.0(3); F1–P–F2 179.4(1), F1–P1–C1 87.3(1), C1–P1–
C3 117.9(1), C1–P1–C5 123.1(1).
Figure 4. Molecular crystal structure of 3; 50 % probability displacement ellip-
soids are shown; selected bond lengths [pm] and angles [°]: P–C 183.8(1)–
185.1(1); C1–P–C8 97.6(1), C1–P–C15 106.6(1), C8–P–C15 103.6(1).
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As can be seen clearly in Table 1, the FIA of (NC5F4)3PF2 is [d(P2–O1) = 150.9(1) and d(P3–O2) = 154.1(1) pm], the cation
comparable to that of PF5. The FIA of (NCC6F4)3PF2 is signifi- can be described as a hydroxyphosphonium ion stabilized by a
cantly higher, but all three are outnumbered by the FIA of phosphane oxide (Figure 8).
(C2F5)3PF2. According to the work of Stelzer and Schmutzler,[13]
these Lewis acids should be reactive enough to abstract a fluor-
ide ion from difluoro(trialkyl)- or -(triaryl)phosphoranes, and the
resulting adducts should serve as appropriate counterions to
stabilize the resulting cations. With this in mind, samples of
phosphoranes 2, 4 and 5 were added to solutions of
[32]
(C6H11)3PF2 in acetonitrile (Scheme 1).
Scheme 1. Reactions of (C6H11)3PF2 with phosphoranes 2, 4 and 5.
The NMR spectra of the reaction mixtures confirm the forma-
tion of fluorophosphonium fluorophosphates. For phosphorane
5, the 31P NMR spectrum reveals
a resonance for the
1
1
[(C2F5)3PF3]– anion at δ = –147.6 ppm (dtm, JP, F = 902, JP, F
=
890 Hz) and a doublet (1JP, F = 991 Hz) at δ = 132.7 ppm for the
cation (Figure 7). In addition, the fluorine atom of the cation is
Figure 8. Molecular crystal structure of 6; 50 % probability displacement ellip-
soids are shown; H atoms are omitted for clarity; selected bond lengths [pm]
and angles [°]: P1–F 161.8(1)–164.1(1), P1–C 189.9(2)–190.3(2), P2–O1
150.9(1), P3–O2 154.1(1); F1–P1–F2 89.9(1), F1–P–F3 179.6(1), F1–P–C1 90.5(1),
O1–P2–C28 109.2(1), C22–P2–C28 109.4(1).
1
2
observed at δ(19F) = –171.5 ppm (dq, JP, F = 992, JP, H = 8 Hz).
The analogous compound [{(C6H11)3PO}2H][(NCC6F4)3PF3] (7)
crystallizes in the monoclinic space group C2/c. The X-ray struc-
ture analysis shows a molecule with a hexacoordinate phos-
phorus atom with nearly the same structural parameters as
those found for the phosphates [(C6F5)3PF3]– and [(NC5F4)3PF3]–
(Figure 9).
Figure 7. 31P NMR spectrum of [(C6H11)3PF][(C2F5)3PF3] in CD2Cl2 at room tem-
perature.
The [(C6H11)3PF]+ cation hydrolyzed during attempts to grow
single crystals, despite the application of Schlenk techniques.
The slow condensation of n-pentane onto acetonitrile solutions
of [(C6H11)3PF][(NC5F4)3PF3] and [(C6H11)3PF][(NCC6F4)3PF3] led
to the formation of hydroxyphosphonium ions [Equation (5)].
The phosphonium salt [{(C6H11)3PO}2H][(NC5F4)3PF3] (6) crystalli-
zes in the orthorhombic space group Pna21. The X-ray diffrac-
tion analysis shows an octahedrally coordinated phosphorus
atom with a meridional arrangement of the fluorine atoms
bound directly to the phosphorus atom. The P–F bond lengths
in [(NC5F4)3PF3]– [161.8(1)–164.1(1) pm] are in the same range
as those in [(C6F5)3PF3]– [160.9(1)–164.3(1) pm], and the F1–P–
F2 angle of 179.4(1)° is nearly linear. As usual, the heterocyclic
substituents of the anion adopt a propeller-blade geometry ow-
ing to pronounced steric hindrance between the ortho-F atoms.
The cation consists of two (C6H11)3PO units bridged by a
proton. Owing to the small difference in the P–O distances
Figure 9. Molecular crystal structure of 7; 50 % probability displacement ellip-
soids are shown; selected bond lengths [pm] and angles [°]: P1–F1 162.8(1),
P1–F2 162.1(1), P1–C 190.6(2)–191.4(2); F1–P1–F2 90.0(1), F2–P1–C1 87.7(1),
F2–P1–C8 180.0(1), C1–P1–C8 92.3(1).
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Furthermore, samples of the phosphoranes (C6F5)3PF2, 2, 4 the phosphoranes and phosphates presented here (aver-
and 5 were combined with solutions of Ph3PF2 in acetonitrile. age 163 pm).
However, the selective formation of a fluorophosphonium
fluorophosphate was detected only for (C2F5)3PF2 (Scheme 2).
The electron-donating character of the three phenyl groups in
Ph3PF2 is not sufficient enough for it to act as a fluoride ion
donor towards weaker Lewis acids than (C2F5)3PF2. In other
words, the FIA of [Ph3PF]+ is higher than that of [(C6H11)3PF]+.
Figure 10. Molecular crystal structure of 8; 50 % probability displacement
ellipsoids are shown; H atoms are omitted for clarity; selected bond lengths
[pm] and angles [°]: P1–F1 154.6(1), P1–C 175.9(1)–177.3(1), P2–F 162.8(1);
F1–P1–C1 105.6(1), F1–P1–C7 109.4(1), C1–P1–C7 112.9(1), C1–P1–C13
112.8(1), C13–P1–C7 110.9(1).
The NMR spectroscopic and mass spectrometric data of se-
Scheme 2. Reactions of Ph3PF2 with phosphoranes 2, 4, 5 and (C6F5)3PF2.
lected fluorophosphate and fluorophosphonium fluorophos-
phate salts are listed in Table 2.
