BISMUTH PERFLUOROALKYLPHOSPHINATES AS LEWIS ACID CATALYSTS

Abstract

The invention relates to bismuth perfluoroalkylphosphinates as Lewis acid catalysts, the compounds, and processes for the preparation thereof.

Ar.sub.xBi[OP(O)(R.sub.f).sub.2].sub.3-x(Ia),

Ar.sub.3Bi[OP(O)(R.sub.f).sub.2].sub.2(Ib).

Claims

1. Compounds the formula (Ia) or (Ib)
Ar.sub.xBi[OP(O)(R.sub.f).sub.2].sub.3-x(Ia),
Ar.sub.3Bi[OP(O)(R.sub.f).sub.2].sub.2(Ib) where Ar in each case, independently of one another, denotes an aryl group having 6 to 12 C atoms, which may be unsubstituted or substituted; R.sub.f in each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms and x denotes 0, 1 or 2.

2. Compounds according to claim 1, where Ar is identical on each occurrence.

3. Compounds according to claim 1, where the perfluoroalkyl group R.sub.f is identical on each occurrence.

4. Compounds according to claim 1, where R.sub.f is selected from pentafluoroethyl or n-nonafluorobutyl.

5. Process for the preparation of compounds of the formula (Ia) according to claim 1, where x denotes 0, characterised in that bismuth is reacted with a compound of the formula (II)
HOP(O)(R.sub.f).sub.2(II), where R.sub.f in each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms.

6. Process for the preparation of compounds of the formula (Ia) according to claim 1, where x denotes 1 or 2, characterised in that a compound of the formula (II)
HOP(O)(R.sub.f).sub.2(II), where R.sub.f in each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms, is reacted with triarylbismuthane, where the aryl in each case, independently of one another, denotes an aryl group having 6 to 12 C atoms.

7. Process for the preparation of compounds of the formula (Ib) according to claim 1, characterised in that triarylbismuthane is converted to triaryldichlorobismuthane, where aryl in each case, independently of one another, denotes an aryl group having 6 to 12 C atoms, which may be unsubstituted or substituted, and triaryldichlorobismuthane is reacted with a compound of the formula (III),
Ag[(R.sub.f).sub.2PO.sub.2](III), where R.sub.f in each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms.

8. Process for the preparation of compounds of the formula (Ib) according to claim 1, characterised in that a compound of the formula (II),
HOP(O)(R.sub.f).sub.2(II), where R.sub.f in each case, independently of one another, denotes a straight-chain or branched perfluoroalkyl group having 1 to 8 C atoms, is reacted with triarylbismuth(V) carbonate, triarylbismuth(V) diacetate or triarylbismuth(V) dichloride, where the aryl in each case, independently of one another, denotes an aryl group having 6 to 12 C atoms.

9. A Lewis acid-catalysed reaction selected from a condensation reaction, alcoholysis, aldol reaction, Mukaiyama aldol reaction, Gattermann-Koch reaction, Beckmann and Fries rearrangement, Friedel-Crafts acylation, Friedel-Crafts alkylation, Mannich reaction, Diels-Alder reaction, aza-Diels-Alder reaction, Baylis-Hillman reaction, Reformatsky reaction, Claisen rearrangement, Prins cyclisation reaction, allylation of carbonayl compounds, cyanation of aldehydes and ketones, cyanosilylation of aldehydes and ketones, Strecker reaction, 1,3-dipolar cycloaddition or Michael reaction, comprising subjecting a feed appropriate for said reaction to reaction conditions in the presence of a compound according to claim 1.

10. A Lewis acid catalyst, comprising compound according to claim 1, which compound is effective as a Lewis acid catalyst.

Description

EXAMPLES

Example 1. Preparation of phenylbis(pentafluoroethylphosphinyl)-bismuth(III), PhBi[O(O)P(C.SUB.2.F.SUB.5.).SUB.2.].SUB.2

[0073] ##STR00001##

[0074] 3.09 g (10.2 mmol) of bis(pentafluoroethyl)phosphinic acid, (C.sub.2F.sub.5).sub.2P(O)OH, in 15 ml of methanol are initially introduced in a 50 ml Schlenk flask in a counterstream of nitrogen, and 1.49 g (3.4 mmol) of triphenylbismuth are slowly added. The reaction mixture is heated under reflux for 24 hours. All volatile constituents of the reaction solution are removed in a high vacuum. The residue washed twice with water, and the residue obtained dried at 90 C. in a high vacuum, giving a colourless, finely powdered solid.

[0075] Yield of PhBi[O(O)P(C.sub.2F.sub.5).sub.2].sub.2 (based on triphenylbismuth): 2.70 g (3.0 mmol, 89%). Decomposition point: >550 C.

