Bismuth Perfluoroalkylphosphinates: New Catalysts for Application in Organic Syntheses

Article abstract of DOI:10.1002/chem.201604914

Commercially available BiPh₃was treated with perfluoroalkylphosphinic acids [for example, (C₂F₅)₂P(O)OH] to generate novel, highly Lewis acidic bismuth(III) perfluoroalkylphosphinates of the type Ph_xBi[R^F₂PO₂]_3?x(x=0, 1, 2) (R^F=-C₂F₅, -C₄F₉). The first bismuth(V) perfluoroalkylphosphinate, Ph₃Bi[(C₂F₅)₂PO₂]₂, was synthesized from Ph₃BiCl₂and Ag[(C₂F₅)₂PO₂]. Examples for the successful application of the catalytically active bismuth(III) and bismuth(V) phosphinates in carbon–carbon bond forming reactions, such as Friedel–Crafts acylation and alkylation, Diels–Alder, Strecker and Mannich reaction, are presented.

Full text of DOI:10.1002/chem.201604914

A Journal of
Accepted Article
Title: Bismuth Perfluoroalkylphosphinates: New Catalysts for
Application in Organic Syntheses
Authors: Sven Solyntjes, Beate Neumann, Hans-Georg Stammler,
Nikolai Ignatiev, and Berthold Hoge
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Bismuth Perfluoroalkylphosphinates: New Catalysts for Applica-
tion in Organic Syntheses
Sven Solyntjes,[a] Beate Neumann,[a] Hans-Georg Stammler,[a] Nikolai Ignat’ev[b] and Berthold Hoge*[a]
Dedication ((optional))
Abstract: Commercially available BiPh3 was treated with perfluoroal-
kylphosphinic acids [e.g. (C2F5)2P(O)OH] to generate novel, highly
Lewis acidic bismuth(III) perfluoroalkylphosphinates of the type
more convenient protocol for large quantities of the acid is based
upon the hydrolysis of (C2F5)3PF2[10] or [H(OH2)5][(C2F5)3PF3].[11]
PhxBi[RF PO2]3-x (x = 0, 1, 2) (RF= -C2F5, -C4F9). The first bismuth(V)
2
perfluoroalkylphosphinate, Ph3Bi[(C2F5)2PO2]2, was synthesized from
Ph3BiCl2 and Ag[(C2F5)2PO2]. Examples for the successful application
of the catalytically active bismuth(III) and bismuth(V) phosphinates in
carbon-carbon bond forming reactions, such as Friedel Crafts acyla-
tion and alkylation, Diels-Alder, Strecker and Mannich reaction, are
presented.
Results and Discussion
In keeping with previous methods[5], BiPh3 reacted with one equiv-
alent of (C2F5)2P(O)OH in dichloromethane to yield
Ph2Bi[(C2F5)2PO2], 1, as a colourless precipitate. The bisphos-
phinate PhBi[(C2F5)2PO2]2, 2, was prepared by prolonged heating
of
a methanol solution of BiPh3 and two equivalents of
(C2F5)2P(O)OH. This protocol, however, failed with the cleavage
of the third phenyl substituent, presumably due to the decreased
reactivity of PhBi[(C2F5)2PO2]2, 2. An effective synthesis of
Bi[(C2F5)2PO2]3, 3, makes use of stirring bismuth powder in a large
excess of the phosphinic acid for 24 h. From the reaction mixture
the bismuth(III) trisphosphinate 3 was isolated in moderate yield
(Eq. 1).
Introduction
Bismuth represents the heaviest and most metallic group 15 ele-
ment and is also the heaviest stable element in the periodic table.
It combines many interesting properties for industrial and every-
day-life applications. It is generally obtained as a byproduct in
copper, lead and tin mining and is therefore, although a rare metal,
relatively inexpensive. The most important point is the remarkably
low toxicity of most bismuth compounds, particularly with respect
to many other heavy metals. Most bismuth(III) salts are even less
toxic than table salt.[1] These advantages make bismuth(III) salts
more attractive as catalysts in industrial organic syntheses than
other Lewis acids, which are often corrosive and are responsible
for a large amount of waste during the course of the process.[2]
Various bismuth(III) salts like bismuth chloride, BiCl3, bismuth ni-
trate, Bi(NO3)3, and bismuth triflate, Bi(OTf)3, have been tested as
Lewis acidic catalysts in diverse organic reactions, whereby
Bi(OTf)3 proved to be the superior one.[3,4]
Treating triphenylbismuth, BiPh3, at room temperature with one,
two or three equivalents of triflic acid selectively leads to the cor-
responding mono-, di- and trisubstituted bismuth triflates.[5]
Bi(OTf)3 is moisture sensitive and also reacts with alcohols and
amines releasing triflic acid, CF3SO2OH.[6,7]
The bismuth(III) phosphinates 1, 2, and 3 are colourless solids.
Their stability is highlighted by the fact that these compounds are
air and moisture stable, showing no change in colour or weight
stored open on the benchtop for more than one day. The mono-
phosphinate 1 melts at 270 °C, whereas compounds 2 and 3
slowly decompose without melting above 550 °C and 490 °C, re-
spectively. The compounds 1, 2, and 3 are soluble without de-
composition in dry ethanol, methanol, DMSO, DMF and only mod-
erately soluble in acetone and acetonitrile. On the other hand in
aqueous solutions of phosphinates 1, 2, and 3 a voluminous pre-
cipitate is formed within 1 h.
