Organometallics
Article
H), 5.87 (d, 3JHP = 50 Hz, 1H, C−H), 5.63 (d, 3JHP = 23 Hz, 1H, C−
1505, 1464, 1443, 1423, 1364, 1297, 1267, 1184, 1170, 1112, 1084,
1026, 966, 897, 834, 805, 753, 728, 705. HRMS ESI−: m/z calculated
for [M − H]− [C50H30BF15O5P]−, 1036.1721; found, 1036.1725.
Compound 2i. Yield: 100 mg, 95.9 μmol, 96%. Mp: 87−99 °C. 1H
NMR (500 MHz, CDCl3, 298 K): 7.30 (d, 3JHH = 8.8 Hz, 2H, Ar o-H),
3
H), 4.36 (d, JHP = 7.4 Hz, 1H, CC−H), 2.30 (s, 3H, phosphine
CH3), 1.79 (s, 3H, phosphine CH3), 1.58 (s, 3H, phosphine CH3). 13
C
NMR (126 MHz, CDCl3, 298 K): 151.5 (s), 150.7 (m), 148.3 (s),
147.7 (s), 145.8 (s), 138.6 (s), 136.5 (s), 133.9 (s), 129.8 (s), 128.1
(s), 127.4 (s), 126.8 (s), 125.3 (s), 114.1 (s), 112.2 (s), 95.2 (m), 21.6
(s), 20.0 (m). 11B NMR (160 MHz, CDCl3, 298 K): −3.6 (s, br). 19F
NMR (282 MHz, CDCl3, 298 K): −132.9 (m, 2F, o-F), −161.2 (t, 3JFF
= 21 Hz, 1F, p-F), −165.7 (m, 2F, m-F). 31P NMR (202 MHz, CDCl3,
298 K): 23.7 (s), 19.7 (s, br). 31P{1H} NMR (202 MHz, CDCl3, 298
K): 23.6 (s), 19.7 (s, br). IR (cm−1): νmax 3055, 2988, 2686, 2522,
2412, 2306, 1712, 1645, 1593, 1566, 1555, 1514, 1466, 1424, 1368,
1265, 1223, 1170, 1137, 1087, 1025, 978, 897, 808, 753, 723, 705.
HRMS ESI−: m/z calculated for [M − H]− [C53H29BClF15O2P]−,
1058.1484; found, 1058.1536.
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7.24−7.20 (m, 6H, phosphine C−H), 7.12 (d, JHH = 8.4 Hz, 2H, Ar
3
m-H), 6.92−6.91 (m, 6H, phosphine C−H), 5.47 (d, JHP = 49 Hz,
1H, C−H), 5.06 (d, 3JHP = 23 Hz, 1H, C−H), 4.54 (d, 3JHP = 8.6
Hz, 1H, CH), 3.78 (s, 9H, phosphine CH3). 13C NMR (126 MHz,
CDCl3, 298 K): 164.6 (m), 148.8 (m), 146.7 (m), 136.0 (m), 135.5
(m), 129.8 (s), 129.1 (s), 128.9 (s), 128.5 (s), 128.1 (s), 125.2 (s),
116.6 (m), 115.7 (m), 108.6 (m), 107.9 (m), 55.6 (m), 31.5 (s), 22.6
(s), 21.3 (s), 14.0 (s). 11B NMR (160 MHz, CDCl3, 298 K): −3.8 (s,
br). 19F NMR (282 MHz, CDCl3, 298 K): −133.1 (m, 2F, o-F),
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−160.9 (t, JFF = 20.7 Hz, 1F, p-F), −165.6 (m, 2F, m-F). 31P NMR
Compound 2f. Yield: 55 mg, 54.9 μmol, 55%. Mp: 151−164 °C. 1H
NMR (500 MHz, CDCl3, 298 K): 7.71−7.48 (m, 3H, phosphine C−
(202 MHz, CDCl3, 298 K): 21.6 (s). 31P{1H} NMR (202 MHz,
CDCl3, 298 K): 21.7 (s). IR (cm−1): νmax 3054, 2988, 2846, 2685,
2309, 1713, 1644, 1594, 1567, 1514, 1504, 1465, 1422, 1366, 1300,
1265, 1223, 1184, 1113, 1088, 1024, 979, 965, 896, 835, 806, 739, 706.