[0076] IR: {tilde over (v)}=3074 (w), 1434 (w), 1309 (m), 1205 (vs), 1164 (s), 1135 (s), 1113 (s), 1070 (s), 999 (s), 963 (s), 750 (w), 728 (w), 689 (w), 634 (w), 599 (w), 569 (s), 498 (s), 442 (w), 428 (w).

TABLE-US-00001 TABLE NMR data of phenylbis(pentafluoroethylphosphinyl)bismuth(III), PhBi[O(O)P(C.sub.2F.sub.5).sub.2].sub.2 in acetone-d.sub.6. Nucleus [ppm] Splitting J [Hz] Assignment .sup.1H 9.2 d .sup.3J.sub.HH = 7.0 ortho H 8.3 t .sup.3J.sub.HH = 7.7 meta H 7.4 t .sup.3J.sub.HH = 7.4 para H .sup.13C-CPD 138.2 ortho C 134.3 meta C 130.4 para C .sup.13C, .sup.19F- 119.4 d .sup.3J.sub.CP = 17.8 CF.sub.3CF.sub.2 DEPT135 112.1 d .sup.2J.sub.CP = 140.6 CF.sub.3CF.sub.2 .sup.19F 81.2 s CF.sub.3CF.sub.2 125.5 d .sup.2J.sub.FP = 77.0 CF.sub.3CF.sub.2 .sup.31P 0.6 qui .sup.2J.sub.FP = 77.0 P

TABLE-US-00002 TABLE Mass spectrometry data of phenylbis(pentafluoroethyl- phosphinyl)bismuth (III), PhBi[O(O)P(C.sub.2F.sub.5).sub.2].sub.2, ESI negative. m/z rel. intensity (%) Fragment 1188.6 100 964.7 90 904.6 30 602.6 40 300.7 40 [P(O)O(C.sub.2F.sub.5).sub.2].sup.

Example 2. Preparation of Bi(III)[C.SUB.2.F.SUB.5.).SUB.2.PO.SUB.2.].SUB.3

[0077] ##STR00002##

[0078] 3.420 g (16.365 mmol) of ground bismuth powder are initially introduced in a 50 ml round-bottomed flask, and 15.544 g (51.469 mmol) of bis(pentafluoroethyl)-phosphinic acid are added via a pipette. The mixture is heated at 140 C. for 24 h. After cooling, the greyish reaction mixture is taken up in 25 ml of methanol, unreacted metal powder (Bi) is separated off by filtration, the filtrate is evaporated in a rotary evaporator and dried overnight in a high vacuum. The residue is taken up in 50 ml of diethyl ether, filtered and washed four times with 20 ml of diethyl ether each time. The colourless solid obtained is dried in a high vacuum. Yield (based on bismuth): 5.09 g (4.58 mmol, 28%).

[0079] Decomposition point: >490 C.

[0080] IR: {tilde over (v)}=1314 (w), 1213 (s), 1174 (m), 1160 (m), 1122 (s), 1083 (m), 1056 (m), 1003 (m), 958 (s), 752 (w), 641 (w), 601 (m), 571 (m), 519 (m), 496 (m), 473 (w), 429 (m).

TABLE-US-00003 TABLE NMR data of Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.3 in methanol with acetone-d.sub.6 as standard at RT. Nucleus [ppm] Splitting J [Hz] Assignment .sup.19F 81.5 s CF.sub.3CF.sub.2 126.0 d .sup.2J.sub.FP = 74.2 CF.sub.3CF.sub.2 .sup.31P 0.6 qui .sup.2J.sub.FP = 74.2 P .sup.13C, .sup.19F- 119.6 d .sup.2J.sub.CP = 17.0 CF.sub.3CF.sub.2 DEPT135 112.4 d .sup.2J.sub.CP = 138.2 CF.sub.3CF.sub.2

[0081] No .sup.1H signals are detected in the .sup.1H-NMR spectrum for the solution Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.3 in acetone-d.sub.6. This result confirms that Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.3 does not react with methanol at room temperature.

Example 3. Preparation of triphenylbis[bis(pentafluoroethyl)-phosphinyl)]bismuth(V), Ph.SUB.3.Bi[(C.SUB.2.F.SUB.5.).SUB.2.PO.SUB.2.].SUB.2

[0082] A) Preparation of Silver(I) bis(pentafluoroethyl)phosphinate, {Ag[(C.sub.2F.sub.5).sub.2PO.sub.2]

##STR00003##

[0083] 6.17 g of silver(I) oxide (26.63 mmol) are added in portions to a solution of (C.sub.2F.sub.5).sub.2P(O)OH (15.03 g, 49.77 mmol) in acetonitrile (50 ml), and the reaction mixture is heated under reflux for 3 h. All insoluble components are filtered off, the solvent is removed under reduced pressure, and the residue is dried overnight in a high vacuum. The residue is taken up in diethyl ether (50 ml) and stirred over active carbon. After filtration and removal of the solvent, the colourless solid obtained is dried in a high vacuum.