The salt [Ph3PF][(C2F5)3PF3] (8) was isolated as a colourless
Generally, the Lewis acidity of the pentafluorides of group
air- and moisture-sensitive solid with a m.p of 55 °C. Single 15 elements increases in the order P < As < Bi < Sb. Therefore,
crystals suitable for X-ray structure analysis were obtained from difluorotriarylbismuth(V) species Ar3BiF2 should be superior Le-
the melt. The X-ray structural parameters and heteronuclear wis acid to their P and As analogues and more reluctant to
NMR spectroscopic data of the [Ph3PF]+ cation are in agreement fluoride ion donation towards difluorotris(perfluoroorgan-
with the literature values.[16]
yl)phosphoranes than Ph3PF2, for example. Most representatives
of the type Ar3BiX2 are crystalline, nonhygroscopic solids that
are highly soluble in many organic solvents.[24,37] However, the
only halogenobismuthonium salt reported to date is
Compound 8 crystallizes in the triclinic space group P1. A
¯
tetrahedral coordination geometry around the cationic phos-
phorus atom and an octahedral environment for the phos-
phorus atom in the anion are present (Figure 10). Owing to the
electron deficiency, the P1–F1 bond length of the phosphon-
[Ph3BiI][AsF6].[38]
[39,40]
Ph3BiF2
is readily obtained by the treatment of Ph3Bi
ium cation is shorter (154.5 pm) than the P–F bond lengths of with XeF2. The condensation of 1 equiv. of (C2F5)3PF2 onto a
Table 2. NMR spectroscopic (room temp.) and mass spectrometric data of selected fluorophosphate and fluorophosphonium fluorophosphate salts.
[a] In acetonitrile/[D6]acetone. [b] In [D]chloroform. [c] In [D3]acetonitrile.
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solution of Ph3BiF2 in acetonitrile [δ(19F) = –159.0 ppm] led to
the formation of [Ph3BiF][(C2F5)3PF3] [9, Equation (5)]. The
fluorine atom bonded directly to the bismuth centre of the cat-
ion gives rise to a broad singlet at significantly higher field
[δ(19F) = –170.6 ppm; Figure 11].
(5)
Figure 12. Molecular crystal structure of the cation of 9; 50 % probability
displacement ellipsoids are shown; H atoms are omitted for clarity; selected
bond lengths [pm] and angles [°]: Bi–F1 224.7(3), Bi–F1′ 226.7(3), Bi–C
217.3(6)–221.4(17); F1–Bi–F1′ 175.5(2), F1–Bi–C1 88.4(2), C1–Bi–C7 115.1(2);
symmetry code for F1′: 1/2 – x, 1/2 + y, 1/2 – z.
Figure 11. 19F NMR spectrum of 9 in a [D2]dichloromethane/[D3]acetonitrile
mixture at room temperature.
The reaction of Ph3BiF2 and (C2F5)3PF2 in dichloromethane
resulted in a precipitate, which dissolved smoothly upon the
addition of 2 equiv. of acetonitrile. Crystals of 9 were obtained
by cooling this concentrated solution to –28 °C. The compound
crystallizes in the monoclinic space group P21/n. Unfortunately,
the molecular structure is highly disordered, and different sol-
vent molecules (60 % CH2Cl2 and 40 % CH3CN) occupy the
same site in the unit cell. The [(C2F5)3PF3]– anion builds H–F
contacts to CH2Cl2 and to a phenyl group of the cation but not
to acetonitrile. As a result, the whole anion and one phenyl
group are disordered with the same ratio of 60:40. Additionally,
one C2F5 group within the main part of the anion is disordered
in a 1:1 ratio, and the C–F and C–C distances in this disordered
part were restrained to be the same, as were the anisotropic
displacement parameters (ADPs) of the atoms at these very
near positions. Thus, although the atom connectivity is un-
doubtedly correct, the metric parameters for 9 (Table 4) should
be viewed with caution.
Nevertheless, the X-ray diffraction analysis discloses the pres-
ence of endless chains for the fluorobismuthonium cation, gen-
erated by a twofold screw axis along b, in which the bismuth
centres are bridged by fluorine atoms (Figure 12). A trigonal-
bipyramidal coordination geometry is observed around the cat-
ionic bismuth atom. Owing to the electron deficiency, the Bi–F
bond lengths of the bismuthonium cation are shorter [d(Bi–
F1) = 224.7(3) and d(Bi–F1′) = 226.7(3) pm] than the Bi–F bond
lengths of Ph3BiF2 [average 259(1) pm].[40]
Scheme 3. Reactions of Ph3BiF2 with phosphoranes 2 and 4.
the monomeric form of this electrophilic species. The employ-
ment of the 2-[(dimethylamino)methyl]phenyl N,C-chelating li-
gand, which has already been successfully used for the genera-
tion of halogenoorganylbismuth(III) compounds, was useful for
this concept.[41–44]
Lithiated dimethylbenzylamine reacts with ClBiPh2 to form
the bismuthane Ph2BiC6H4CH2NMe2 (10), which was subse-
quently converted into the difluorotriarylbismuthane
Ph2BiC6H4CH2NMe2F2 (11) by XeF2 in acetonitrile [δ(19F) =
–144.7 ppm; Equation (6)].
(6)
The perfluoroaryl phosphoranes 2 and 4 reacted with
Ph3BiF2 in an acetonitrile solution, and fluoride transfers of the
discussed type were observed. However, if the product was ex-
posed to nondonating solvents, such as difluorobenzene or di-
chloromethane, the reverse reaction occurred. Crystallization
experiments with [Ph3BiF][(EWG)3PF3] (EWG = electron-with-
drawing group) resulted in crystals of Ph3BiF2 (Scheme 3).
Compound 10 crystallizes in the triclinic space group P1¯. The
molecular structure reveals a clear orientation of the amino
function towards the bismuth centre (Figure 13). Although the
Bi–N distance [285.1(1) pm] is too long for a covalent bond
[Σrcov(Bi,N) = 220 pm],[23] it is significantly shorter than the sum
of the van der Waals radii [ΣrvdW(Bi,N) = 400 pm][23] or the Bi–
N distances in Bi(C6H4CH2NMe2)3 (average 305 pm).[44] Notably,
It became clear that an internal Lewis base, preferably an N- the Bi–N distances in compounds of the type
donor function, is required for the stabilization and isolation of (Ar)XBi(C6H4CH2NMe2)3 (X = Cl, Br, I) are much shorter (aver-
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age 253 pm), presumably because of the trans arrangement of The evaporation of solutions of [Ph2BiC6H4CH2NMe2F]-
the N–Bi–Cl bonds and the presence of pentavalent bis- [(C2F5)3PF3] in pentafluorobutane led to the quantitative forma-
muth.[41,43,44]
tion of a colourless, voluminous foam with a melting point
above 150 °C.
Figure 13. Molecular crystal structure of 10; 50 % probability displacement
ellipsoids are shown; H atoms are omitted for clarity; selected bond lengths
[pm] and angles [°]: Bi–C 225.5(4)–229.5(4), Bi–N 285.1(3); C1–Bi–N 69.1(1),
C1–Bi–C10 93.1(1), C10–Bi–C16 92.9(1), C1–Bi–C16 93.8(1).