HRMS ESI−: m/z calculated for [M − H]− [C49H27BClF15O4P]−,
1040.1225; found, 1040.1245.
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H), 7.39 (t, br, JHH = 8.1 Hz, 3H, phosphine C−H), 7.34 (d, JHH
=
8.2 Hz, 2H, o-H), 7.16 (m, 3H, phosphine C−H), 7.05 (m, 3H,
phosphine C−H), 6.74 (d, 3JHH = 8.2 Hz, 2H, m-H), 5.63 (d, 3JHP = 53
Hz, 1H, C−H), 5.06 (d, 3JHP = 25 Hz, 1H, C−H), 4.45 (d, 3JHP
=
9.8 Hz, 1H, C−H), 3.67 (s, 3H, OCH3). 13C NMR (126 MHz,
CDCl3, 298 K): 166.0 (m), 163.8 (m), 161.9 (m), 160.0 (s), 148.6 (s),
139.6 (s), 137.5 (m), 135.4 (m), 132.9 (s), 132.6 (m), 131.1 (s), 129.7
(s), 129.7 (s), 129.4 (s), 123.1 (m), 120.6 (m), 119.4 (s), 118.8 (s),
114.0 (s), 92.3 (m), 55.1 (s). 11B NMR (160 MHz, CDCl3, 298 K):
−3.8 (s, br). 19F NMR (282 MHz, CDCl3, 298 K): −105.5 (m, 1F,
phosphine), −133.2 (d, 3JFF = 22 Hz, 2F, o-F), 160.8 (t, 3JFF = 21 Hz,
Compound 2j. Yield: 62 mg, 62.6 μmol, 63%. Mp: 168−181 °C. 1H
NMR (500 MHz, CDCl3, 298 K): 7.39−7.34 (m, 9H, phosphine C−
H), 7.39−7.34 (m, 2H, Ar o-H) 6.89 (m, 6H, phosphine C−H), 6.80
(d, 3JHH = 8.8 Hz, 2H, Ar m-H), 5.58 (d, 3JHP = 47 Hz, 1H, C−H),
3
3
5.19 (d, JHP = 20 Hz, 1H, C−H), 4.87 (d, JHP = 8.3 Hz, 1H,
3
CH), 3.78 (s, 3H, OCH3), 3.20 (d, JHP = 13 Hz, 6H, phosphine
CH2). 13C NMR (126 MHz, CDCl3, 298 K): 196.9 (s), 164.5 (m),
149.1 (s, br) 147.2 (s, br) 137.9 (s, br), 137.3 (s), 135.9 (m), 134.7
(s), 133.3 (s), 130.3 (m), 129.2 (m), 128.7 (m), 126.1 (s), 91.3 (m),
28.6 (m), 26.0 (m). 11B NMR (160 MHz, CDCl3, 298 K): −3.57 (s,
br). 19F NMR (282 MHz, CDCl3, 298 K): −132.9 (m, 2F, o-F),
1F, p-F), 165.6 (t, JFF = 21 Hz, 2F, m-F). 31P NMR (202 MHz,
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CDCl3, 298 K): 22.6 (s). 31P{1H} NMR (202 MHz, CDCl3, 298 K):
22.7 (s). IR (cm−1): νmax 3055, 2987, 2686, 2411, 2306, 1644, 1610,
1585, 1556, 1514, 1480, 1465, 1423, 1270, 1262, 1237, 1175, 1098,
1090, 1033, 999, 981, 925, 897, 844, 794, 757, 723, 706. HRMS AP+:
m/z calculated for [M]+ [C47H22BF18O2P]+, 1002.1163; found,
1002.1166. Anal. Calcd for C47H22BF18O2P: C, 56.31; H, 2.21.
Found: C, 56.27; H, 2.18.