[0084] The yield is 15.50 g (38.01 mmol, 76% based on (C.sub.2F.sub.5).sub.2P(O)OH).

[0085] .sup.13C{.sup.19F} NMR (CD.sub.3CN, RT), , ppm: 112.5 (d, .sup.1J(C,P)=127 Hz; CF2), 119.5 (d, .sup.2J(C,P)=16 Hz; CF3);

[0086] .sup.19F NMR (CD.sub.3CN, RT), , ppm: 125.7 (d, .sup.2J(P,F)=69 Hz, 4F; CF2), 81.1 (s, 6F; CF3);

[0087] .sup.31P NMR (CD.sub.3CN, RT), , ppm: 0.2 (quint, .sup.2J(P,F)=69 Hz).

B) Preparation of Triphenylbismuthane, Ph.SUB.3.Bi

[0088] 5.52 g (795 mmol) of lithium in 250 ml of diethyl ether (Et.sub.2O) are initially introduced in a 1 l three-necked flask with reflux condenser. 44 ml (420 mmol) of bromobenzene are slowly added dropwise via a 250 ml dropping funnel with stirring, so that the diethyl ether boils continuously. When the addition is complete, the grey-brown suspension is heated under reflux for 30 min, and 32.74 g (104 mmol) of bismuth trichloride are subsequently added. The mixture is stirred at RT for 15 h.

[0089] The suspension is hydrolysed using distilled water with ice-bath cooling and neutralised using a saturated ammonium chloride solution. The organic phase is separated off, and the aqueous phase is extracted twice with Et.sub.2O. The combined organic phases are dried over MgSO.sub.4, and the solvent is removed in a high vacuum. The residue is recrystallised from 80 ml of Et.sub.2O. Repeated decantation and evaporation of the mother liquor and drying in a high vacuum gives triphenylbismuthane in the form of colourless needles.

[0090] The yield is 39.26 g (89.21 mmol, 86% based on bismuth trichloride).

[0091] .sup.1H NMR (CDCl.sub.3), , ppm: 7.8 (m, Hortho), 7.4 (m, Hmeta, Hpara).

C) Conversion to triphenylbis[bis(pentafluoroethyl)phosphinyl)]bismuth(V), Ph.sub.3Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.2

##STR00004##

[0092] 0.68 g (5.00 mmol) of SO.sub.2Cl.sub.2 are condensed onto a solution of triphenylbismuthane (1.58 g, 3.59 mmol) in dichloromethane (20 ml), and the reaction mixture is stirred at room temperature (RT) for one hour. All volatile constituents are removed in a high vacuum, until Ph.sub.3BiCl.sub.2 is obtained as a colourless solid. The residue is taken up in dichloromethane (20 ml), 3.24 g (7.20 mmol) of Ag[(C.sub.2F.sub.5).sub.2PO.sub.2] are added, and the reaction mixture is stirred at room temperature for one hour. The solid which precipitates out is filtered off, and the filtrate is evaporated under reduced pressure. The crude product is recrystallised from cyclohexane, and drying in a high vacuum gives Ph.sub.3Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.2 as colourless needles.

[0093] The yield is 2.61 g (2.50 mmol, 70% based on BiPh.sub.3).

[0094] Melting point: 130-133 C., decomposition: >170 C.

[0095] .sup.1H NMR ([D.sub.6]acetone, RT), , ppm: 7.7 (t, .sup.3J(H,H)=7 Hz, 3H; Hpara), 7.9 (t, .sup.3J(H,H)=8 Hz, 6H; Hmeta), 8.1 (d, .sup.3J(H,H)=8 Hz, 6H; Hortho);

[0096] .sup.13C{.sup.1H} NMR ([D.sub.6]acetone, RT), , ppm: 133.0 (s; Cpara), 133.6 (s; Cmeta), 134.1 (s; Cortho), 155.2 (s, Cquart);

[0097] .sup.13C{.sup.19F} NMR ([D.sub.6]acetone, RT), , ppm: 110.9 (d, .sup.1J(C,P)=145 Hz; CF.sub.2), 118.1 (d, .sup.2J(C,P)=20 Hz; CF.sub.3);

[0098] .sup.19F NMR ([D.sub.6]acetone, RT), , ppm: 124.3 (d, .sup.2J(P,F)=83 Hz, 8F; CF.sub.2), 80.7 (m, 12F; CF.sub.3);

[0099] .sup.31P NMR ([D.sub.6]acetone, RT), , ppm: 0.6 (quint, .sup.2J(P,F)=83 Hz);

[0100] IR (solid): {tilde over (v)}=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.sup.1;