Single crystals of 11 suitable for the X-ray diffraction analysis
were grown from a methanolic solution at –28 °C. The com-
pound crystallizes in the monoclinic space group C2/c. Similarly
to the bismuth(III) compound 10, the molecular structure of the
bismuth(V) species 11 reveals a clear orientation of the amino
function towards the bismuth centre, and the C1–Bi–C10 angle
is widened to 150.8(1)°. The Bi–N distance is slightly shorter
[278.7(1) pm] than that in 10, probably because of the higher
oxidation state and the associated increased Lewis acidity.
Therefore, the coordination geometry around the bismuth atom
should be referred to as pseudo-octahedral rather than dis-
torted trigonal bipyramidal (Figure 14).
Scheme 4. Reactions of 11 with phosphoranes 2, 4, 5 and (C6F5)3PF2.
As the 4-(dimethylamino)pyridine (DMAP) and Ph3PO ad-
ducts of the triphenylbismuth dication [Ph3Bi]2+ are known,[45]
the quest for doubly charged [Ph3Bi(LB)2]2+ moieties is obvious.
When (C2F5)3PF2 (2 equiv.) was combined with Ph3BiF2 in aceto-
nitrile solution, the salt [Ph3Bi(NCCH3)2][(C2F5)3PF3]2 (12) formed
quantitatively [Equation (7)].
(7)
The salt 12 crystallizes in the monoclinic space group C2/c.
The cation shows a trigonal-bipyramidal coordination geometry
about the bismuth atom (Figure 15). The Bi–N distances
[238.3(1) pm] exceed the sum of the covalent radii of the two
elements [Σrcov(Bi,N) 220 pm][23] but are shorter than those in
the [BiCl([18]crown-6)(NCCH3)2]2+ ion [282(2) pm][46] and com-
parable to those in [Ph3Bi(OTf)(DMAP)2]+ [237.3(2) pm, OTf =
triflate].[45]
Figure 14. Molecular crystal structure of 11; 50 % probability displacement
ellipsoids are shown; H atoms are omitted for clarity; selected bond lengths
[pm] and angles [°]: Bi–F 211.8(1)–213.3(1), Bi–C 219.6(1)–220.7(1), Bi–N
278.7(1); F1–Bi–F2 177.0(1), C1–Bi–N 84.4(1), C1–Bi–F1 89.1(1), C1–Bi–C10
150.8(1), C10–Bi–C16 105.4(1), C1–Bi–C16 103.9(1).
Although Ph3BiF2 resists fluoride donation towards
(C6F5)3PF2, Ph2BiC6H4CH2NMe2F2 reacts readily with the phos-
phoranes 2, 4, 5 and (C6F5)3PF2 to afford fluorobismuthonium
phosphates, which can be detected by 31P and 19F NMR spec-
troscopy (Scheme 4). The fluorine atom bonded directly to the
bismuth centre of the cation gives rise to a broad singlet at δ =
–149.8 ppm in dichloromethane. This is in accord with a more
prominent Bi–N interaction and
a lowered FIA of the
[Ph2BiC6H4CH2NMe2F]+ ion. In addition to acetonitrile, these bis-
muthonium salts are also soluble in dichloromethane and
1,1,1,3,3-pentafluorobutane. However, the slow concentration
of these solutions yielded only oily residues, and the slow con-
densation of diethyl ether onto acetonitrile solutions or n-pent-
Figure 15. Molecular crystal structure of the cation of 12; 50 % probability
displacement ellipsoids are shown; H atoms are omitted for clarity; selected
bond lengths [pm] and angles [°]: Bi–N 238.3(1), Bi–C 219.1(2); N–Bi–N
179.3(1), N1–Bi–C1 89.9(1), C1–Bi–C7 116.3(1).
Notably, the storage of an identically prepared sample of
ane onto dichloromethane solutions caused phase separations. [Ph2BiC6H4CH2NMe2(NCCH3)2][(C2F5)3PF3]2 (0.4 mmol) in dry
Eur. J. Inorg. Chem. 2016, 3999–4010
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Full Paper
The NMR spectra were recorded with a Bruker Avance III 300 spec-
trometer (31P 111.92 MHz; 19F 282.40 MHz; 13C 75.47 MHz, 1H
300.13 MHz) with positive shifts downfield from the external stan-
dards [85 % orthophosphoric acid (31P), CCl3F (19F), and tetrameth-
ylsilane (TMS, 1H)]. The IR spectra were recorded with an ALPHA
FTIR spectrometer (Bruker Daltonik GmbH, Bremen) equipped with
an attenuated total reflectance (ATR) unit with a diamond crystal
for liquids and solids. EI mass spectra were recorded with an Auto-
spec X magnetic sector mass spectrometer with EBE geometry (Vac-
uum Generators, Manchester) equipped with a standard EI source.
The samples in aluminium crucibles (standard) were introduced by
a push rod, and the ions were accelerated by 8 kV. The spectra were
recorded and processed with the OPUS software (V3.6, Micromass
1998) through the accumulation and averaging of several single
spectra. The ESI mass spectra were recorded with an Esquire 3000
ion-trap mass spectrometer (Bruker Daltonik GmbH, Bremen)
equipped with a standard ESI/atmospheric pressure chemical ioni-
zation (ESI/APCI) source. The samples were introduced by direct
infusion with a syringe pump. Nitrogen as the nebulizer gas and
the dry gas was generated by a Bruker NGM 11 nitrogen generator.
Helium served as the cooling gas for the ion trap and collision gas
for MS experiments. The spectra were recorded with the Bruker
Daltonik esquireNT 5.2 esquireControl software by the accumula-
tion and averaging of several single spectra. Data analysis software
3.4 was used to process the spectra. C, H and N analyses were
performed with a HEKAtech Euro EA 3000 instrument.
tetrahydrofuran (10 mL) over several days at room temperature
resulted in a black, gelatinous rubbery substance. Clearly, a
ring-opening polymerization of the acyclic ether was induced
by the cation. This interesting observation merits a more thor-
ough investigation in future work.
Conclusions
In this contribution, we have reported the beneficial application
of the concept of fluoride ion affinity (FIA) derived from quan-
tum chemical methods on the construction of difluoro(per-
fluoroorganyl)phosphoranes. The ability of these compounds to
abstract fluoride ions from suitable fluoride ion donors allowed
the synthesis of the highly reactive fluorophosphonium cation
[Ph3PF]+ and the previously unknown fluorobismuthonium cat-
ion [Ph3BiF]+. Furthermore, we devised an efficient protocol to
generate base-stabilized triarylbismuth(V) cations from the
readily available Ph3BiF2.