Single crystals of 2 suitable for X-ray diffraction analysis were ob-
tained by slowly concentrating an ethanolic solution. The com-
pound crystallizes in the monoclinic space group P21/n. The X-ray
diffraction analysis shows the picture of endless chains of eight-
membered rings. Each ring consists of two PhBi fragments
bridged by two phosphinate groups in a kO:kO’ mode. The coor-
dination geometry around the bismuth is that of a pseudo-octahe-
dron, with an apical phenyl group and four oxygen atoms in the
The less toxic and less corrosive bis(pentafluoroethyl)phosphinic
acid, (C2F5)2P(O)OH, is of similar acidity and should represent an
excellent alternative to triflic acid.[8] (C2F5)2P(O)OH was first syn-
thesized by Shreeve at al. via hydrolysis of (C2F5)2P(O)Cl.[9]
A
[a]
[b]
S. Solyntjes, B. Neumann, Dr. H.-G. Stammler, Prof. Dr. B. Hoge
Centrum für Molekulare Materialien
Fakultät für Chemie, Anorganische Chemie
Universität Bielefeld, Universitätsstraße 25, 33615 Bielefeld (Ger-
many)
E-mail: b.hoge@uni-bielefeld.de
Dr. N. Ignat’ev,
Consulter Merck KGaA
Frankfurter Straße 250, 64293 Darmstadt (Germany)
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10.1002/chem.201604914
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square plane. The sixth position at the metal atom is occupied by
a lone pair (Figure 1). The Bi-O bond lengths range from 232 to
236 pm and are thus shorter than the shortest Bi-O distance in
Ph2Bi(OTf) [253(1) pm][12] or in Bi(OTf)3·(H2O)4 [254(5) pm][13], in-
dicating a stronger Bi-O bonding in bismuth perfluoroalkyl-
phosphinates than in triflates.
Product 4 is well soluble in alcohols and decomposes at temper-
atures above 490 °C. As expected PhBi[(C4F9)2PO2]2 is less mois-
ture sensitive than PhBi[(C2F5)2PO2]2. The solubility of 4 in organic
solvents, however, decreases in comparison to that of 2.
Figure 2. Molecular structure of [Bi{(C2F5)2PO2}2([18]crown-6)(OHCH3]
[(C2F5)2PO2]; 50 % probability amplitude displacement ellipsoids are shown;
[18]crown-6 ether pictured in wires/sticks mode with H atoms omitted for clarity;
selected bond lengths [pm] and angles [°]: Bi1–O1 230.2(4), Bi1–O3 248.0(5),
Bi1–O11 239.8(4), Bi1–O([18]crown-6) 253.5(4)-270.2(4), O11-C21 144.6(8);
O1–Bi1-O3 151.0(2).
Figure 1. Molecular structure of PhBi[(C2F5)2PO2]2, (2); 50 % probability ampli-
tude displacement ellipsoids are shown; H atoms omitted for clarity; selected
bond lengths [pm] and angles [°]: Bi1–O1-4 232.2(7)-235.7(7), Bi1–C9 219.6(8),
Bi2–O5-9 233.7(7)-236.3(7), Bi2–C23 219.3(8), P1–O1/9 150.7(7)/145.1(7),
P2–O2/8
149.8(7)/146.8(7),
P3–O3/5
148.0(8)/146.8(7),
P4–O4/6
148.6(7)/148.8(7); O1–Bi1–O2 92.4(3), O1–Bi1–O3 86.2(3), O2–Bi1–O4
86.7(3), O4–Bi1–O3 93.8(3), C9–Bi1–O1-4 84.8(5)-87.7(4), O5–Bi2–O6 90.3(3),
O5–Bi2–O8 96.0(3), O6–Bi2–O9 83.9(2), O8–Bi2–O9 89.1(3), C23–Bi2–O5-9
85.9(3)-88.4(3), O9–P1–O1 120.4(4), O8–P2–O2 120.3(5), O5–P3–O3
121.9(5), O4–P4–O6 121.7(4).
Most triarylbismuth(V) compounds of the Ar3BiX2 type are crystal-
line, non-hygroscopic solids which are soluble in many organic
solvents. The preparation, properties and applications of a large
number of these compounds have been summarized in several
reviews. Typically their oxidizing and arylating abilities are high-
lighted.[15] A frequently observed decomposition reaction is the re-
ductive elimination giving Ar2BiX and ArX. The thermal stability of
these Ar3BiX2 derivatives depends on the ancillary substituents
X.[1]
The introduction of perfluoroalkylphosphinate substituents was
carried out via a metathesis. Treating a solution of Ph3BiCl2 with
two equivalents of Ag[(C2F5)2PO2], 5, made from Ag2O and
(C2F5)2P(O)OH, leads to the first bismuth(V) perfluoroalkyl-
phosphinate Ph3Bi[(C2F5)2PO2]2, 6 (Eq. 3). This compound is ob-
tained as an air stable, colourless, hydrophobic, crystalline solid
melting at 132 °C. Product 6 is well soluble in various organic sol-
vents and solutions of 6 in water/ethanol mixtures are surprisingly
stable.
Crystals of 3 were only obtained in a poor quality from a methanol
solution, probably due to the high bridging tendency of the phos-
phinate units which was also observed for PhBi[(C2F5)2PO2]2 (see
Figure 1). However, single crystals suitable for the X-ray diffrac-
tion analysis were grown by adding one equivalent of [18]crown-6
to the methanol solution of 3, forming a salt consisting of a
[Bi{(C2F5)2PO2}2([18]crown-6)(CH3OH)]+ cation and a bis-(pen-
tafluoroethyl)phosphinate anion, [(C2F5)2PO2]-. In the cation the
bismuth(III) centre is coordinated by nine oxygen atoms (Figure
2).
In order to increase the stability of bismuth perfluoroalkyl-
phosphinates against water the introduction of longer perfluoroal-
kyl chains was envisaged. Bis(nonafluorobutyl)phosphinic acid,
(C4F9)2P(O)OH was chosen as a reactant.[14] Following the reac-
tion conditions yielding compound 2 PhBi[(C4F9)2PO2]2, 4, is ob-
tained as an air stable, colourless, hydrophobic powder (Eq. 2).
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While there are recent examples for the benzylation of arenes with
phenylethyl alcohols[4,18], examples for bismuth(III) catalysed
Friedel-Crafts alkylations with alkyl mesylates are hardly known.