−160.3 (t, JFF = 21.1, 1F, p-F), 165.1 (m, 2F, m-F). 31P NMR (202
3
MHz, CDCl3, 298 K): 25.1 (m). 31P{1H} NMR (202 MHz, CDCl3,
298 K): 25.0 (s). IR (cm−1): νmax 3055, 2987, 2961, 2926, 2855, 2687,
2411, 2359, 2308, 1716, 1643, 1609, 1588, 1565, 1514, 1498, 1465,
1423, 1365, 1266, 1175, 1088, 1032, 980, 925, 896, 865, 845, 808, 751,
730, 706. HRMS ESI−: m/z calculated for [M − H]−
[C50H30BF15O2P]−, 988.1873; found, 988.1896. Anal. Calcd for
C50H31BF15O2P: C, 60.63; H, 3.15. Found: C, 60.48; H, 2.94.
Compound 2g. Yield: 93 mg, 92.4 μmol, 92%. Mp: 119−141 °C.
1H NMR (500 MHz, CDCl3, 298 K): 7.54−7.02 (m, 12H, phosphine
3
C−H) 7.54−7.02 (m, 4H, Ar−H), 5.62 (d, JHH = 53 Hz, 1H, C−
H), 5.11 (d, 3JHH = 25 Hz, 1H, C−H), 4.52 (d, 3JHH = 9.4 Hz, 1H,
CH). 13C NMR (126 MHz, CDCl3, 298 K): 165.3 (m), 164.4 (m),
162.3 (m), 149.1 (m), 147.2 (m), 140.2 (m), 137.9 (m), 137.7 (s),
135.8 (m), 135.2 (s), 134.2 (m), 133.1 (m), 130.8 (m), 130.0 (m),
129.4 (m), 127.9 (s), 127.3 (s), 123.8 (m), 121.2 (m), 119.7 (m),
119.0 (m), 117.0 (m), 93.6 (m). 11B NMR (160 MHz, CDCl3, 298 K):
−3.8 (s, br). 19F NMR (282 MHz, CDCl3, 298 K): −105.2 (m, 1F,
P(m-FC6H4)3), −133.3 (m, 2F, o-F), −160.4 (t, 3JFF = 20.3 Hz, 1F, p-
F), −165.4 (m, 2F, m-F). 31P NMR (202 MHz, CDCl3, 298 K): 22.9
(s, br). 31P{1H} NMR (202 MHz, CDCl3, 298 K): 22.8 (s). IR
(cm−1): νmax 3055, 2988, 2964, 2932, 2874, 2861, 2686, 2411, 2307,
1720, 1682, 1644, 1585, 1556, 1514, 1480, 1465, 1424, 1370, 1267,
1235, 1100, 1056, 1015, 998, 979, 966, 926, 898, 843, 794, 752, 731,
707. HRMS ESI−: m/z calculated for [M − H]− [C46H18BClF18OP]−,
1004.0626; found, 1004.0672.
Compound 2k. Yield: 87 mg, 87.4 μmol, 87%. Mp: 91−103 °C. 1H
NMR (500 MHz, CDCl3, 298 K): 7.29−7.21 (m, 9H, phosphine C−
H), 7.29−7.21 (m, 2H, Ar o-H), 7.14 (m, 2H, Ar m-H), 6.77 (m, 6H,
phosphine C−H), 5.42 (d, 3JHP = 47 Hz, 1H, C−H), 5.09 (d, 3JHP = 20
Hz, 1, C−H), 4.8 (d, 3JHP = 8.1 Hz, 1H, CH), 3.13 (d, 3JHP = 13 Hz,
6H, phosphine CH2). 13C NMR (126 MHz, CDCl3, 298 K): 186.7 (s),
167.5 (s), 155.9 (s), 148.3 (s), 139.8 (s), 138.1 (s), 130.3 (m), 129.6
(m), 128.8 (m), 126.2 (s), 93.6 (s), 34.5 (m), 22.4 (m). 11B NMR
(160 MHz, CDCl3, 298 K): −3.5 (s, br). 19F NMR (282 MHz, CDCl3,
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298 K): −132.9 (m, 2F, o-F), −160.1 (t, JFF = 20.6 Hz, 1F, p-F),
−164.9 (m, 2F, m-F). 31P NMR (202 MHz, CDCl3, 298 K): 25.4 (m).