Experimental Section
General: All chemicals were purchased from commercial sources
and used without further purification. Standard high-vacuum tech-
niques were employed throughout all experiments (p
=
1 × 10–3 mbar). Nonvolatile compounds were handled under a dry
N2 atmosphere by Schlenk techniques.
The crystal data for 1, 2, 4, 6, 8, 9, 10, 11 and 12 were collected
with an Agilent SuperNova diffractometer, and those for 3, 5 and 7
Table 3. Structure and refinement data of 1–6.
1
2
3
4
5
6
Empirical formula
a /pm
b /pm
c /pm
α /°
C30H24F18KO6P
1104.12(5)
1200.58(6)
1367.00(6)
100.592(4)
95.418(4)
107.892(4)
1672.84(14)
2
C15F14N3P
1089.307(5)
946.379(4)
1613.640(7)
90
90.9840(4)
90
1663.252(13)
4
2.073
monoclinic
P21/c
colourless
irregular
0.31 × 0.22 × 0.17
Cu-Kα
C21F12N3P
1497.56(10)
1173.49(16)
1153.27(8)
90
104.287(7)
90
1964.0(3)
4
1.871
monoclinic
Cc
colourless
fragment
0.30 × 0.19 × 0.11
Mo-Kα
C21F14N3P
1027.00(2)
1784.50(4)
1199.28(3)
90
106.7863(14)
90
2104.24(8)
4
1.866
monoclinic
P21/c
colourless
fragment
0.30 × 0.17 × 0.13
Mo-Kα
C6F17
P
C51H67F15N3O2P3
1938.20(3)
1398.11(3)
1914.58(3)
90
945.45(3)
1110.46(3)
1200.46(4)
75.8697(18)
83.9896(18)
89.9720(19)
1215.08(6)
4
ꢀ /°
γ /°
90
90
V /106 Å3
Z
5188.15(15)
4
1.449
orthorhombic
Pna21
colourless
fragment
0.45 × 0.24 × 0.13
Mo-Kα
ρcalcd. /Mg m–3
Crystal system
Space group
Colour
1.772
triclinic
2.329
triclinic
P1
P1
¯
¯
colourless
fragment
0.41 × 0.35 × 0.20
Mo-Kα
colourless
cylindrical
0.30 × 0.30 × 0.30
Mo-Kα
Shape
Crystal size /mm–3
Radiation used
Wavelength /pm
μ /mm–1
F(000)
71.073
0.352
896.0
154.178
3.059
1008.0
71.073
0.271
1080
71.073
0.272
1152
71.073
0.446
816
71.073
0.212
2360.0
2θ range for data collection [°] 4.6 to 60.0
9.7 to 152.5
–13 ≤ h ≤ 12,
–11 ≤ k ≤ 11,
–20 ≤ l ≤ 20
61648
6.9 to 55
–19 ≤ h ≤ 19,
–15 ≤ k ≤ 15,
–14 ≤ l ≤ 14
21556
6.2 to 60.0
–14 ≤ h ≤ 14,
–25 ≤ k ≤ 25,
–16 ≤ l ≤ 16
34128
5.8 to 60.0
–13 ≤ h ≤ 11,
–15 ≤ k ≤ 13,
–16 ≤ l ≤ 16
25928
4.3 to 60.0
–27 h ≤ 27,
–19 ≤ k ≤ 18,
–26 ≤ l 26
77733
Index ranges
–15 ≤ h ≤ 15,
–16 ≤ k ≤ 16,
–19 ≤ l ≤ 19
99300
Reflections collected
Independent reflections
9751 [R(int) =
0.0300]
3464 [R(int) =
0.0243]
4462 [R(int) =
0.0217]
6136 [R(int) =
0.044]
6703 [R(int) =
0.031]
14815 [R(int) =
0.0332]
Data/restraints/parameters
Goodness-of-fit on F2
R1/wR2 [I ≤ 2σ(I)]
9751/0/505
1.047
0.0262 / 0.0677
0.0292 / 0.0694
0.41 /–0.31
–
3464/0/298
1.101
0.0245 / 0.0662
0.0247 / 0.0664
0.38 /–0.33
–
4462/2/334
1.044
0.0234 / 0.0559
0.0274 / 0.0578
0.21 /–0.25
0.07(6)
6136/0/352
1.025
0.0373 / 0.0877
0.0580 / 0.0966
0.34 /–0.41
–
6703/364/485
1.032
0.0584 / 0.1579
0.0707 / 0.1691
1.09 /–0.56
–
14815/1/869
1.037
0.0307 / 0.0775
0.0336 / 0.0794
0.63 /–0.36
–0.014(15)
1469048
R1/wR2 (all data)
Δρmax/min /e Å–3
Flack parameter
CCDC number
1469043
1469044
1469045
1469046
1469047
Eur. J. Inorg. Chem. 2016, 3999–4010
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4006
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
Table 4. Structure and refinement data of 7–12.