For an alkylation reaction cyclohexyl methane sulfonate and ani-
sole were treated with 6.5 mol% of compound 2 at 90 °C without
solvent. After 3 h no more cyclohexyl methane sulfonate was ob-
served by 1H and 13C NMR spectroscopy. The alkylated products
were identified by comparison with literature NMR data (Eq. 4).
[19]
The same Friedel-Crafts alkylation with Sc(OTf)3
and
Cu(OTf)2[20] as catalysts show comparable results, however, with
higher catalyst loadings (10 mol%). In the absence of a catalyst
no reaction occurs under the given conditions.
Single crystals of Ph3Bi[(C2F5)2PO2]2 suitable for X-ray diffraction
analysis were obtained by slowly evaporating a solution of the
compound in ethanol. Product 6 crystallizes in the orthorhombic
space group Pbca. The bismuth centre resides in a trigonal-bi-
pyramidal environment, with three phenyl groups in equatorial
and the oxygen atoms of the monodentate phosphinates in axial
positions. The Bi-C distances fall in the range of 217(1)-220(1) pm
[16]
as observed in Ph3Bi(OSO2Ph)2
or in Ph3Bi(OTf)2
(218(1) pm)[17]. As already observed for compound 2 the Bi-O
distances of Ph3Bi[(C2F5)2PO2]2 are slightly shorter than for those
of analogous Ph3Bi(OTf)2 (232.5 pm)[17]
.
The Diels-Alder reaction is a powerful method for the construction
of cyclic or polycyclic systems. For the synthesis of natural
products this [4+2] cycloaddition requires mild conditions which
these bismuth catalysts can provide. Despite the numerous
examples of Diels-Alder and hetero Diels-Alder reactions
compiled in review articles[2] we focussed our interest on the basic
reaction of maleic anhydride with 2,3-dimethyl-1,3-butadiene or
1,3-cyclohexadiene in dichloromethane (Eq. 5). The transfor-
mations were carried out in dry dichloromethane under nitrogen
atmosphere.
Figure 3. Molecular structure of Ph3Bi[(C2F5)2PO2]2, (6); 50 % probability ampli-
tude displacement ellipsoids are shown; H atoms omitted for clarity; selected
bond lengths [pm] and angles [°]: Bi1-O1 226.0(2), Bi1-O3 225.4(2), Bi1-C9
219.3(2), Bi1-C15 218.3(2), Bi1-C21 218.4(2), P1-O1 150.5(2), P1-O2 146.4(2),
P2-O3 149.5(2), P2-O4 145.8(2); O3-Bi1-O1 175.7(1), C9-Bi1-O1 88.6(1), C9-
Bi1-O3 88.7(1), C9-Bi1-C15 114.7(1), C9-Bi1-C21 122.4(1), C15-Bi1-C21
122.9(1), O2-P1-O1 122.6(1).
The reaction was monitored by 1H and 13C NMR spectroscopy and
the products were identified by comparison with NMR data from
the literature. The conversions are quantitative after 0.5 or 1 h,
respectively. Thereby the Diels-Alder reaction is impressively ac-
celerated by only small amounts of bismuth phosphinate 2
(0.15 mol%). Without the catalyst the reaction of maleic anhydride
with 1,3-cyclohexadiene takes 6.5 h under the same conditions.
Unexpectedly, the catalytic activity of the bismuth(V) compound 6
in the Diels-Alder reaction of maleic anhydride with 1,3-cyclohex-
adiene (Eq. 6) is inferior to the one catalysed with the bismuth(III)
compound 2. Thereby the complete conversion of maleic anhy-
dride was only achieved after a reaction time of 1.5 h and with the
threefold amount of catalyst loading.
Bismuth perfluoroalkylphosphinates in carbon-carbon bond
forming reactions
To elucidate the catalytic activity of the bismuth phosphinate 2 a
number of common organic transformations were selected. The
focus was rather on a broad and versatile applicability of the cat-
alyst than on optimisation of conditions or yields of a particular
process.
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Table 1. Friedel-Crafts acylation of anisole and benzoyl chloride by various
bismuth catalysts under identical conditions.[a]
En-
try
Conversion[b]
(%)
Catalyst
Conditions
1
2
Bi(OTf)3
Inert atmosphere
24 h exp. to air
Inert atmosphere
Inert atmosphere
Inert atmosphere
Inert atmosphere
24 h exp. to air
Inert atmosphere
24 h exp. to air
Inert atmosphere
24 h exp. to air
Inert atmosphere
80
72
29
63
72
81
83
86
88
90
85
0
In order to get an impression of the degree of moisture sensitivity,
freshly prepared samples of the synthesized phosphinates 2, 3, 6
and Bi(OTf)3 were exposed to ambient air for 24 h. A sample of
Bi(OTf)3 (250 mg), synthesized under inert conditions[5], was
placed on a watch glass. Within 24 h a crumbly, clay-coloured
solid was formed, showing an increase of weight of 66 mg. This
amounts to 9.6 equivalents of water. However, for compounds 2,
3 and 6 no colour change and only an insignificant increase of
weight was observed (Figure 4).
Bi(OTf)3·n H2O
3
(C2F5)2P(O)OH
4
Ph2Bi[(C2F5)2PO2] (1)
PhBi[(C4F9)2PO2]2 (4)
PhBi[(C2F5)2PO2]2 (2)
PhBi[(C2F5)2PO2]2 (2)
Ph3Bi[(C2F5)2PO2]2 (6)
Ph3Bi[(C2F5)2PO2]2 (6)
Bi[(C2F5)2PO2]3 (3)
Bi[(C2F5)2PO2]3 (3)
no catalyst
5
6
7
8
9
10
11
12
[a] Time: 1.5 h; temperature: 140 °C; amount of catalyst: 5 mol%; [b] Con-
version followed by 1H and 13C NMR spectroscopy.
As expected a multiple substitution of phenyl groups by perfluoro-
alkylphosphinate units at the bismuth(III) centre leads to a higher
conversion in the Friedel-Crafts reaction. Longer perfluoroalkyl
chains, like e.g. the nonafluorobutyl substituent, give lower con-
versions probably due to steric effects (Entry 5). Unlike the
Ph3Bi[(C2F5)2PO2]2 catalysed Diels-Alder reaction, the Friedel-
Crafts acylation also proceeds very efficiently under the selected
conditions.