31P{1H} NMR (202 MHz, CDCl3, 298 K): 25.2 (s). IR (cm−1): νmax
3055, 2987, 2927, 2854, 2687, 2412, 2361, 2307, 1714, 1678, 1645,
1589, 1515, 1464, 1423, 1364, 1266, 1222, 1088, 978, 964, 897, 751,
728, 707. HRMS ESI−: m/z calculated for [M − H]−
[C49H27BClF15OP]−, 992.1378; found, 992.1357. Anal. Calcd for
C49H28BClF15OP: C, 59.15; H, 2.84. Found: C, 59.02; H, 2.86.
Alternative Synthesis of 2c. B(C6F5)3 (103 mg, 0.2 mmol), P(o-
tol)3 (60 mg, 0.2 mmol), and 1-(4-methoxyphenyl)buta-2,3-dien-1-
one 1c (36 mg, 0.2 mmol) were mixed in toluene (2 mL), giving a
yellow solution. The reaction mixture was left to stand at room
temperature for 24 h. Removal of the solvent afforded an orange oil.
Washing with hexane (3 × 2 mL) yielded the product 2c (159 mg,
0.16 mmol, 80%). The addition of hot hexane (ca. 2 mL) and a few
drops of hot toluene to give a clear solution gave, upon cooling and
prolonged storage (3−4 days), a few colorless needle-shaped crystals
of 2c.
Compound 2h. Yield: 70 mg, 67.4 μmol, 67%. Mp: 110−122 °C.
1H NMR (500 MHz, CDCl3, 298 K): 7.32 (d, 3JHH = 8.4 Hz, 2H, Ar o-
H), 7.24 (m, 6H, phosphine m-H), 6.89 (dd, 3JHH = 8.8 Hz, 4JHH = 2.5
Hz, 6H, phosphine o-H), 6.70 (d, 3JHH = 8.7 Hz, 2H, Ar m-H), 5.47 (d,
3JHP = 50 Hz, 1H, C−H), 5.00 (d, 3JHP = 24 Hz, 1H, C−H), 4.47
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(d, JHP = 9.0 Hz, 1H, CH), 3.77 (s, 9H, phosphine CH3), 3.66 (s,
3H, OCH3). 13C NMR (126 MHz, CDCl3, 298 K): 164.8 (s), 164.11
(m), 159.9 (s), 149.0 (s, br), 147.1 (s, br), 137.7 (m), 135.8 (m),
132.0 (s), 131.7 (s), 130.8 (s), 129.9 (s), 115.8 (m), 113.9 (s), 109.2
(s), 108.4 (s), 94.0 (m), 55.7 (s), 55.3 (s). 11B NMR (160 MHz,
CDCl3, 298 K): −3.8 (s, br). 19F NMR (282 MHz, CDCl3, 298 K):
−133.0 (m, 2F, o-F), −161.2 (t, 3JFF = 21 Hz, 1F, p-F), −165.8 (t, 3JFF
= 21 Hz, 2F, m-F). 31P NMR (202 MHz, CDCl3, 298 K): 21.8 (s, br).
31P{1H} NMR (202 MHz, CDCl3, 298 K): 21.7 (s). IR (cm−1): νmax
3055, 2988, 2845, 2687, 2410, 2307, 1713, 1643, 1596, 1568, 1513,
Synthesis of Compounds 3a−e. General Procedure. B(C6F5)3
(51 mg, 0.1 mmol, 1 equiv) in CDCl3 (0.5 mL) was added to 3 (0.1
4134
Organometallics 2015, 34, 4127−4137