7
8
9
10
11
12
Empirical formula
C57H67F15N3O2P3
1731.22(9)
1466.68(5)
2322.04(13)
90
102.185(5)
90
5763.1(5)
4
C24H15F19P2
936.006(16)
1016.245(17)
1438.91(3)
78.2595(15)
88.4996(15)
86.1834(14)
1336.99(4)
2
C25.4H17.4BiCl1.2F19N0.4
1500.76(3)
838.62(1)
2520.01(5)
90
96.0100(17)
90
3154.15(9)
4
P
C21H22BiN
819.48(5)
1093.51(6)
1179.63(6)
114.899(5)
93.220(5)
106.432(5)
900.80(10)
2
C21H22BiF2N
1630.08(5)
1084.50(2)
2171.78(8)
90
99.794(3)
90
3783.4(2)
8
C34H21BiF36N2P2
a /pm
b /pm
c /pm
α /°
1885.43(3)
1454.942(14)
1778.84(2)
90
111.1046(15)
90
4552.40(11)
4
2.061
ꢀ /°
γ /°
V / 106 Å3
Z
ρ
calcd. /Mg m–3
1.388
1.804
2.047
1.834
1.880
Crystal system
Space group
Colour
monoclinic
C2/c
colourless
fragment
0.25 × 0.11 × 0.04
Mo-Kα
triclinic
monoclinic
P21/n
colourless
plank
0.44 × 0.15 × 0.11
Mo-Kα
71.073
triclinic
monoclinic
C2/c
colourless
needle
0.49 × 0.16 × 0.13
Mo-Kα
71.073
monoclinic
C2/c
yellow
irregular
0.29 × 0.24 × 0.14
Mo-Kα
P1
P1
¯
¯
colourless
irregular
colourless
needle
Shape
Crystal size /mm–3
Radiation used
Wavelength /pm
μ /mm–1
0.33 × 0.20 × 0.06
Mo-Kα
71.073
0.58 × 0.21 × 0.09
Mo-Kα
71.073
71.073
0.196
71.073
4.122
0.312
5.874
9.786
9.342
F(000)
2504.0
720.0
1848.0
476.0
2048.0
2704.0
2θ range for data collection [°] 3.9 to 50.0
5.8 to 60
5.1 to 60.1
–21 ≤ h ≤ 21,
–11 ≤ k ≤ 11,
–35 ≤ l ≤ 35
176983
3.9 to 60.0
–11 ≤ h ≤ 11,
–15 ≤ k ≤ 15,
–16 ≤ l ≤ 16
52154
3.8 to 60.0
–22 ≤ h ≤ 22,
–15 ≤ k ≤ 15,
–30 ≤ l ≤ 30
108028
5.4 to 60.1
–26 ≤ h ≤ 26,
–20 ≤ k ≤ 20,
–25 ≤ l ≤ 25
118540
Index ranges
–19 ≤ h ≤ 20,
–17 ≤ k ≤ 17,
–27 ≤ l ≤ 19
19664
–13 ≤ h ≤ 13,
–14 ≤ k ≤ 14,
–20 ≤ l ≤ 20
78354
Reflections collected
Independent reflections
5080 [R(int) =
0.0461]
7769 [R(int) =
0.0327]
9205 [R(int) = 0.0576]
5275 [R(int) =
0.1089]
5531 [R(int) =
0.0392]
6656 [R(int) =
0.0430]
Data/restraints/parameters
Goodness-of-fit on F2
R1 / wR2 [I ≤ 2σ(I)]
R1 / wR2 (all data)
Δρmax/min /e Å–3
5080/0/365
1.040
0.0468 / 0.0966
0.0704 / 0.1065
0.33 /–0.31
1469049
7769/0/406
1.051
0.0285 / 0.0722
0.0329 / 0.0754
0.53 /–0.30
1469050
9205/16/687
1.191
0.0412 / 0.1013
0.0492 / 0.1043
2.53 /–3.64
1469051
5275/0/210
1.066
0.0354 / 0.0752
0.0388 / 0.0772
3.37 /–3.77
1469052
5531/0/228
1.082
0.0147 / 0.0361
0.0161 / 0.0367
2.17 /–0.89
1469053
6656/0/341
1.088
0.0161 / 0.0413
0.0166 / 0.0415
0.72 /–0.58
1469054
CCDC number
were collected with
a
Nonius KappaCCD diffractometer at
ether/[D6]acetone, r.t.): δ = –72.4 [sept, 3J(P,F) = 27 Hz] ppm. MS
(EI-TOF, +, 70 eV): m/z (%) = 481 (100) [(NC5F4)3P]·+, 462 (7)
100.0(1) K. Suitable crystals were selected (except those of 5),
coated with Paratone oil, and mounted onto the diffractometer. [(NC5F4)2P(NC5F3)]+, 331 (20) [(NC5F4)2P]+.
Crystals of 5 were created by in situ crystallization of the liquid
(NCC6F4)3P (3): A sample of P(SiMe3)3 (2.9 mL, 10.0 mmol) was
inside a sealed capillary through the manual generation of a crystal
seed just under the melting temperature and subsequent slow cool-
ing to 100 K. Olex2[47] was used to solve the structures with the
SHELXS[48] structure solution program by direct methods, and re-
finement was performed with the SHELXL[48] refinement package
through least-squares minimization. Details of the X-ray investiga-
tion are listed in Tables 3 and 4.
added to a solution of pentafluorobenzonitrile (4.0 mL, 33.0 mmol)
in acetonitrile (50 mL). The reaction mixture was heated under re-
flux for 72 h and the cooled to room temperature. The off-white
precipitate was removed by filtration, and the filter cake was
washed with dichloromethane (3 × 5 mL) and dried in vacuo to
yield 3 as an off-white solid (2.69 g, 4.86 mmol, 49 %). 13C{19F} NMR
(acetonitrile/[D6]acetone, r.t.): δ = 148.0 (s, Cortho), 148.1 (s, Cmeta
ppm. 13C,19
HMBC NMR (acetonitrile/[D6]acetone, r.t.):
97.8/–132.4 (C–CN), 118.1/–127.4 (C–P) ppm. 19F NMR (acetonitrile/
)
CCDC 1469043 (for 1), 1469044 (for 2), 1469045 (for 3), 1469046
(for 4), 1469047 (for 5), 1469048 (for 6), 1469049 (for 7), 1469050
(for 8), 1469051 (for 9), 1469052 (for 10), 1469053 (for 11) and
1469054 (for 12) contain the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre.
F
δ =
[D6]acetone, r.t.): δ = –132.4 (m, 6 F, Fmeta), –127.4 (m, 6 F, Fortho
)
ppm. 31P NMR (acetonitrile/[D6]acetone, r.t.): δ = –68.7 [sept,
3J(P,F) = 34 Hz] ppm. MS (EI-TOF, +, 70 eV): m/z (%) = 553 (100)
[(NCC6F4)3P]·+, 379 (27) [(NCC6F4)2P]+, 224 (10) [(NCC6F4)PF]+, 69 (76)
[PF ]+. IR (solid): ν = 507 (w), 541 (w), 647 (m), 801 (w), 972 (vs),
˜
2
(NC5F4)3P: A solution of n-butyllithium in n-hexane (1.6 M, 12.0 mL,
1022 (m), 1287 (s), 1463 (vs), 1665 (w), 2247 (w) cm–1. Single crystals
suitable for X-ray structure analysis were grown from an acetonitrile
solution of 3 at –28 °C.
19.0 mmol) was added dropwise to a stirred solution of 2,3,5,6-
tetrafluoropyridine (NC5F4H, 1.9 mL, 19.0 mmol) in diethyl ether
(150 mL) over 45 min at –80 °C. After additional stirring for 30 min,
a solution of PCl3 (0.5 mL, 5.7 mmol) in diethyl ether was added at
–80 °C, and the reaction mixture was warmed to 0 °C over 4 h. A
colourless precipitate was removed by filtration, the filter cake was
Typical Procedure for the Direct Fluorination of Triorganylphos-
phanes: Synthesis of (NC5F4)3PF2 (2): A sample of (NC5F4)3P
(465 mg, 0.97 mmol) was dissolved in acetonitrile (10 mL) in a Teflon
washed twice with diethyl ether (5 mL), and the filtrate was re- reactor equipped with a stainless-steel valve. A mixture of fluorine
moved under reduced pressure. The recrystallization of the residue in helium (5 %, 2.5 mmol) was repeatedly injected into the reaction
from chloroform yielded the product as a pale yellow solid (1.10 g,
solution over 1 h at 0 °C. After the removal of all volatiles in vacuo,
2 was obtained as an off-white solid (464 mg, 0.89 mmol, 89 %).
