Organometallics
Article
round-bottom flask were placed 4-methylaniline (2.27 g, 21.15 mmol)
Synthesis and Characterization of [L1AuS ]BF . A 6.6 mg amount
c
4
and NaHCO (2.67 g, 31.7 mmol) in 30 mL of water. The mixture was
of AgBF (0.034 mmol) was loaded into a Schlenk vessel under a
3
4
stirred and cooled to 10−15 °C. Then, powdered and resublimed
iodine (5.37 g, 21.15 mmol) was introduced in 1 g portions. The
reaction mixture was stirred overnight at room temperature. The
organic phase was extracted from the reaction mixture with diethyl
nitrogen atmosphere. A solution containing 18.6 mg of L1AuCl (0.03
mmol) and 6.4 mg of S (0.03 mmol) dissolved in 1 mL of dry CD
Cl
2
2
was added. The resulting mixture was stirred for 20 min, then filtered
1
directly in a screw-cap NMR tube. H NMR (400.13 MHz, CD
Cl
=
,
2
2
HH
HH
ether. The extracts were combined and dried with MgSO . The
298 K, J in Hz): δ = 7.76 (t, 2H, J
3
= 7.7, H23), 7.58 (d, 1H, J
3
4
HH
mixture was concentrated, and then the product was precipitated and
washed with cold pentane, obtaining a brown solid: yield 3.92 g
7.3, H9), 7.57 (s, 2H, H19), 7.53 (d, 4H, J
3
= 7.7, H22), 7.28 (d,
= 7.3, H10), 6.83 (s, 1H, H12), 3.32 (s, 6H, H14), 2.71 (sept,
HH
1H, J
4H, J
3
HH
(
79.6%). Spectroscopic data are consistent with those obtained in the
3
= 7.0, H16), 2.48 (m, 2H, H4), 2.36 (s, 3H, H13), 1.48 (m,
12
HH
HH
2
H, H3), 1.43 (d, 12H, J3
= 6.9, H15), 1.33 (d, 12H, J
= 6.9,
= 7.4, H1). C{ H} NMR
100.5 MHz, CD Cl , 298 K): δ = 190.1 (s, C18), 168.3 (s, C5), 147.1
literature.
3
HH
13
1
Synthesis of 2-Iodo-N,N,4-trimethylaniline (P2). 2-Iodo-N,N,4-
H17), 1.31 (m, 2H, H2), 0.88 (t, 3H, J3
4
8
(
(
trimethylaniline was prepared according to a literature procedure. To
a solution of P1 (1.8 g, 8 mmol) and iodomethane (1.5 mL, 24 mmol)
in DMF (10 mL) was added K CO (2.23 g, 16 mmol). The resulting
2
2
s, C21), 145.6 (s, C8), 141.8 (s, C11), 140.6 (s, C7), 137.1 (s, C6),
33.9 (s, C20), 130.3 (s, C23), 128.7 (s, C10), 126.6 (s, C12), 124.5
s, C19), 123.7 (s, C22), 116.3 (s, C9), 52.4 (s, C14), 34.7 (s, C3),
1
(
2
3
mixture was stirred at room temperature for 48 h. Water (10 mL) was
added to the reaction mixture. The resulting solution was extracted
with diethyl ether (3 × 10 mL). The organic layers were combined and
washed with water to remove any remaining DMF and dried over
2
2
9.2 (s, C16), 26.2 (s, C4), 24.6 (s, C15), 23.8 (s, C17), 22.7 (s, C2),
19
1.0 (s, C13), 13.1 (s, C1). F NMR (376.42 MHz, CD Cl , 298 K):
2
2
10
11
δ = −152.60 (br, BF ), −152.64 (br, BF4).
4
Synthesis and Characterization of [L2AuS ]BF . A 6.6 mg amount
anhydrous MgSO . The solvent was removed under vacuum, and the
c
4
4
of AgBF (0.034 mmol) was loaded into a Schlenk vessel under a
residue was purified by flash column chromatography on silica gel
using ethyl acetate/pentane (1:5−1:1) as eluent. We obtain the
product as dark brown oil; yield 1.6 g (75%). Anal. Calcd for C H IN
4
nitrogen atmosphere. A solution containing 27 mg of L2AuCl (0.03
mmol) and 6.4 mg of S (0.03 mmol) dissolved in 1 mL of dry CD Cl
2
2
9
12
was added. The resulting mixture was stirred for 20 min, then filtered
(
261.10): C, 41.40; H, 4.63; I, 48.60; N, 5.36. Found: C, 41.39; H,
1
1
directly in a screw-cap NMR tube. H NMR (400.13 MHz, CD
2
Cl
2
,
4
7
3
1
.65; N, 5.38. H NMR (200 MHz, CDCl , J in Hz): δ = 7.67 (s, 1H),
3
HP
HH
1
HH
298 K, J in Hz): δ = 8.30 (d, 3H, H18), 8.15 (d, J
= 8.1, H9), 7.52 (s, 1H, H12), 7.35 (d, 1H, J
.1, H10), 3.46 (s, 6H, H14), 2.73 (t, 2H, J3 = 7.9, H4), 2.49 (s, 3H,
3
= 12.0, H16),
.09 (d, J
= 1.3, 1H), 6.98 (d, J3 = 8.1, 1H), 2.72 (s, 6H), 2.25 (s,
3
HH
HH
H). 1 C{ H} NMR (CD Cl, 50 MHz): δ = 152.30 (s), 140.26 (s),
3
7.71 (d, 1H, J
8
3
3
=
3
HH
34.66 (s), 129.59 (s), 119.90 (s), 97.28 (s), 45.02 (s), 20.00 (s).