[0101] MS (ESI): m/z (%): 741 (100) [Ph.sub.3Bi(C.sub.2F.sub.5).sub.2PO.sub.2].sup.+, 587 (10) [PhBi(C.sub.2F.sub.5).sub.2PO.sub.2].sup.+, 363 (50) [Ph.sub.2Bi].sup.+, 286 (90) [BiPh].sup.+, 209 (30) [Bi].sup.+; 301 (100) [(C.sub.2F.sub.5).sub.2PO.sub.2].sup., 201 (20) [(C.sub.2F.sub.5)PFO.sub.2].sup.;

[0102] Elemental analysis calculated (found) [%] for C.sub.26H.sub.15BiF.sub.20O.sub.4P.sub.2: C, 29.96 (C, 29.80); H, 1.45 (H, 1.53); (N, 0.13).

Comparative Example 4. Preparation of Bi(OTf).SUB.3 .(Anhydrous)

[0103] ##STR00005##

[0104] 4.50 g (10.0 mmol) of triphenylbismuth in 100 ml of dried dichloromethane are initially introduced in a 250 ml Schlenk flask in a counterstream of nitrogen and cooled to 70 C. in a cooling bath. 2.7 ml (31.0 mmol) of trifluoromethanesulfonic acid (triflic acid) are then added slowly, and the reaction mixture is warmed to room temperature overnight. The reaction mixture is filtered under an inert atmosphere. The residue obtained is washed twice with dichloromethane and dried in a high vacuum, giving 5.59 g (8.5 mmol) of a beige solid. The yield of Bi(OTf).sub.3 is 85%.

[0105] The NMR analytical data correspond to the values indicated in the literature [M. Labrouillere, et al., Tetrahedron Lett., 40 (1999), p. 285-286].

Examples for the Determination of the Catalytic Activity:

[0106] The catalysis reactions selected are carried out in 10-25 ml Schlenk tubes and under standard Schlenk conditions. Firstly, the bismuth perfluoroalkylphosphinate is weighed in and the corresponding stoichiometry of the starting materials and of the solvent is adjusted.

[0107] In order to calculate the conversion, a component having previously selected, characteristic NMR signals is employed in a sub-stoichiometric amount. If these marker signals are no longer detected in the NMR signal spectrum, quantitative conversion can be assumed. No further work-up or determination of isolated yields is carried out. The times are taken after addition of the starting material employed in sub-stoichiometric amount. The end point is sampling.

[0108] Blank samples were carried out for confirmation of the catalytic activity.

Comparative Example 5. Friedel-Crafts Acylation with Bi(OSO.SUB.2.CF.SUB.3.).SUB.3 .as Catalyst

[0109] ##STR00006##

[0110] 225 mg (0.343 mmol) of Bi(OTf).sub.3 and 1.051 g (7.48 mmol) of benzoyl chloride are initially introduced in a 25 ml Schlenk tube in a counterstream of nitrogen. 735 mg (6.80 mmol) of anisole are added, and the mixture is stirred at 140 C. for 1.5 hours. The reaction mixture rapidly becomes yellow, later becomes a dark red colour and is solid at room temperature.

[0111] According to .sup.1H- and .sup.13C-NMR spectroscopy investigations, the conversion to 4-methoxybenzophenone is 80%.

Example 6. Friedel-Crafts Acylation with Bi[(C.SUB.2.F.SUB.5.).SUB.2.PO.SUB.2.].SUB.3 .as Catalyst

[0112] ##STR00007##

[0113] 149 mg (0.134 mmol) of Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.3 and 441 mg (3.137 mmol) of benzoyl chloride are initially introduced in a 25 ml Schlenk tube in a counterstream of nitrogen. 293 mg (2.710 mmol) of anisole are added, and the mixture is stirred at 140 C. for 1.5 hours. The solution rapidly becomes yellow, later dark red.

[0114] The conversion to 4-methoxybenzophenone detected by .sup.1H- and .sup.13C-NMR spectroscopy is 90%.

[0115] The reaction product is obtained by extraction of the reaction mixture with diethyl ether. The extract is washed twice with water and concentrated NaHCO.sub.3 solution. The organic phase is dried over magnesium sulfate, and the solvent is distilled off under reduced pressure. The residue is crystallised from n-hexane/diethyl ether (2:1).

Example 7. Friedel-Crafts Acylation with PhBi[(C.SUB.2.F.SUB.5.).SUB.2.P(O)O].SUB.2 .as Catalyst

[0116] ##STR00008##

[0117] 119 mg (0.134 mmol) of PhBi(III) bis(perfluoroalkylphosphinate) and 850 mg (6.05 mmol) of benzoyl chloride are initially introduced in a 25 ml Schlenk tube in a counterstream of nitrogen. 280 mg (2.59 mmol) of anisole are added, and the mixture is stirred at 140 C. for 1.5 hours. The solution rapidly becomes yellow, later dark red.