2.30 mmol, 40 %). 19F NMR (diethyl ether/[D6]acetone, r.t.): δ =
–131.7 (m, 6 F, Fortho), –88.9 (m, 6 F, Fmeta) ppm. 31P NMR (diethyl 13C{19F} NMR (acetonitrile/[D6]acetone, r.t.): δ = 141.4 (s, Cortho),
Eur. J. Inorg. Chem. 2016, 3999–4010
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© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
144.7 (s, Cmeta) ppm. 19F NMR (acetonitrile/[D6]acetone, r.t.): δ =
–134.0 (m, 6 F, Fmeta), –88.4 (m, 6 F, Fortho), –4.3 [dsept, 1J(P,F) = 717,
4J(F,F) = 13 Hz, 2 F, PF2] ppm. 31P NMR (acetonitrile/[D6]acetone, r.t.):
δ = –48.4 [tm, 1J(P,F) = 717 Hz] ppm. MS (EI-TOF, +, 70 eV): m/z
(%) = 519 (2) [(NC5F4)3PF2]·+, 500 (1) [(NC5F4)3PF]+, 481 (3)
[(NC5F4)3P]·+, 369 (100) [(NC5F4)2PF2]+, 238 (16) [(NC5F4)PF3]+, 69 (16)
[C2F4]–. Single crystals suitable for X-ray structure analysis were se-
lected from the melt of 8 at 55 °C.
Ph2BiC6H4CH2NMe2 (10): A sample of Ph2BiCl (2.00 g, 5.0 mmol)
was added to
a
vigorously stirred suspension of {2-
[(dimethylamino)methyl]phenyl}lithium[49] (6.76 g, 50.0 mmol) in di-
ethyl ether (50 mL) at –50 °C. Subsequently, the reaction mixture
was stirred at room temperature for 20 h. After the addition of
water (30 mL), the aqueous phase was extracted twice with di-
chloromethane (10 mL). The combined organic phases were dried
with MgSO4, and the solvent was removed under reduced pressure.
The crude product was recrystallized from ethanol and dried in
vacuo to yield 10 as a colourless, crystalline solid (2.01 g, 4.0 mmol,
[PF2]+. IR (solid): ν = 491 (vs), 556 (s), 588 (s), 614 (vs), 695 (m), 727
˜
(m), 770 (s), 950 (s), 1248 (vs), 1405 (m), 1450 (vs) cm–1. Single crys-
tals suitable for X-ray structure analysis were grown from an aceto-
nitrile solution of 2 at –28 °C.
(C6F5)3PF2: t = 1 h, yield 76 %. 19F NMR (acetonitrile/[D6]acetone,
r.t.): δ = –159.5 (m, 6 F, Fmeta), –146.5 (m, 3 F, Fpara), –132.7 (m, 6 F,
1
4
1
Fortho), 1.5 [d, J(P,F) = 695, J(P,F) = 16 Hz, 2 F, PF2] ppm. 31P NMR
80 %), m.p. 90 °C. H NMR ([D]chloroform, r.t.): δ = 2.0 (s, 6 H, CH3),
1
(acetonitrile/[D6]acetone, r.t.): δ = –48.1 [tm, J(P,F) = 695 Hz] ppm.
3.4 (s, 2 H, CH2), 7.2 [dm, 3J(H,H) = 8 Hz, 1 H, CBnH], 7.3–7.4 (m, 7
3
3
H, CBnH/CPhH), 7.4 [t, J(H,H) = 8 Hz, 1 H, CPhHpara], 7.8 [d, J(H,H) =
Ph3PF2: t = 45 min, yield 91 %. 19F NMR (acetonitrile/[D6]acetone,
8 Hz, 4 H, CPhHortho], 7.8 [d, J(H,H) = 7 Hz, 1 H, CBnH] ppm. 13C{1H}
3
r.t.): δ = –39.6 [d, 1J(P,F) = 660 Hz, 2 F, PF2] ppm. 31P NMR (aceto-
NMR ([D]chloroform, r.t.): δ = 44.6 (s, CH3), 67.3 (s, CH2), 127.0 (s,
CPhH), 127.4 (s, CBnH), 129.4 (s, CBnH), 129.7 (s, CBnH), 133.0 (s, CPhH),
137.7 (s, CPhH), 139.7 (s, CBnH), 145.2 (s, Cquart), 159.0 (s, Cquart), 160.0
1
nitrile/[D6]acetone, r.t.): δ = –55.0 [tm, J(P,F) = 660 Hz] ppm.
Typical Procedure for the Fluorination of Triorganylphosphanes
with XeF2: Synthesis of (NCC6F4)3PF2 (4): A sample of (NCC6F4)3P
(552 mg, 1.00 mmol) was added to a solution of XeF2 (210 mg,
1.24 mmol) in acetonitrile (10 mL) at 0 °C. The reaction mixture was
stirred for 3 h at room temperature. After the removal of all volatiles
in vacuo, 4 was obtained as an off-white solid (549 mg, 0.93 mmol,
93 %). 13C{19F} NMR (acetonitrile/[D6]acetone, r.t.): δ = 100.1 [d,
4J(C,P) = 3 Hz, C–CN], 107.6 (s, CN), 118.6 [d, 1J(C,P) = 198 Hz, Cquart],
145.9 [d, 3J(C,P) = 4 Hz, Cmeta], 148.5 [d, 2J(C,P) = 19 Hz, Cortho] ppm.
19F NMR (acetonitrile/[D6]acetone, r.t.): δ = –130.9 (m, 6 F, Fmeta),
(s, Cquart) ppm. IR (solid): ν = 424 (m), 446 (m), 698 (s), 724 (s), 749
˜
(s), 824 (m), 847 (m), 1151 (m), 1267 (m), 1300 (m), 1424 (m), 1452
(m), 1468 (w), 1566 (w), 2784 (w), 2822 (w), 2854 (w), 2939 (w),
2972 (w), 3045 (w) cm–1. MS (EI-TOF, +, 70 eV): m/z (%) = 420 (100)
[PhBi{C6H4CH2N(CH3)2}]+, 342 (11) [Bi{C6H4CH2N(CH3)2}]+, 209 (30)
[Bi]·+, 134 (36) [C6H4CH2N(CH3)2]+. C21H22BiN (497.39): calcd. C 50.71,
H 4.46, N 2.82; found C 50.01, H 4.59, N 2.83. Single crystals suitable
for X-ray structure analysis were grown from an ethanolic solution
of 10 at –28 °C.