HH
HH
H13), 2.05 (quintet, 2H, J3 1 = 7.5, H3), 1.52 (sextet, 2H, J3 = 7.5,
Synthesis of 2-(1-Hexynyl)-N,N,4-trimethylaniline (S). 2-(1-Hex-
H2), 0.85 (s, 3H, H1). 13C{ H} NMR (100.5 MHz, CD Cl , 298 K, J
2
2
ynyl)-N,N,4-trimethylaniline was prepared according to a literature
CP
12
in Hz): δ = 163.1 (br, C5), 152.8 (d, J
42.0. (s, C11), 140.6 (s, C7), 134.0 (d, J
quartet of d, J3 = 11.4, J2 = 35.3, C17), 130.1 (d, J1 = 53.1,
2
= 108, C6), 145.9 (s, C8),
procedure. To a mixture of Pd(OAc) (2 mol %, 52.44 mg), CuI (3
2
CP
1
(
= 16.0, C16), 133.8
2
mol %, 66.73 mg), and PPh (5 mol %, 153.18 mg) in CH CN (6 mL)
3
3
CP
CF
CP
were successively added a solution of P2 (3.05 g, 11.68 mmol) in
C15), 128.8 (s, C10), 127.6 (br s, C18), 126.9 (s, C12), 122.3
CH CN (8 mL), Et N (4.06 mL, 29.20 mmol), and 1-hexyne (2.01
CF
3
3
(
2
quartet, J1 = 273.6, C19), 116.1 (s, C9), 52.0 (s, C14), 34.2 (s, C3),
mL, 17.52 mmol). The reaction mixture was stirred overnight a room
19
5.6 (s, C4), 22.5 (s, C2), 21.0 (s, C13), 13.3 (s, C1). F NMR
temperature. Then a saturated aqueous solution of NH Cl was added,
4
(
376.42 MHz, CD Cl , 298 K): δ = −63.43 (s, m-CF ), −152.41 (br,
2
2
3
and the mixture was extracted with Et O (3 × 15 mL). The combined
10
11
31
1
2
BF ), −152.45 (br, BF ). P{ H} NMR (161.97 MHz, CD Cl ,
4
4
2
2
organic layers were washed with brine and dried over MgSO . Solvent
4
2
98 K): δ = 47.56 (s).
Synthesis and Characterization of [L3AuS ]BF . A 6.6 mg amount
was then removed under reduced pressure, and the residue was
purified by column chromatography (silica gel, hexane/ethyl acetate =
c
4
of AgBF (0.034 mmol) was loaded into a Schlenk vessel under a
4
95:5) to afford the product as a brown liquid; yield 1.61 g (63.8%).
nitrogen atmosphere. A solution containing 26.4 mg of L3AuCl (0.03
mmol) and 6.4 mg of S (0.03 mmol) dissolved in 1 mL of dry CD Cl
2
Anal. Calcd for C H N (215.33): C, 83.67; H, 9.83; N, 6.50. Found:
15
21
1
2
C, 83.68; H, 9.86; N, 6.51. H NMR (CD Cl, 200 MHz, J in Hz): δ =
3
was added. The resulting mixture was stirred for 20 min, then filtered
HH
7
=
.23 (d, J = 2.1, 1H, H ), 7.03 (dd, J = 8.3, 1.6, 1H, H ), 6.83 (d, J
8.3, 1H, H ), 2.91 (s, 6H, H ), 2.52 (t, J
H, H ), 1.77−1.42 (m, 4H, H ), 0.99 (t, J
C{ H} NMR (50 MHz, CDCl ): δ = 152.21 (s), 134.54 (s), 130.00
1
9
12
3
directly in a screw-cap NMR tube. H NMR (400.13 MHz, CD Cl ,
HH
2
2
= 6.9, 2H, H ), 2.27 (s,
HH
10
14
3
4
2
7
(
98 K, J in Hz): δ = 7.65 (d, 1H, J
= 8.2, H9), 7.56 (s, 3H, H17),
HH
3
3
= 7.2, 3H, H1).