Figure 4. Illustrations of the 24 h hygroscopicity studies of Bi(OTf)3 and bis-
muth(III) compounds 2 and 3; A Bi(OTf)3 before, B after storing at ambient air;
C PhBi[(C2F5)2PO2]2 before, D after storing at ambient air; E Bi[(C2F5)2PO2]3 be-
fore, F after storing at ambient air.
Up to this point of our studies we investigated only the catalytic
activity of bismuth(III) and bismuth(V) compounds in bimolecular
reactions. One of the most important one-pot multi-component
condensation reactions is the synthesis of a-aminonitriles, which
are useful precursors for the synthesis of a-amino acids and can
efficiently be realised by the Strecker reaction. These reactions
are often characterised by their high atom economy, by mild and
simplified conditions and environmental friendliness.[22] Few bis-
muth(III) catalysed examples with Bi(NO3)3 and BiCl3 are known
to date.[23] We studied the one-pot reaction of benzaldehyde, ani-
line and trimethylsilyl cyanide in dichloromethane at room temper-
ature in the presence of phosphinate 2 as a catalyst (Eq. 8).
In order to test the influence of moisture on the catalytic activity of
the compounds listed in Table 1 we chose the Friedel-Crafts ac-
ylation between anisole and benzoyl chloride as a model reaction
(Eq. 7). The Friedel-Crafts acylation was performed under a N2
atmosphere with the air exposed bismuth catalyst as well as with
(C2F5)2P(O)OH. The degree of conversion of anisole and for-
1
mation of 4-methoxybenzophenone was ascertained by H and
13C NMR spectroscopy. Typical procedures are given in the ex-
perimental section.
Table 1 illustrates that moisture and partial hydrolysis of the new
catalysts have a small retarding effect on the process. This effect
is stronger for Bi(OTf)3 than for the bismuth phosphinates.[21]
In addition the catalytic activity of pure phosphinic acid is very low,
confirming that the here performed reactions are not promoted by
free acid (Entry 3).
The selective and quantitative conversion to the a-aminonitrile
was confirmed by 1H and 13C NMR spectroscopy after 30 minutes,
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which is four times faster than the non-catalysed one-pot Strecker
reaction under identical conditions (2 h).
We reported that previously unknown bismuth perfluoroalkyl-
phosphinate compounds, PhxBi[RF PO2]3-x (x = 0, 1, 2) (RF= -C2F5),
2
Another important multi-component C-C bond forming reaction is
the Mannich reaction, which is a classical method for the prepa-
ration of β-amino ketones and aldehydes. These β-amino carbon-
yls are of pharmaceutical interest because of their wide use as
biologically active molecules.[24] A few articles of bismuth cata-
lysed direct Mannich reactions are available in particular with air-
PhBi[(C4F9)2PO2]2 and Ph3Bi[(C2F5)2PO2]2 are very active cata-
lysts for a whole series of organic transformations.[21] The pre-
sented bismuth(III) phosphinates were successfully applied in
Friedel-Crafts alkylations and acylations, as well as in Diels-Alder,
Strecker and Mannich reactions. As an improvement over other
catalytic systems the complexes are easily available, non-hygro-
scopic, soluble in a few organic solvents and they are stable to-
wards moisture, air oxidation and heat. This allows their use of
theses new catalysts working under air without protection from
moisture.[21]
stable cationic bismuth containing heterocyclic complexes.[25]
A
smooth Mannich type reaction occurred with various silyl enolates
and silyl ketene acetals when assisted by Bi(OTf)3·(H2O)4 as a
catalyst.[26] Here the formation of trimethylsilyl triflate as the true
catalytic system is conceivable, as it is also discussed for the
Mukaiyama-aldol reaction.[7,27]
However, we performed a multi component reaction with a stoi-
chiometric mixture of benzaldehyde and aniline. Cyclohexanone
was used in excess and acted as reagent and the solvent, while
compound 3 (5 mol%) was used as the catalyst. The reaction mix-
ture was stirred at room temperature for 4 h, whereby the poorly
soluble β-amino ketone precipitated (Eq. 9). The crude product
was collected in water, stirred for 10 minutes and was then filtered
off via a glass frit. After washing with small amounts of water and
n-hexane the pure β-amino ketone was obtained as a colourless
solid with an isolated yield of 93 %. The product was identified by
1H and 13C NMR spectroscopy and mass spectrometry. The Man-
nich reaction in the absence of a catalyst showed only a 50 %
conversion after 24 h under identical conditions.
Experimental Section
Bis(pentafluoroethyl)phosphinic acid and bis(nonafluorobutyl)phosphinic
acid (Tivida® TM FL 2100) were provided by Merck KGaA (Darmstadt,
Germany). Benzaldehyde, aniline, anisole and cyclohexanone were
freshly distilled prior to use. Other reagents and solvents were obtained
from commercial sources and were used without further purification.
Standard high-vacuum techniques were employed throughout all experi-
ments with nitrogen as the inert gas.
The NMR spectra were recorded on a Bruker Model Avance III 300 spec-
trometer
(
31P 111.92 MHz; 19F 282.40 MHz; 13C 75.47 MHz; 1H
300.13 MHz) with positive shifts being downfield from the external stand-
ards (85 % orthophosphoric acid (31P), CCl3F (19F) and TMS (1H)).
IR spectra were recorded on an ALPHA-FT-IR spectrometer (Bruker). De-
termination of melting points was carried out with a Mettler Toledo MP70.