1
4
–130.2 (m, 6 F, Fortho), –0.4 [dsept, J(P,F) = 712, J(F,F) = 15 Hz, 2 F,
Ph2BiC6H4CH2NMe2F2 (11): A sample of Ph2BiC6H4CH2N(CH3)2
(940 mg, 1.90 mmol) was added to a solution of XeF2 (491 mg,
2.90 mmol) in acetonitrile (10 mL) at –30 °C. The reaction mixture
was stirred for 3 h at room temperature. After the removal of all
volatiles in vacuo, 11 was obtained as an off-white solid (1.01 g,
PF2] ppm. 31P NMR (acetonitrile/[D6]acetone, r.t.): δ = –46.8 [tsept,
1J(P,F) = 712, J(F,F) = 11 Hz] ppm. MS (EI-TOF, +, 70 eV): m/z (%) =
3
591 (1) [(NCC6F4)3PF2]·+, 572 (1) [(NCC6F4)3PF]+, 417 (100)
[(NCC6F4)2PF2]+, 261 (5) [(NCC6F4)PF3]+, 174 (5) [NCC6F4]+, 69 (20)
[PF2]+. IR (solid): ν = 450 (s), 573 (vs), 649 (s), 762 (s), 979 (s), 1044
˜
1
1.88 mmol, 99 %), m.p. 135 °C. H NMR ([D]chloroform, r.t.): δ = 2.0
(m), 1257 (w), 1298 (s), 1401 (w), 1479 (vs), 2247 (w) cm–1. Single
crystals suitable for X-ray structure analysis were grown from an
acetonitrile solution of 4 at –28 °C.
(s, 6 H, CH3), 3.7 (s, 2 H, CH2), 7.3 (m, 4 H, CH), 7.5–7.6 (m, 5 H, CH),
8.0 (m, 4 H, CPhH), 8.1 (m, 1 H, CBnH) ppm. 13C{1H} NMR ([D]chloro-
form, r.t.): δ = 44.5 (s, CH3), 61.9 (s, CH2), 130.2 (s, CBnH), 130.7 (s,
CPhH), 130.9 (s, CPhH), 131.0 (s, CBnH), 131.3 (s, CBnH) 133.3 (s, CBnH),
133.5 (s, CPhH), 138.9 (s, Cquart), 159.0 (s, Cquart), 160.0 (s, Cquart) ppm.
1
(C6H11)3PF2: t = 1.5 h, yield 88 %. H NMR (dichloromethane/[D6]-
acetone, r.t.): δ = 1.1–2.1 (m, 33 H, CH and CH2) ppm. 19F NMR
(dichloromethane/[D6]acetone, r.t.): δ = –63.7 [dq, 1J(P,F) = 638,
4J(F,F) = 9 Hz, 2 F, PF2] ppm. 31P NMR (dichloromethane/[D6]acetone,
19F NMR ([D]chloroform, r.t.): δ = –149.3 (m, 2 F) ppm. IR (solid): ν =
˜
438 (s), 454 (s), 687 (s), 725 (s), 990 (m), 1019 (m), 1175 (w), 1248
(w), 1302 (w), 1366 (w), 1437 (m), 1457 (w), 1559 (w), 1672 (w),
2783 (w), 2830 (w), 2863 (w), 2956 (w), 2986 (w), 3054 (w),
3076 (w) cm–1. MS (EI-TOF, +, 70 eV): m/z (%) = 420 (30) [PhBi-
{C6H4CH2N(CH3)2}]+, 362 (7) [Bi{C6H4CH2N(CH3)2}F]+, 343 (7)
[Bi{C6H4CH2N(CH3)2}]+ 286 (85) [PhBi]+, 209 (100) [Bi]·+, 134 (36)
[C6H4CH2N(CH3)2]+, 78 (30) [Ph]+. C21H22BiF2N (535.39): calcd. C
47.11, H 4.14, N 2.62; found C 45.52, H 4.15, N 2.99. Single crystals
suitable for X-ray structure analysis were grown from a methanolic
solution of 11 at –28 °C.
1
r.t.): δ = –22.0 [tm, J(P,F) = 632 Hz] ppm.
Typical Procedure for the Synthesis of Fluorophosphonium
Salts [R3PF][(EWG)3PF3]: Synthesis of [Ph3PF][(C2F5)3PF3] (8): A
sample of (C2F5)3PF2 (852 mg, 2.00 mmol) was condensed onto a
suspension of Ph3PF2 (193 mg, 0.64 mmol) in 1,1,1,3,3-pentafluoro-
butane (2 mL) at –193 °C. The mixture was stirred for 10 min at
room temperature, and all volatiles were removed under reduced
pressure. The residue was dried in vacuo at 50 °C to yield 8 as a
colourless, crystalline solid (430 mg, 0.59 mmol, 92 %), m.p. 55 °C.