[0118] According to .sup.1H- and .sup.13C-NMR spectroscopy investigations, the conversion to 4-methoxybenzophenone is 81%.

Comparative Example 8. Friedel-Crafts Acylation with (C.SUB.2.F.SUB.5.).SUB.2.P(O)OH as Catalyst

[0119] ##STR00009##

[0120] 85 mg (0.281 mmol) of bis(pentafluoroethyl)phosphinic acid, (C.sub.2F.sub.5).sub.2P(O)OH, and 880 mg (6.26 mmol) of benzoyl chloride are initially introduced in a 25 ml Schlenk tube in a counterstream of nitrogen. 610 mg (5.64 mmol) of anisole are added, and the mixture is stirred at 140 C. for 1.5 hours. The solution becomes dark red after a short time.

[0121] According to .sup.1H- and .sup.13C-NMR spectroscopy investigations, the conversion to 4-methoxybenzophenone is 29%.

Example 9. Investigations of the Hygroscopy of Bi(OTf).SUB.3., Bi[(C.SUB.2.F.SUB.5.).SUB.2.P(O)O].SUB.3 .and PhBi[(C.SUB.2.F.SUB.5.).SUB.2.P(O)O].SUB.2 .on Storage in Air

[0122] a) Finally powdered, ochre-coloured bismuth tris(trifluoromethanesulfonate), Bi(OTf).sub.3, (anhydrous; 278 mg; 0.40 mmol) is stored on a watch glass in ambient air. After 24 hours, an increase in weight of 67 mg is observed. This corresponds to the weight of nine equivalents of H.sub.2O (3.6 mmol). The product changes visually.

[0123] b) In a comparable experiment, 181 mg (0.20 mmol) of finely powdered, colourless PhBi bis(pentafluoroethylphosphinate), PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2 (anhydrous) are stored on a watch glass in ambient air. After 24 hours, an increase in weight of 1 mg is observed. The product does not change visually.

[0124] c) Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.3: 188 mg (0.169 mmol) of finely powdered, colourless Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.3 (anhydrous) are stored on a watch glass in ambient air. After 24 h, an increase in weight of 2 mg is detected. The product does not change visually.

[0125] These experiments show that Bi[(C.sub.2F.sub.5).sub.2P(O)O].sub.3 and PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2 are virtually non-hygroscopic compared with bismuth triflate, Bi(OTf).sub.3.

Comparative Example 10. Friedel-Crafts Acylation with Bi(OSO.SUB.2.CF.SUB.3.).SUB.2..nH.SUB.2.O (Stored in Air for 24 Hours) as Catalyst

[0126] ##STR00010##

[0127] For reproduction of the above results, 250 mg (0.381 mmol) of finely powdered, ochre-coloured Bi(OTf).sub.3 (anhydrous) are stored on a watch glass in ambient air. After 24 h, an increase in weight of 66 mg is detected. This corresponds to the weight of 9.6 equivalents of H.sub.2O (3.442 mmol). The crumbly and clay-coloured solid is transferred into a 25 ml Schlenk tube and employed as catalyst in a Friedel-Crafts acylation. 1.298 mg (9.271 mmol) of benzoyl chloride and 806 mg (7.459 mmol) of anisole are added under ambient air, and the mixture is stirred at 140 C. for 1.5 h. The reaction mixture becomes a dark red colour and is solid at RT. The conversion to 4-methoxybenzophenone detected by .sup.1H- and .sup.13C-NMR spectroscopy is 72%.

Example 11. Friedel-Crafts Acylation with Bi[(C.SUB.2.F.SUB.5.).SUB.2.PO.SUB.2.].SUB.3 .(Stored in Air for 24 Hours) as Catalyst

[0128] Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.3: 188 mg (0.169 mmol) of finely powdered, colourless Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.3 (anhydrous) are stored on a watch glass in ambient air. After 24 h, an increase in weight of 2 mg is detected. The colourless, finely powdered solid obtained is transferred into a 25 ml Schlenk tube and employed as catalyst in a Friedel-Crafts acylation.

##STR00011##

[0129] 571 mg (64.062 mmol) of benzoyl chloride and 372 mg (3.440 mmol) of anisole are added under ambient air, and the mixture is stirred at 140 C. for 1.5 h. The reaction mixture rapidly becomes a yellow colour and later deep red. The conversion to 4-methoxybenzophenone detected by .sup.1H- and .sup.13C-NMR spectroscopy is 85%, with the advantage that a smaller amount of catalyst can be employed than in Comparative Example 9.

Example 12. Friedel-Crafts Acylation with PhBi[(C.SUB.2.F.SUB.5.).SUB.2.P(O)O].SUB.2 .(Stored in Air for 24 Hours) as Catalyst

[0130] ##STR00012##

[0131] 268 mg (0.302 mmol) of finely powdered, colourless PhBi bis(pentafluoroethylphosphinate), PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2, (anhydrous) are stored on a watch glass in ambient air. After 24 hours, an increase in weight of 3 mg is observed. The colourless, finely powdered solid obtained is employed in a Friedel-Crafts acylation. 924 mg (6.57 mmol) of benzoyl chloride and 648 mg (5.99 mmol) of anisole are added under ambient air, and the mixture is stirred at 140 C. for 1.5 hours. The reaction mixture rapidly becomes a yellow colour and later deep red. According to .sup.1H- and .sup.13C-NMR spectroscopy investigations, conversion to 4-methoxybenzophenone is 83%.

TABLE-US-00004 TABLE Overview of the Friedel-Crafts acylations of anisole and benzoyl chloride carried out with various catalyst systems. Catalyst.sup.a) Conversion.sup.b) Bi(OTf).sub.3 (anhydrous) 80% Bi(OTf).sub.3 * n H.sub.2O 72% (stored in air for 24 h) (C.sub.2F.sub.5).sub.2P(O)OH 29% PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2 81% PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2 83% (stored in air for 24 h) Bi[(C.sub.2F.sub.5).sub.2P(O)O].sub.3 90% Bi[(C.sub.2F.sub.5).sub.2P(O)O].sub.3 85% (stored in air for 24 h) .sup.a)Amount of catalyst: about 5 mol %; reaction conditions: 1.5 h, 140 C.; .sup.b)Conversion calculations are based on .sup.1H- and .sup.13C-NMR spectroscopy measurements based on anisole.

Example 13. Friedel-Crafts Alkylation with PhBi[(C.SUB.2.F.SUB.5.).SUB.2.P(O)O].SUB.2 .as Catalyst

[0132] ##STR00013##

[0133] 335 mg (0.377 mmol) of Bi(III) phosphinate complex, PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2, and 1.036 g (5.812 mmol) of cyclohexylmethanesulfonate are initially introduced in a 25 ml Schlenk tube in a counterstream of nitrogen. 1.295 g (11.974 mmol) of anisole are added, and the mixture is stirred at 90 C. After 3 h, quantitative conversion is detected via .sup.1H- and .sup.13C-NMR spectroscopy investigations. The NMR analysis data correspond to the values known from the literature [R. P. Singh, R. M. Kamble, K. L. Chandra, P. Saravanan, V. K. Singh, Tetrahedron, 2001, 57, 241-247; H. Kotsuki, T. Oshisi, M. Inoue, Synlett, 1998, 1998, 255-256].

Example 14. Diels-Alder Addition with PhBi[(C.SUB.2.F.SUB.5.).SUB.2.P(O)O].SUB.2 .as Catalyst

[0134] ##STR00014##

[0135] 13 mg (0.0146 mmol) of Bi(III) phosphinate complex, PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2, and 993 mg (10.127 mmol) of maleic anhydride are suspended in 5 ml of dichloromethane in a 25 ml Schlenk tube in a counterstream of nitrogen. 2.45 g (3.37 ml, 29.83 mmol) of 2,3-dimethylbutadiene are added, and the mixture is stirred at room temperature. After 30 min, quantitative conversion is detected via .sup.1H- and .sup.13C-NMR spectroscopy investigations.

[0136] The NMR analysis data correspond to the values known from the literature [C. E. Song, E. J. Roh, S.-g. Lee, W. H. Shim, J. H. Choi, Chem. Commun. 2001, p. 1122-1123].

Example 15. Diels-Alder Addition with PhBi[(C.SUB.2.F.SUB.5.).SUB.2.P(O)O].SUB.2 .as Catalyst

[0137] ##STR00015##

[0138] 12 mg (0.0135 mmol) of Bi(III) phosphinate complex, PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2, and 893 mg (9.107 mmol) of maleic anhydride are suspended in 5 ml of dichloromethane in a 25 ml Schlenk tube in a counterstream of nitrogen. 2.20 g (2.6 ml, 27.48 mmol) of 1,3-cyclohexadiene are added, and the mixture is stirred at room temperature. The solution immediately becomes a yellow colour. After 1 h, quantitative conversion is detected via .sup.1H- and .sup.13C-NMR spectroscopy investigations.

[0139] The NMR analysis data correspond to the values known from the literature [C. E. Song, E. J. Roh, S.-g. Lee, W. H. Shim, J. H. Choi, Chem. Commun. 2001, p. 1122-1123].

Example 16. Strecker Reaction Catalysed by PhBi[(C.SUB.2.F.SUB.5.).SUB.2.P(O)O].SUB.2

[0140] ##STR00016##

[0141] 117 mg (0.132 mmol) of Bi(III) phosphinate complex, PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2, are suspended in 5 ml of dichloromethane in a 25 ml Schlenk tube, and 0.20 ml (210 mg; 1.978 mmol) of benzaldehyde and 0.18 ml (184 mg; 1.972 mmol) of aniline are added, and the mixture is stirred at room temperature. In order to initiate the reaction, 0.37 ml (292 mg; 2.946 mmol) of trimethylsilyl cyanide are added. After 30 min, quantitative conversion is detected via .sup.1H- and .sup.13C-NMR spectroscopy investigations. The NMR analysis data correspond to the values known from the literature.

[0142] The results are summarised in the following table in comparison with data known from the literature.

TABLE-US-00005 TABLE Comparison of the reaction conditions, amounts of catalyst and conversions of the Strecker reaction of benzaldehyde and aniline of catalysts known from the literature and of the Bi(III) phosphinate complex. Catalyst [mol %] Solvent Time Conversion [1] BiCl.sub.3 10 CH.sub.3CN 10 h 84% [2] Bi(NO.sub.3).sub.3 10 CH.sub.3CN 1 h 94% PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2 6.7 CH.sub.2Cl.sub.2 0.5 h >97%* *Conversion calculations are based on .sup.1H- and .sup.13C-NMR spectroscopy measurements based on benzaldehyde. [0143] [6] S. K. De, R. A. Gibbs, Tetrahedron Letters, 2004, 45, 7407-7408. [0144] [7] N. M. Leonard, L. C. Wieland, R. S. Mohan, Tetrahedron, 2002, 58, 8373-8397.

Example 17. Strecker Reaction Catalysed by PhBi[(C.SUB.2.F.SUB.5.).SUB.2.P(O)O].SUB.2

[0145] ##STR00017##

[0146] 107 mg (0.121 mmol) of Bi(III) phosphinate complex, PhBi[(C.sub.2F.sub.5).sub.2P(O)O].sub.2, are suspended in 5 ml of dichloromethane in a 25 ml Schlenk tube in a counterstream of nitrogen and 0.18 ml (0.171 mg; 1.742 mmol) of cyclohexanone and 0.18 ml (0.184 mg; 1.972 mmol) of aniline are added, and the mixture is stirred at room temperature. In order to initiate the reaction, 0.32 ml (253 mg; 2.548 mmol) of trimethylsilyl cyanide are added. After 30 min, quantitative conversion is detected via .sup.1H- and .sup.13C-NMR spectroscopy investigations. The NMR analysis data correspond to the values known from the literature [G. K. S. Prakash, T. Mathew, C. Panja, S. Alconcel, H. Vaghoo, C. Do, G. A. Olah, Proceedings of the National Academy of Sciences, 2007, 104, 3703-3706].

Example 18. Diels-Alder Addition with Ph.SUB.3.Bi[(C.SUB.2.F.SUB.5.).SUB.2.PO.SUB.2.].SUB.2 .as Catalyst

[0147] ##STR00018##

[0148] 28 mg (0.027 mmol) of Ph.sub.3Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.2 and 624 mg (6.364 mmol) of maleic anhydride are dissolved in 4 ml of acetonitrile in a 25 ml Schlenk tube in a counterstream of nitrogen. 862 mg (1.0 ml, 10.753 mmol) of 1,3-cyclohexadiene are added, and the mixture is stirred at room temperature. The solution immediately becomes a yellow colour and becomes cloudy. After 1.5 h, quantitative conversion is detected via .sup.1H- and .sup.13C-NMR spectroscopy investigations. The NMR analysis data correspond to the values known from the literature [C. E. Song, E. J. Roh, S.-G. Lee, W. H. Shim, J. H. Choi, Chem. Commun. 2001, p. 1122-1123].

Example 19. Friedel-Crafts Acylation with Ph.SUB.3.Bi[(C.SUB.2.F.SUB.5.).SUB.2.PO.SUB.2.].SUB.2 .as Catalyst

[0149] ##STR00019##

[0150] 59 mg (0.057 mmol) of Ph.sub.3Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.2 and 299 mg (2.127 mmol) of benzoyl chloride are initially introduced in a 25 ml Schlenk tube in a counterstream of nitrogen. 128 mg (1.184 mmol) of anisole are added, and the mixture is stirred at 140 C. for 1.5 hours. The solution rapidly becomes yellow, later dark red. The conversion to 4-methoxybenzophenone detected by .sup.1H- and .sup.13C-NMR spectroscopy is 86%.