HH
.55 (dd, 3H, J3
HH
HP
13
2,3
3
= 8.5, J4 = 1.3, H20), 7.27 (m, 1H, H10), 7.26
dd, 3H, J3 = 8.5, J5 = 2.5, H19), 7.16 (s, 1H, H12), 3.37 (s, 6H,
H14), 2.56 (t, 2H, J3 = 7.7, H4), 2.44 (s, 3H, H13), 1.85 (quintet,
H, J3 = 7.5, H3), 1.54 (s, 27H, H21), 1.40 (m, 2H, H2), 1.33 (s,
7H, H22), 0.88 (t, 3H, J3 = 7.3, H1). C{ H} NMR (100.5 MHz,
CD Cl , 298 K, J in Hz): δ = 161.6 (d, J = 14.0, C5), 154.5 (d, J2
= 171.1, C6), 148.7 (s, C18), 147.4 (d, J2 = 5.4, C7), 146.0 (d, J4
6.5, C8), 141.2 (s, C11), 139.4 (d, J3 = 6.2, C16), 128.2 (s, C10),
1
3
1
HP
3
(
s), 128.88 (s), 116.82 (s), 116.56 (s), 95.20 (s), 43.61 (s), 30.80 (s),
HH
21.94 (s), 20.07 (s), 19.41 (s), 13.49 (s).
HH
2
Synthesis of 2-(1-Hexynyl)aniline (S2). 2-(1-Hexynyl)aniline was
HH
13
1
2
12
prepared according to a literature procedure. To a mixture of
Pd(OAc) (2 mol %, 42.5 mg), CuI (3 mol %, 52.0 mg), and PPh (5
CP
CP
2
2
3
CP
CP
2
3
=
CP
mol %, 121.0 mg) in CH CN (6 mL) were successively added a
3
CP
solution of 2-iodoaniline (2003 mg, 9.15 mmol) in CH CN (5 mL),
3
126.6 (s, C12), 125.8 (s, C17), 125.3 (d, J2 = 186.6, C15), 123.8 (s,
C19), 118.9 (d, J3 = 9.2, C20), 116.0 (s, C9), 51.5 (s, C14), 35.1 (s,
CP
Et N (3.18 mL, 22.88 mmol), and 1-hexyne (1.58 mL, 13.75 mmol).
3
The reaction mixture was stirred overnight at room temperature. Then
C24), 34.6 (s, C23), 33.5 (s, C3), 31.1 (s, C22), 30.3 (s, C21), 25.3 (s,
19
saturated aqueous NH Cl was added, and the mixture was extracted
C4), 22.5 (s, C2), 21.3 (s, C13), 13.5 (s, C1). F NMR (376.42 MHz,
4
1
0
11
with Et O (3 × 10 mL). The combined organic layers were washed
CD Cl , 298 K): δ = −152.09 (br, BF ), −152.13 (br, BF4).
2
2
2
4
3
1 1
with brine and dried over MgSO . Solvent was then removed under
P{ H} NMR (161.97 MHz, CD Cl , 298 K): δ = 136.37 (s).
4
2 2
reduced pressure, and the residue was purified by column
chromatography (silica gel, pentane/ethyl acetate = 3:1) to afford
the product as a brown liquid; yield 1.51 g (95%). Anal. Calcd for
C H N (173.25): C, 83.19; H, 8.73; N, 8.08. Found: C, 83.20; H,
Synthesis and Characterization of [ClAuS]. A solution containing
30.0 mg of (THT)AuCl (0.094 mmol) and 20.1 mg of S (0.094
mmol) dissolved in 5 mL of dry CH Cl was stirred for 20 min, then
2
2
12
15
filtered on a Celite pad. The volume of the solution was reduced to 2
mL, and 10 mL of hexane was added to precipitate the product as a
white powder, which was filtered, washed with hexane (3 × 3 mL), and
1
8
.75; N, 8.09. H NMR (CD Cl, 200 MHz, J in Hz): δ = 7.29−7.19
3
HH
(
m, 1H), 7.13−7.00 (m, 1H), 6.66 (td, J
= 7.7, 0.9, 2H), 4.16 (s,
3
HH
HH
1
2
3
1
3
H), 2.47 (t, J
= 6.9, 2H), 1.71−1.40 (m, 4H), 0.95 (t, J3 = 7.2,
dried under reduced pressure. Yield: 37.8 mg (90%). H NMR (400.13
3
H). 13C{ H} NMR (CD Cl , 50 MHz): δ = 148.28 (s), 132.20 (s),
1
2
2
MHz, CD Cl , 298 K, J in Hz): δ = 7.62 (s, 1H, H12), 7.41 (d, 1H,
2
2
HH
HH
HH
29.13 (s), 117.88 (s), 114.29 (s), 109.06 (s), 96.13 (s), 77.13 (s),
1.45 (s), 22.44 (s), 19.59 (s), 13.77 (s).
J3 = 8.1, H9), 7.21 (dd, 1H, J3 = 8.2, J4 = 1.1, H10), 3.31 (s,
6H, H14), 2.55 (m, 2H, C4), 2.45 (s, 3H, H13), 2.09 (m, 2H, H3),
H
Organometallics XXXX, XXX, XXX−XXX