ESI mass spectra were recorded using an Esquire 3000 ion-trap mass
spectrometer (Bruker Daltonik GmbH, Bremen, Germany) equipped with a
standard ESI/APCI source. Samples were introduced by direct infusion
with a syringe pump. Nitrogen served both as the nebulizer gas and the
dry gas and was generated by a Bruker nitrogen generator NGM 11. He-
lium served as the cooling gas for the ion trap and collision gas for MS
experiments. The spectra were recorded with Bruker Daltonik esquireNT
5.2 esquireControl software by the accumulation and averaging of several
single spectra. Data analysis software 3.4 was used for processing the
spectra. C, H, and N analyses were carried out with a HEKAtech Euro EA
3000.
The crystal data for compounds 2, 3 and 6 were collected on an Agilent
SuperNova diffractometer at 100.0(1) K. Radiation used was MoKa radia-
tion (l = 71.073 pm). Suitable crystals were selected, coated with paratone
oil and mounted onto the diffractometer. Using Olex2[28] the structures
were solved with the SHELXS[29] structure solution program using direct
methods and refined with the SHELXL[29] refinement package using least-
squares minimization. Details of the X-ray investigation are given in Table
2. CCDC-1433863 (2), CCDC-1433864 (3) and CCDC-1433865 (6) con-
tain 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.
Performing this reaction with (C2F5)2P(O)OH as Brønsted acidic
catalyst under the same conditions and workup showed a signifi-
cant decrease in the isolated yield of 68 % after 4 h (Eq. 9). The
employed amount of 15 mol% phosphinic acid represents a very
high catalyst loading, but is equal to the theoretically obtained
amount of acid after complete hydrolysis of Bi[(C2F5)2PO2]3
(5.0 mol%). These experiments indicate again that the high cata-
lytic activity is not primarily caused by phosphinic acid, resulting
from hydrolysis, but rather by the bismuth(III) phosphinate deriv-
ative itself.
Synthesis of Ph2Bi[(C2F5)2PO2] (1): A sample of (C2F5)2P(O)OH (0.82 g,
2.72 mmol) was added dropwise to a solution of BiPh3 (1.25 g, 2.84 mmol)
in dichloromethane (30 mL) at room temperature. The reaction mixture
was heated under reflux for 5 h. The supernatant liquid was decanted and
the resulting solid was washed twice with dichloromethane (10 mL) and
dried in vacuo yielding 1 (1.41 g, 2.13 mmol, 78 %) as a colourless solid.
1
m. p. 270 °C; H NMR ([D4]methanol, RT): d = 7.5 (m, 2H; Hpara), 7.9 (m,
4H; Hmeta), 8.4 ppm (m, 4H; Hortho); 13C{1H} NMR ([D4]methanol, RT):
d = 129.1 (s; Cpara), 132.1 (s; Cmeta), 136.8 (s; Cortho); 194.3 ppm (s; Cquart);
13C{19F} NMR ([D4]methanol, RT): d = 111.8 (d, 1J(C,P)=137 Hz; CF2),
Conclusions
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119.0 ppm (d, 2J(C,P)=17 Hz; CF3); 19F NMR ([D4]methanol, RT):
d = -126.7 (d, 2J(P,F)=74 Hz, 4F; CF2), -82.0 ppm (m, 6F; CF3); 31P NMR
([D4]methanol, RT): d = -0.2 ppm (quint, 2J(P,F)=74 Hz); IR (solid): ꢀ = 435
(m), 447 (m), 502 (s), 567 (m), 597 (m), 638 (m), 690 (s), 721 (s), 750 (w),
909 (w), 964 (s), 996 (m), 1069 (s), 1112 (s), 1126 (s), 1163 (m), 1205 (vs),
1311 (m), 1432 (w), 1477 (w), 1572 (w), 3071 (w) cm-1; MS (ESI, pos.):
m/z (%): 665 (20) [M]+, 363 [Ph2Bi]+, 209 (50) [Bi]+.
CF3CF2CF2CF2), 111.3 (d, 2J(C,P)=10 Hz; CF3CF2CF2CF2), 114.5 (d,
1J(C,P)=134 Hz; CF3CF2CF2CF2), 117.5 ppm (s; CF3); 19F NMR
([D4]methanol, RT): d = -127.1 (m, 8F; CF3CF2CF2CF2), -122.9 (dm,
2J(P,F)=75 Hz,
8F;
CF3CF2CF2CF2),
-121.9
(m,
8F;
CF3CF2CF2CF2), -82.6 ppm (m, 12F; CF3); 31P NMR ([D4]methanol, RT):
d = 1.1 ppm (quint, 2J(P,F)=75 Hz); IR (solid): ꢀ = 400 (w), 454 (m), 489
(w), 533 (w), 558 (w), 575 (w), 693 (m), 729 (s), 750 (w), 792 (w), 815 (w),
849 (w), 1009 (m), 1031 (s), 1069 (s), 1095 (m), 1133 (vs), 1210 (vs), 1349
(w), 3061 (vw) cm-1; elemental analysis calcd (%) for C22H5BiF36O4P2: C
20.51, H 0.39; found: C 20.13.
Synthesis of PhBi[(C2F5)2PO2]2 (2): A sample of (C2F5)2P(O)OH (3.09 g,
10.23 mmol) was added dropwise to
a solution of BiPh3 (1.49 g,
3.38 mmol) in methanol (15 mL) at room temperature. The reaction mix-
ture was heated under reflux for 24 h. After removal of all volatile com-
pounds under reduced pressure, the crude product was washed twice with
water (20 mL) and diethyl ether (20 mL) and dried in vacuo at 90 °C yield-
ing 2 (2.70 g, 3.04 mmol, 89 %) as a colourless powder. dec. p. >550 °C;
1H NMR ([D6]acetone, RT): d = 7.4 (t, 3J(H,H)=7 Hz, 1H; Hpara), 8.3 (t,
3J(H,H)=8 Hz, 2H; Hmeta), 9.2 ppm (d, 3J(H,H)=7 Hz, 2H; Hortho);
13C{1H} NMR ([D6]acetone, RT): d = 130.4 (s; Cpara), 134.3 (s; Cmeta), 138.2
(s; Cortho), 230.9 ppm (s; Cquart); 13C{19F} NMR ([D6]acetone, RT): d = 112.1
(d, 1J(C,P)=141 Hz; CF2), 119.4 ppm (d, 2J(C,P)=18 Hz; CF3); 19F NMR
([D6]acetone, RT): d = -126.0 (d, 2J(P,F)=77 Hz, 8F; CF2), -81.2 ppm (m,
12F; CF3); 31P NMR ([D6]acetone, RT): d = 0.6 ppm (quint, 2J(P,F)=77 Hz);
IR (solid): ꢀ = 428 (w), 442 (w), 498 (s), 569 (s), 599 (w), 634 (w), 689 (w),
728 (w), 750 (w), 963 (s), 999 (s), 1070 (s), 1113 (s), 1135 (s), 1164 (s),
1205 (vs), 1309 (m), 1434 (w), 3074 (w) cm-1; MS (ESI, pos.): m/z (%): 889
(50) [M]+, 587 (60) [PhBi(C2F5)2PO2]+, 209 (75) [Bi]+; MS (ESI, neg.): m/z
(%): 1189 (100) [M+(C2F5)2PO2]–, 965 (90) [Ph2Bi{(C2F5)2PO2}2]–, 301 (40)
[(C2F5)2PO2]–; elemental analysis calcd (%) for C14H5BiF20O4P2: C 18.93,
H 0.57; found: C 18.11. H 0.45. Crystals were obtained by slowly concen-
trating a solution of compound 2 in ethanol.
Synthesis of Ag[(C2F5)2PO2] (5): A sample of Ag2O (6.17 g, 26.63 mmol)
was added portionwise to
a solution of (C2F5)2P(O)OH (15.03 g,
49.77 mmol) in acetonitrile (50 mL) at room temperature. The reaction mix-
ture was heated under reflux for 3 h, not soluble components were filtered
off, the solvent was removed under reduced pressure and the residue was
dried in vacuo overnight. After adding diethyl ether (50 mL) the solution
was stirred over charcoal and filtered. Removing the solvent under re-
duced pressure and drying in vacuo yielded silver phosphinate 5 (15.50 g,
38.01 mmol, 76 %) as an off-white solid. 13C NMR ([D3]acetonitrile, RT):
d = 112.5 (d, 1J(C,P)=127 Hz; CF2), 119.5 ppm (d, 2J(C,P)=16 Hz; CF3);
19F NMR ([D3]acetonitrile, RT): d = -125.7 (d, 2J(P,F)=69 Hz, 4F;
CF2), -81.1 ppm (s, 6F; CF3); 31P NMR ([D3]acetonitrile, RT ): d = -0.2 ppm
(quint, 2J(P,F)=69 Hz); IR (solid): ꢀ = 430 (w), 497 (s), 559 (m), 631 (vw),
753 (w), 966 (m), 983 (m), 1078 (s), 1118 (m), 1147 (m), 1159 (m), 1204
(w), 1267 (m), 1292 (w), 1373 (w), 1661 (vw), 2285 (vw), 2951 (vw) cm-1;
MS (ESI, pos.): m/z (%): 599 (50) [Ag2(C2F5)2PO2(CH3CN)2]+, 301 (10)
[(C2F5)2PO2H2]+, 189 (100) [Ag(CH3CN)2]+, 150 (10) [Ag(CH3CN)]+,
107/109 (5) [Ag]+; MS (ESI, neg.): m/z (%): 303 (100) [(C2F5)2PO2]–, 201
(20)
[(C2F5)PFO2]–;
elemental
analysis
calcd
(%)
for
C4AgF10O2P + 0.06 CH3CN: C 12.04, N 0.21; found: C 12.41, N 0.21.
Synthesis of Bi[(C2F5)2PO2]3 (3): A sample of (C2F5)2P(O)OH (24.02 g,
79.55 mmol) was added dropwise to freshly pestled bismuth powder
(3.43 g, 16.39 mmol) at room temperature. The reaction mixture was
heated at 140 °C for 24 h, cooled to room temperature and was then
solved in methanol (25 mL). Unreacted bismuth powder was filtered off
and the solvent was removed under reduced pressure. After adding diethyl
ether (50 mL) to the residue, the resulting precipitate was filtered off. The
residue was washed four times with diethyl ether (20 mL) and dried in
vacuo yielding 3 (5.98 g, 5.38 mmol, 33 %) as a colourless solid. dec. p.
>490 °C; 13C{19F} NMR (methanol/[D6]acetone, RT): d = 112.4 (d,
1J(C,P)=138 Hz; CF2), 119.6 ppm (d, 2J(C,P)=17 Hz; CF3); 19F NMR meth-
anol/[D6]acetone, RT): d = -126.2 (d, 2J(P,F)=74 Hz, 12F; CF2), -81.5 ppm
(s, 18F; CF3); 31P NMR (methanol/ [D6]acetone, RT): d = 0.6 ppm (quint,
2J(P,F)=74 Hz); IR (solid): ꢀ = 429 (m), 473 (w), 496 (m), 519 (m), 571 (m),
601 (m), 641 (w), 752 (w), 958 (s), 1003 (m), 1056 (m), 1083 (m), 1160
(m), 1122 (s), 1174 (m), 1213 (s), 1314 (w) cm-1; elemental analysis calcd
(%) for C12BiF30O6P3: C 12.96; found: C 13.01. Crystals were obtained by
adding one equivalent of [18]crown-6 to a methanol solution of 3, forming
[Bi{(C2F5)2PO2}2([18]crown-6)(OHCH3)][(C2F5)2PO2].
Synthesis of Ph3Bi[(C2F5)2PO2]2 (6): A sample of SO2Cl2 (0.68 g,
5.0 mmol) was condensed onto a solution of BiPh3 (1.58 g, 3.59 mmol) in
dichloromethane (20 mL) and stirred at room temperature for 1 h. All vola-
tile compounds were removed in vacuo leaving Ph3BiCl2 as an off-white
solid in quantitative yield. A solution of Ph3BiCl2 in dichloromethane
(20 mL) was combined with Ag[(C2F5)2PO2] (3.24 g, 7.20 mmol) and the
reaction mixture was stirred at room temperature for 1 h. The resulting pre-
cipitate was filtered off and the filtrate was freed from all volatile com-
pounds under reduced pressure. Recrystallization of the crude product
from cyclohexane yields 6 (2.61 g, 2.50 mmol, 70 % yield related to BiPh3)
as colourless needles. m. p. 130-133 °C; dec. >170 °C; 1H NMR ([D6]ace-
tone, RT): d = 7.7 (t, 3J(H,H)=7 Hz, 3H; Hpara), 7.9 (t, 3J(H,H)=8 Hz, 6H;
Hmeta), 8.1 ppm (d, 3J(H,H)=8 Hz, 6H; Hortho); 13C{1H} NMR ([D6]acetone,
RT): d = 133.0 (s; Cpara), 133.6 (s; Cmeta), 134.1 (s; Cortho), 155.2 ppm (s;
Cquart); 13C{19F} NMR ([D6]acetone, RT): d = 110.9 (d, 1J(C,P)=145 Hz;
CF2), 118.1 ppm (d, 2J(C,P)=20 Hz; CF3); 19F NMR ([D6]acetone, RT):
d = -124.3 (d, 2J(P,F)=83 Hz, 8F; CF2), -80.7 ppm (m, 12F; CF3); 31P NMR
([D6]acetone, RT): d = 0.6 ppm (quint, 2J(P,F)=83 Hz); IR (solid): ꢀ = 408
(w), 445 (s), 501 (s), 512 (s), 547 (w), 567 (s), 597 (m), 636 (w), 651 (w),
677 (m), 727 (m), 750 (w), 962 (s), 985 (s), 992 (s), 1047 (s), 1069 (m),
1105 (s), 1128 (s), 1147 (s), 1205 (vs), 1289 (s), 1442 (w), 1472 (w), 1561
(w), 3070 (vw) cm-1; MS (ESI, pos.): m/z (%): 741 (100) [Ph3Bi(C2F5)2PO2]+,
587 (10) [PhBi(C2F5)2PO2]+, 363 (50) [Ph2Bi]+, 286 (90) [BiPh]+, 209 (30)
[Bi]+; MS (ESI, neg.): m/z (%): 301 (100) [(C2F5)2PO2]–, 201 (20)
[(C2F5)PFO2]–; elemental analysis calcd (%) for C26H15BiF20O4P2: C 29.96,
H 1.45; found: C 29.80, H 1.53, N 0.13. Crystals were obtained by slowly
evaporating a solution of compound 6 in ethanol.
Synthesis of PhBi[(C4F9)2PO2]2 (4): An aqueous solution of
(C4F9)2P(O)OHwas evaporated to dryness for 24 h yielding the phosphinic
acid (7.63 g, 15.21 mmol) as a colourless solid. The obtained solid was
then added to a solution of BiPh3 (2.20 g, 5.00 mmol) in methanol (50 mL)
and the reaction mixture was heated under reflux for 20 h. Non-soluble
components were filtered off and the solvent was removed under reduced
pressure. After adding diethyl ether (50 mL) to the residue, the resulting
precipitate was filtered off, washed four times with diethyl ether (20 mL)
and dried in vacuo to yield 4 (4.35 g, 3.37 mmol, 68 %) as a colourless
solid. dec. p. >490 °C; 1H NMR ([D4]methanol, RT): d = 7.6 (m, 1H; Hpara),
8.3 (m, 2H; Hmeta), 8.8 ppm (m, 2H; Hortho); 13C{1H} NMR ([D4]methanol,
RT): d = 129.9 (s; Cpara), 134.2 (s; Cmeta), 137.1 (s; Cortho), 230.9 ppm (s;
Cquart); 13C{19F} NMR ([D4]methanol, RT): d = 109.0 (d, 3J(C,P)=3 Hz;
Bi phosphinate catalysed C-C bond forming reactions:
Typical procedure for a Bi phosphinate catalysed Friedel Crafts alkyl-
ation: Cyclohexyl methane sulfonate (1.036 g, 5.812 mmol) was added
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10.1002/chem.201604914
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to PhBi[(C2F5)2PO2]2 (335 mg, 0.377 mmol, 6.49 mol%) in a 25 mL
Schlenk tube. Anisole (1.295 g, 11.974 mmol) was added and the reaction
mixture was stirred at 90 °C for 3 h. The conversion of cyclohexyl methane
4.839 mmol, 68 %). The product was identified according to literature
known NMR spectroscopic data.
sulfonate and formation of cyclohexyl anisole were followed by 1H and 13
NMR spectroscopy.
C
Table 2. Structure and refinement data of PhBi[(C2F5)2PO2]2, 2;
Bi[(C2F5)2PO2]3, 3 and Ph3Bi[(C2F5)2PO2]2, 6.
2
3
6
Typical procedure for a Bi phosphinate catalysed Diels-Alder reac-
tion: Maleic anhydride (993 mg, 10.127 mmol) was added to
PhBi[(C2F5)2PO2]2 (13 mg, 0.015 mmol, 0.15 mol%) in a 25 mL Schlenk
tube. 2,3-Dimethyl-1,3-butadiene (2.468 g, 30.050 mmol) was added and
the reaction mixture was stirred at room temperature for 30 min. The con-
version to the Diels-Alder adduct was followed by 1H and 13C NMR spec-
troscopy.
Crystallographic Section
C14H5BiF20O4P2 C25H28BiF30O13P3
empirical for-
mula
C26H15BiF20O4P2
a / pm
1544.7(4)
2058.4(2)
1543.9(3)
90
1200.30(2)
1555.70(2)
2408.83(4)
89.1804(12)
88.0205(12)
88.9555(12)
4494.19(12)
4
1589.07(3)
1716.37(4)
2408.96(4)
90
b / pm
Typical procedure for a Bi phosphinate catalysed Friedel Crafts acyl-
ation: Benzoyl chloride (441 mg, 3.14 mmol) was added to
Bi[(C2F5)2PO2]3 (149 mg, 0.134 mmol, 4.95 mol%) in a 25 mL Schlenk
tube under a nitrogen atmosphere. Anisole (293 mg, 2.71 mmol) was
added and the reaction mixture was stirred at 140 °C for 1.5 h. The colour
changes rapidly to pale yellow and then to dark red. The conversion to
4-methoxybenzophenone was followed by 1H and 13C NMR spectroscopy.
For reactions under ambient atmosphere a weighted amount of catalysts
was stored for 24 h on a watch glass in air. Catalyst loadings and substrate
stoichiometry were calculated with the originally determined weights.
The pure product was obtained by extracting the reaction mixture with di-
ethyl ether. This extract was washed twice with water and concentrated
NaHCO3 solution. After drying the organic phase over MgSO4 and remov-
ing the solvent under reduced pressure the orange residue was crystal-
lised from n-hexane/diethyl ether (2:1) yielding 4-methoxybenzophenone
as a colourless solid identified by 1H and 13C NMR spectroscopy and mass
spectrometry.
c / pm
a / °
96.37(3)
90
90
b / °
90
g /°
V / 106 Å3
Z
4878.5(18)
8
6570.3(2)
8
ρcalc / mg∙mm-3
crystal system
space group
2.418
2.081
2.107
monoclinic
P21/n
triclinic
orthorhombic
Pbca
P1¯
colourless frag-
ment
colourless frag-
ment
shape / color
colourless block
Typical procedure for a Bi phosphinate catalysed Strecker reaction:
Benzaldehyde (distilled) (210 mg, 1.978 mmol) and aniline (distilled)
(184 mg, 1.972 mmol) were added to PhBi[(C2F5)2PO2]2 (117 mg,
0.132 mmol, 6.67 mol%) in a 25 mL Schlenk tube. Trimethylsilyl cyanide
(292 mg, 2.946 mmol) was added and the reaction mixture was stirred at
room temperature for 30 min. The conversion to the α-aminonitrile was fol-
lowed by 1H and 13C NMR spectroscopy.
crystal size /
mm-3.
0.36
0.09
x
0.14
x
0.31
0.16
x
0.28
x
0.35
0.23
x 0.29 x
Data Collection
4.210
μ / mm-1
F(000)
5.550
5.612
3312.0
2720.0
3968.0
Typical procedure for a Bi phosphinate catalysed Mannich type reac-
tion: A sample of Bi[(C2F5)2PO2]3 (364 mg, 0.327 mmol, 5.00 mol%) was
combined with a mixture of benzaldehyde (694 mg, 6.540 mmol), aniline
(606 mg, 6.507 mmol) and cyclohexanone (2.584 g, 26.329 mmol) in a
50 mL Schlenk flask. The reaction mixture was stirred for 4 h at room tem-
perature, whereby a colourless solid precipitated. Water (10 mL) was
added and the mixture was stirred for 10 min. The crude product was fil-
tered off via a frit, and the filter cake was washed four times with water
(5 mL) as well as n-hexane (5 mL). The residue was dried in vacuo yielding
the b-aminoketone as a colourless solid (1.697 g, 6.074 mmol, 93 %). The
product was identified according to literature known NMR spectroscopic
and mass spectrometric data.
2θ range for
data collection
3.31 to 59.998°
4876 to 59.998°
3.382 to 60.162°
−21 ≤ h ≤ 21
−28 ≤ k ≤ 28
−21 ≤ l ≤ 21
−16≤ h ≤ 16
−21 ≤ k ≤ 21
−33 ≤ l ≤ 33
−15 ≤ h ≤ 22
−24 ≤ k ≤ 22
−33 ≤ l ≤ 33
index ranges
reflections
collected
284807
261486
59963
independent
reflections
14223
[R(int) = 0.0868]
26174
9634
[R(int) = 0.0332]
[R(int) = 0.0878]
26174/4/1305
data/re-
straints/
parameters
Typical procedure for a (C2F5)2P(O)OH catalysed Mannich type reac-
tion: A sample of (C2F5)2P(O)OH (336 mg, 1.113 mmol, 15.6 mol%) was
added to a mixture of benzaldehyde (760 mg, 7.162 mmol), aniline
(665 mg, 7.140 mmol) and cyclohexanone (2.051 g, 20.898 mmol) in a
50 mL Schlenk flask. The reaction mixture was stirred at room temperature
for 4 h while a colourless solid precipitated. Water (10 mL) was added, the
supernatant was removed and the residue was collected in diethyl ether.
The crude product was filtered off via a frit and the filter cake was washed
four times with water (5 mL) as well as n-hexane (5 mL). The residue was
dried in vacuo yielding the b-aminoketone as a colourless solid (1.352 g,
14223/0/648
9634/23/503
goodness-of-
fit on F2
1.109
0.991
1.038
R1 / wR2
[I≤2σ(I)]
0.0535 / 0.1305
0.0573 / 0.1342
0.0557 / 0.1424
0.0669 / 0.1513
0.0227 / 0.0485
0.0325 / 0.0516
R1 / wR2
(all data)
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Entry for the Table of Contents (Please choose one layout)
Layout 2:
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Sven Solyntjes, Beate Neumann, Hans-
Georg Stammler, Nikolai Ignat’ev and
Berthold Hoge*
Page No. – Page No.
Bismuth Perfluoroalkylphosphinates:
New Catalysts for Application in Or-
ganic Syntheses
Bismuth perfluoroalkylphosphinate compounds, PhxBi[RF PO2]3-x (x = 0, 1, 2)
2
(RF= -C2F5, -C4F8), and Ph3Bi[(C2F5)2PO2]2 are very active catalysts for a whole series
of organic transformations, such as Friedel-Crafts alkylations and acylations, as well
as Diels-Alder, Strecker and Mannich type reactions. As an improvement over other
catalytic systems the complexes are easily available, non-hygroscopic, soluble in a
few organic solvents and they are stable towards moisture, air oxidation and heat.
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