Example 20. Friedel-Crafts Acylation with Ph.SUB.3.Bi[(C.SUB.2.F.SUB.5.).SUB.2.PO.SUB.2.].SUB.2 .(Stored in Air for 24 Hours) as Catalyst

[0151] ##STR00020##

[0152] In order to investigate the hygroscopy behaviour, 145 mg (0.139 mmol) of colourless, needle-shaped Ph.sub.3Bi[(C.sub.2F.sub.5).sub.2PO.sub.2].sub.2 are stored on a watch glass in ambient air. After 24 h, no increase in weight is detected. The colourless, needle-shaped solid obtained is transferred into a 25 ml Schlenk tube and employed as catalyst in a Friedel-Crafts acylation. 614 mg (4.368 mmol) of benzoyl chloride and 304 mg (2.811 mmol) of anisole are added under ambient air, and the mixture is stirred at 140 C. for 1.5 h. The solution rapidly becomes yellow, later dark red. The conversion to 4-methoxybenzophenone detected by .sup.1H- and .sup.13C-NMR spectroscopy is 88%.

Example 21. Preparation of Ph.SUB.2.Bi[O(O)P(C.SUB.2.F.SUB.5.).SUB.2.]

[0153] 0.82 g (2.7 mmol) of bis(pentafluoroethyl)phosphinic acid are added dropwise to a solution of 1.25 g (2.84 mmol) of tiphenylbismuth in dichloromethane (30 ml). The reaction mixture is heated under reflux for 5 hours. The supernatant solution is decanted, and the solid which remains is washed twice with dichloromethane (10 ml) and dried in a high vacuum, giving a colourless, finely powdered solid. Yield of Ph.sub.2Bi[O(O)P(C.sub.2F.sub.5).sub.2]: 1.41 g (2.1 mmol, 78%). Melting point: 270 C.

TABLE-US-00006 TABLE NMR data of Ph.sub.2Bi[O(O)P(C.sub.2F.sub.5).sub.2] in [D.sub.4]methanol, RT Nucleus [ppm] Splitting J [Hz] Assignment .sup.1H 8.4 m ortho H 7.9 m meta H 7.5 m para H .sup.13C{.sup.1H} 194.3 s C.sub.quart 136.8 s C.sub.ortho 132.1 s C.sub.meta 129.1 s C.sub.para .sup.13C{.sup.19F} 119.0 d .sup.2J.sub.CP = 17.0 CF.sub.3CF.sub.2 111.8 d .sup.1J.sub.CP = 137.0 CF.sub.3CF.sub.2 .sup.19F 82.0 m CF.sub.3CF.sub.2 126.7 d .sup.2J.sub.PF = 74.0 CF.sub.3CF.sub.2 .sup.31P 0.2 qui .sup.2J.sub.FP = 74.0 P

Example 22: Preparation of PhBi[O(O)P(C.SUB.4.F.SUB.9.).SUB.2.].SUB.2

[0154] An aqueous solution of bis(nonafluorobutyl)phosphinic acid is evaporated to dryness over the course 24 hours, giving 7.63 g (15.2 mmol) of the acid as a solid. This acid is added to a solution of 2.20 g (5 mmol) of tiphenylbismuth in methanol (50 ml), and the reaction mixture is heated under reflux for 20 hours. Insoluble components are filtered, and the solvent is removed under reduced pressure. After addition of diethyl ether (50 ml), the solid which has precipitated out is filtered, washed four times with diethyl ether (20 ml) and dried in a high vacuum.

[0155] Yield of PhBi[O(O)P(C.sub.4F.sub.9).sub.2].sub.2: 4.35 g (3.4 mmol, 68%).

[0156] Decomposition point: >490 C.

TABLE-US-00007 TABLE NMR data of PhBi[O(O)P(C.sub.4F.sub.9).sub.2].sub.2 in [D.sub.4]methanol, RT Nucleus [ppm] Splitting J [Hz] Assignment .sup.1H 8.8 m ortho H 8.3 m meta H 7.6 m para H .sup.13C{.sup.1H} 230.9 s C.sub.quart 137.1 s C.sub.ortho 134.2 s C.sub.meta 129.9 s C.sub.para .sup.13C{.sup.19F} 109.0 d .sup.3J.sub.CP = 3 CF.sub.3CF.sub.2CF.sub.2CF.sub.2 111.3 d .sup.2J.sub.CP = 10 CF.sub.3CF.sub.2CF.sub.2CF.sub.2 114.5 d .sup.1J.sub.CP = 134 CF.sub.3CF.sub.2CF.sub.2CF.sub.2 117.5 s CF.sub.3 .sup.19F 82.6 m CF.sub.3 121.9 m CF.sub.3CF.sub.2CF.sub.2CF.sub.2 122.9 dm .sup.2J.sub.PF = 75 CF.sub.3CF.sub.2CF.sub.2CF.sub.2 127.1 m CF.sub.3CF.sub.2CF.sub.2CF.sub.2 .sup.31P 1.1 qui .sup.2J.sub.PF = 75 P