1H NMR ([D3]acetonitrile, r.t.): δ = 7.9–8.0 (m, 12 H, CH), 8.1 (m, 3 H,
Typical Procedure for the Synthesis of Fluorobismuthonium
Salts [Ar3BiF][(EWG)3PF3]: Synthesis of [Ph3BiF][(C2F5)3PF3] (9):
1
CH) ppm. 13C{1H} NMR ([D3]acetonitrile, r.t.): δ = 116.6 [dd, J(C,P) =
2
2
109, J(C,F) = 14 Hz, Cquart], 130.5 [d, J(C,P) = 15 Hz, CH], 134.3 [d, A sample of (C2F5)3PF2 (117 mg, 0.28 mmol) was condensed onto a
3J(C,P) = 13 Hz, CH], 138.1 [d, 4J(C,P) = 3 Hz, CH] ppm. 19F NMR solution of Ph3BiF2 (134 mg, 0.28 mmol) in a mixture of 1,1,1,3,3-
([D3]acetonitrile, r.t.): δ = –128.7 [d, 1J(P,F) = 995 Hz, 1 F, PF+], –116.7
pentafluorobutane (0.5 mL) and acetonitrile (0.1 mL) at –193 °C. The
[dm, 2J(P,F) = 98 Hz, 4 F, CF2(A)], –116.1 [dm, 2J(P,F) = 80 Hz, 2 F, mixture was stored for 10 min at room temperature, and all volatiles
CF2(B)], –88.1 [dm, J(P,F) = 902 Hz, 2 F, PF2–], –82.4 [m, 6 F, CF3(A)],
were removed under reduced pressure. The residue was dried in
1
–80.7 [m, 3 F, CF3(B)], –44.7 [dm, J(P,F) = 890 Hz, 1 F, PF–] ppm. 31P
vacuo for 3 h to yield 9 as a colourless solid (251 mg, 0.28 mmol,
1
1
3
NMR ([D3]acetonitrile, r.t.): δ = –147.8 [dtm, 1J(P,F) = 902, 1J(P,F) =
890 Hz, 1 P, P–], 94.8 [dm, 1J(P,F) = 995 Hz, 1 P, PF+] ppm. MS
(ESI, +): m/z (%) = 557 (20) [(Ph3PO)2H]+, 279 (100) [Ph3POH]+. MS
(ESI, –): m/z (%): 445 (100) [(C2F5)3PF3]–, 301 (5) [Ph3PF2]–, 119 (5)
100 %). H NMR ([D3]acetonitrile, r.t.): δ = 7.8 [tm, J(H,H) = 7 Hz, 3
3
3
H, CH], 8.0 [tm, J(H,H) = 8 Hz, 6 H, CH], 8.2 [dm, J(H,H) = 8 Hz, 6
H, CH] ppm. 13C{1H} NMR ([D3]acetonitrile, r.t.): δ = 133.5 (s, CH),
133.8 (s, CH), 134.5 (s, CH), 154.6 (s, CH) ppm. 19F NMR ([D3]aceto-
Eur. J. Inorg. Chem. 2016, 3999–4010
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2
nitrile, r.t.): δ = –173.8 (s, 1 F, BiF+), –116.7 [dm, J(P,F) = 98 Hz, 4 F,
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1
CF2(A)], –116.1 [dm, J(P,F) = 80 Hz, 2 F, CF2(B)], –88.1 [dm, J(P,F) =
902 Hz, 2 F, PF2–], –82.4 [m, 6 F, CF3(A)], –80.7 [m, 3 F, CF3(B)], –44.7
[5]
[6]
[dm, J(P,F) = 890 Hz, 1 F, PF–] ppm. 31P NMR ([D3]acetonitrile, r.t.):
1
1
1
δ = –147.8 [dtm, J(P,F) = 902, J(P,F) = 890 Hz, 1 P, P] ppm. Single
crystals suitable for X-ray structure analysis were grown from a solu-
tion of 9 in dichloromethane at –28 °C.
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[Ph2BiC6H4CH2NMe2F][(C2F5)3PF3]:
A
sample of (C2F5)3PF2
solution of
(138 mg, 0.33 mmol) was condensed onto
a
Ph2BiC6H4CH2NMe2F2 (174 mg, 0.32 mmol) in 1,1,1,3,3-pentafluoro-
butane (0.5 mL) at –193 °C. The mixture was stored for 10 min at
room temperature, and all volatiles were removed under reduced
pressure. The residue was dried in vacuo for 3 h to yield the product
as a voluminous colourless foam (307 mg, 0.32 mmol, 98 %), m.p.
>150 °C. 1H NMR (dichloromethane/[D6]acetone, r.t.): δ = 2.2 (s, 6
H, CH3), 3.9 (s, 2 H, CH2), 7.5–7.8 (m, 13 H, CH), 8.1 (m, 1 H, CH)
ppm. 19F NMR (dichloromethane/[D6]acetone, r.t.): δ = –149.8 (s, 1
[8]
[9]
[10]
[11]
F, BiF+), –116.9 to –115.6 (m, 6 F, CF2), –116.1 [dm, J(P,F) = 80 Hz,
2
2 F, CF2(B)], –88.3 [dm, 1J(P,F) = 902 Hz, 2 F, PF2–], –82.1 [m, 6 F,
CF3(A)], –80.5 [m, 3 F, CF3(B)], –44.7 [dm, 1J(P,F) = 890 Hz, 1 F, PF–]
ppm.
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[Ph3Bi(NCCH3)2][(C2F5)3PF3]2 (12): A sample of (C2F5)3PF2 (69 mg,
0.15 mmol) was condensed onto a suspension of Ph3BiF2 (36 mg,
0.07 mmol) in acetonitrile (2 mL). The mixture was stirred for 10 min
at room temperature, and all volatiles were removed under reduced
pressure. The residue was dried in vacuo to yield a colourless oily
residue (105 mg, 0.07 mmol, 100 %). Recrystallization from 1,1,1,3,3-
pentafluorobutane (2 mL) yielded 12 as colourless crystals. 1H NMR
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([D3]acetonitrile, r.t.): δ = 7.9 [tm, J(H,H) = 7 Hz, 3 H, CH], 8.0 [tm,
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3J(H,H) = 8 Hz, 6 H, CH], 8.0 [dm, 3J(H,H) = 9 Hz, 6 H, CH] ppm.
13C{1H} NMR ([D3]acetonitrile, r.t.): δ = 132.7 (s, CH), 132.8 (s, CH),
133.0 (s, CH), 151.0 (s, C) ppm. 19F NMR ([D3]acetonitrile, r.t.): δ =
–128.7 [d, J(P,F) = 995 Hz, 1 F, PF+], –116.7 [dm, J(P,F) = 98 Hz, 4
F, CF2(A)], –116.1 [dm, 2J(P,F) = 80 Hz, 2 F, CF2(B)], –88.1 [dm, 1J(P,F) =
902 Hz, 2 F, PF2–], –82.4 [m, 6 F, CF3(A)], –80.7 [m, 3 F, CF3(B)], –44.7
1
2
[dm, J(P,F) = 890 Hz, 1 F, PF–] ppm. 31P NMR ([D3]acetonitrile, r.t.):
1
[19]
[20]
[21]
δ = –147.8 [dtm, 1J(P,F) = 902, 1J(P,F) = 890 Hz, 1 P, P–] ppm. MS
(ESI, +): m/z (%) = 457 (100) [Ph3BiOH]+. MS (ESI, –): m/z (%): 445
(100) [(C2F5)3PF3]–.
Acknowledgments
This work was financially supported by Merck KGaA, Darmstadt,
Germany. The delivery of (C2F5)3PF2 from Merck KGaA is grate-
fully appreciated. We are grateful to Solvay GmbH (Hannover,
Germany) for providing elemental fluorine. Support by the
Deutsche Forschungsgemeinschaft (DFG), Core Facility GED@BI,
Mi477/21-1 is acknowledged, and Prof. Dr. Lothar Weber and
Dr. Julia Bader are thanked for helpful discussions. Moreover,
the authors are thankful to Dr. Julia Bader for the reactions with
elemental fluorine and to Dr. Simon Steinhauer for providing
(C2F5)3PF2 for the X-ray diffraction analysis.
[22]
[23]
[24]
[25]
[26]
[27]
[28]
Keywords: Phosphorus · Bismuth · Fluorine · Lewis acids ·
Perfluoroaryls · Structure elucidation
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Received: May 9, 2016
Published Online: June 27, 2016
Eur. J. Inorg. Chem. 2016, 3999–4010
www.eurjic.org
4010
© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim