Page 7 of 12
The Journal of Organic Chemistry
(s), 1326 (w), 1282 (w), 1265 (w), 1217 (m), 1175 (w), 1129 (w), (w), 742 (w), 730 (m), 693 (w), 569 (m), 519 (w), 502 (w).
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3
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5
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1108 (w), 1074 (w), 1050 (w), 1006 (m), 974 (m), 899 (s),
885 (s), 846 (m), 813 (w), 791 (w), 747 (w), 725 (s), 569 (w),
543 (s), 523 (w), 512 (w). m.p.: 157.8 – 160.9 °C.
m.p.: 177.0 – 181.5 °C.
Synthesis of L2·AuCl. To ligand L2 (150 mg, 0.27 mmol,
1.05 eq.) and (THT)AuCl (82.7 mg, 0.26 mmol, 1 eq.), 5 mL
of pentane was added. The suspension was stirred for
3 days at room temperature. The solid was filtered and
washed with 5 mL of pentane. The solid was dried at 50°C
with an oil bath in vacuo. The product was obtained as a
Synthesis of ligand L3. Phosphonium salt 1b (5.0 g, 9.3
mmol, 1.0 eq.) was suspended in 70 mL of toluene and
5.82 mL of n-butyllithium (1.59 M in hexane, 1.0 eq.) was
added dropwise. The remaining solid was filtered off and
washed with 10 mL of toluene. Half of the solvent was
removed at reduced pressure and 2.1 mL (2.2 g, 1.0 eq.) of
chlorodicyclohexylphosphine were added. The solution
was stirred for 3 days at room temperature and the result-
ing colorless solid was filtered off and washed with pen-
tane (2 x 10 mL), dried in vacuo, thus giving the interme-
diate phosphonium salt (4.3 g, 5.8 mmol, 63 %). 0.64 mg
(5.8 mmol, 1.0 eq.) of NaBF4 was added to the phosphoni-
um salt and the mixture was redissolved in 50 mL of ace-
tonitrile and stirred overnight at room temperature. The
resulting solid was filtered off, washed several times with
MeCN (3 x 5 mL) and the solvent was removed at reduced
pressure. The oily residue was suspended in 80 mL of
diethyl ether and the suspension was stirred overnight
until a white solid precipitated from the solution. The
colorless BF4 salt was filtered off and dried in vacuo.
(4.0 g, 5.7 mmol, 98 %). 0.50 g (0.7 mmol, 1.0 eq.) of the
BF4 salt were suspended in 40 mL of toluene and 0.081 g
(0.7 mmol, 1.0 eq.) of potassium tert-butoxide were dis-
solved in a second flask in 40 mL of toluene. Both solu-
tions were cooled to –78 °C (dry ice/acetone bath) and
stirred for 30 minutes at that temperature. The potassium
tert-butoxide solution was transferred into the suspension
and the mixture was allowed to warm to room tempera-
ture slowly overnight. The residue was filtered off and the
solvent was removed in vacuo. The solid was washed with
20 mL of acetonitrile and dried in vacuo to yield the lig-
and as a colorless solid (0.29 g, 0.5 mmol, 66 %, overall
1
colorless solid (116 mg, 0.14 mmol, 55 %). H NMR (400
MHz, CD2Cl2) δ 7.40 (d, 3JHH = 7.5 Hz, 1H, CHTol, ortho’), 7.20
9
3
3
(d, JHH = 7.5 Hz, 1H, CHTol, meta), 7.10 (t, JHH = 7.5 Hz, 1H,
CHTol, meta’), 7.02 (t, 3JHH = 7.5 Hz, 1H, CHTol, para), 2.56 – 2.85
(m, 3H, CH, PCy3, H1), 2.50 (s, 3H, CH3), 2.41 – 2.32 (m, 1H,
CH2, PCy2, H2), 2.32 – 2.23 (m, 1H, CH2, PCy2, H2), 2.17 – 2.00 (m,
6H, CH2, PCy3, H2), 1.99 – 1.41 (m, 26H, CH2, PCy3, H2 + H3 + H4 +
PCy2, H2 + H3 + H4 + CH, PCy2, H1), 1.35 – 1.02 (m, 18H, CH2, PCy3, H3 +
H4 + PCy2, H2 + H3 + H4). 13C {1H} NMR (101 MHz, CD2Cl2) δ 143.7
(dd, 3JCP = 5.7 Hz, 3JCP = 2.9 Hz, CTol, ortho), 140.9 (d, 3JCP = 2.6
10
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12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
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38
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56
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58
59
60
2
2
Hz, CHTol, ortho’), 139.5 (dd, JCP = 4.8 Hz, JCP = 3.0 Hz, CTol,
4
4
ipso), 131.4 (dd, JCP = 1.9 Hz, JCP = 1.9 Hz, CHTol, meta), 126.9
5
5
(d, JCP = 2.2 Hz, JCP = 2.2 Hz, CHTol, para), 125.3 (dd, 4JCP
=
2.3 Hz, 4JCP = 2.3 Hz, CHTol, meta’), 42.0 (d, 1JCP =37.0 Hz, CH,
PCy2, C1), 40.5 (dd, JCP = 38.8 Hz, JCP = 3.8 Hz, CH, PCy2, C1),
38.4 (dd, 1JCP = 47.7 Hz, 3JCP = 1.8 Hz, CH, PCy3, C1), 34.1 (d, 2JCP
1
3
2
= 2.5 Hz, CH2, PCy2, C2), 34.0 (d, JCP = 2.8 Hz, CH2, PCy2, C2),
31.2 (CH2, PCy2, C2), 30.6 (CH2, PCy2, C2), 29.6 (dd, 2JCP = 8.7 Hz,
4JCP = 3.3 Hz, CH2, PCy3, C2), 28.5 (d, JCP = 13.8 Hz, CH2, PCy2,
3
3
C3), 28.2 (d, JCP = 11.4 Hz, CH2, PCy3, C3), 28.0 – 27.6 (m, CH2,
PCy2, C3), 26.9 – 26.4 (m, CH2, PCy3, C4 + PCy2, C4), 22.7 (CH3), 14.8
(dd, 1JCP = 97.8 Hz, 1JCP = 60.4 Hz). 31P {1H} NMR (162 MHz,
2
2
CD2Cl2) δ 34.4 (d, JPP = 60.5 Hz, PCy3), 25.7 (d, JPP = 60.5
Hz, PCy2). Anal. calc. For C38H62P2ClAu: C 56.12, H 7.68;
found: C 55.63, H 7.82. IR(ATR): 2917 (s), 2846 (s), 1739
(s), 1447 (s), 1365 (m), 1228 (s), 1217 (s), 1205 (s), 1108 (w),
1009 (s), 990 (s), 919 (m), 888 (s), 846 (m), 738 (m), 729
(m), 545 (s), 510 (m). m.p.: 214.1 – 219.3 °C (decomposi-
tion).
1
yield: 41 %). H NMR (400 MHz, C6D6) δ 6.99 (s, 2H, CH,
Mes, meta), 2.76 (d, 5JHH = 1.4 Hz, 6H, CH3, Mes, ortho), 2.49 – 2.32
(m, 2H, CH2, PCy2, H2), 2.21 (s, 3H, CH3, Mes, para), 2.22 – 2.12
(m, 6H, CH2, PCy3, H2), 2.14 – 4.98 (m, 5H, CH, PCy2, H1 + PCy3, H1),
1.98 – 1.80 (m, 4H, CH2, PCy2, H2 + H3), 1.82 – 1.65 (m, 10H,
CH2, PCy3, H3 + CH2, PCy2, H3 + H4), 1.66 – 1.40 (m, 15H, CH2, PCy3, H2
Synthesis of L3·AuCl. To ligand L3 (70 mg, 1.05 eq.,
0.12 mmol) and (THT)AuCl (35.1 mg, 1 eq., 0.11 mmol), 5
mL of THF was added and the colorless suspension was
stirred for 2 days at room temperature. To the solution,
toluene (5 mL) was added and the suspension was stirred
for another 30 min. The resulting solid was filtered and
washed with pentane (3 x 5 mL) to yield the gold complex
+ CH2, PCy2, H2 + H3), 1.38 – 1.22 (m, 4H, CH2, PCy2, H3 + H4 ),
+ H4
1.20 – 0.91 (m, 9H, CH2, PCy3, H3 + H4). 13C {1H} NMR (101 MHz,
4
2
1
C6D6) δ 142.7 (d, JCP = 4.6 Hz, CH, Mes, meta), 140.8 (d, JCP
=
as a colorless solid (50 mg, 0.06 mmol, 54 %). H NMR
9.5 Hz, C, Mes, ipso), 133.4 (d, 5JCP = 2.7 Hz, C, Mes, para), 129.0 (d,
(400 MHz, CD2Cl2) δ 6.88 (s, 2H, CH, Mes, meta), 2.75 – 2.52
(m, 3H, CH, PCy3, H1), 2.51 (s, 6H, CH3, Mes, para), 2.41 – 2.24 (m,
8H, CH2, PCy3, H2 + CH2, PCy2, H2), 2.22 (s, 3H, CH3, Mes, para), 1.96
– 1.84 (m, 2H, CH, PCy2, H1), 1.90 – 1.73 (m, 9H, CH2, PCy3, H3 +
H4), 1.73 – 1.65 (m, 4H, CH2, PCy2, H3 + H4), 1.64 – 1.53 (m, 4H,
CH2, PCy2, H3 + H4), 1.52 – 1.38 (m, 2H, CH2, PCy2, H2), 1.36 – 1.00
(m, 23H, CH2, PCy3, H2 + H3 + H4 + CH2, PCy2, H2 + H3). 13C {1H} NMR
(101 MHz, CD2Cl2) δ 145.6 – 142.7 (m, C, Mes, ortho), 137.6 –
136.3 (m, C, Mes, ipso), 136.2 – 135.5 (m, C, Mes, para), 129.7 (t, 3JCP
= 2.1 Hz, CH, Mes, meta), 40.5 (dd, 1JCP = 37.0 Hz, 3JCP = 1.7 Hz,
3JCP = 1.9 Hz, C, Mes, ortho), 41.4 (dd, JCP = 17.8 Hz, JCP = 6.2
Hz, CH2, PCy2, C1), 39.6 (dd, 1JCP = 46.5 Hz, 3JCP = 6.3 Hz, CH2,
PCy3, C1), 35.0 (d, 2JCP = 24.8 Hz, CH2, PCy2, C2), 32.1 (d, 2JCP = 3.6
1
3
3
Hz, CH2, PCy2, C2), 29.5 (d, JCP = 15.4 Hz, CH2, PCy2, C3), 29.3
(dd, JCP = 5.8 Hz, JCP = 3.6 Hz, CH2, PCy3, C2), 29.0 (d, JCP
2
4
3
3
= 4.3 Hz, CH2, PCy2, C3), 28.2 (d, JCP = 10.4 Hz, CH2, PCy3, C3),
27.6 (CH2, PCy2, C4), 26.9 (CH2, PCy3, C4), 24.1 (CH3, Mes, ortho),
21.0 (CH3, Mes, para), 14.5 (dd, 1JCP = 103.4 Hz, 1JCP = 30.2 Hz, P-
31
2
C--P). P {1H} NMR (162 MHz, C6D6) δ 13.8 (d, JPP = 145.3
2
2
Hz, PCy3), 6.1 (d, JPP = 145.3 Hz, PCy2). CHNS: Anal. calc.
CH, PCy2, C1), 40.4 – 38.7 (br, CH, PCy3, C1), 35.4 (d, JCP = 3.9
For C40H66P2: C 78.90, H 10.93; found: C 78.68, H 10.88. IR
(ATR): 2922 (s), 2849 (m), 1444 (m), 1262 (w), 1216 (w),
1202 (w), 1154 (w), 1105 (w), 1071 (w), 1048 (w), 1005 (w),
969 (s), 942 (m), 897 (w), 883 (w), 870 (m), 851 (m), 808
Hz, CH2, PCy2, C2), 30.5 (CH2, PCy2, C2), 29.6 (CH2, PCy3, C2), 28.3
3
3
(d, JCP = 14.4 Hz, CH2, PCy2, C3), 28.0 (d, JCP = 11.0 Hz, CH2,
3
PCy3, C3), 27.8 (d, JCP = 11.3 Hz, CH2, PCy2, C3), 26.7 (d, 4JCP = 1.6
Hz, CH2, PCy2, C4), 26.6 (d, 4JCP = 1.7 Hz, CH2, PCy3, C4), 24.3 (d,
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