10.1002/chem.201604914
Chemistry - A European Journal
FULL PAPER
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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