Organometallics
Article
Preparation of [(DiPP-NHC-Trop)AuCl] (DiPP-2). DiPP-1 (91.0
Preparation of [(Me-NHC-Trop)Au(NTf )] (Me-3). Gold com-
2
mg, 200 μmol), [(DMS)AuCl] (58.9 mg, 200 μmol), and K CO3
plex Me-2 (25.2 mg, 50.0 μmol) and AgNTf (23.3 mg, 60.0 μmol)
2
2
(
55.3 mg, 400 μmol) were suspended in dry acetone (3 mL) and were
stirred at 60 °C for 7 h. The mixture was filtered through a pad of silica
glass pipet: one-third filled) and the filtrate was evaporated to dryness
were dried under vacuum for 15 min. Under an atmosphere of argon,
dry dichloromethane (3 mL) was added and the mixture was stirred in
the dark for 10 min. The suspension was filtered through a pad of
Celite (glass pipet: one-third filled), which was subsequently rinsed
with dichloromethane (3 × 1 mL), and the filtrate was concentrated to
approximately 0.2 mL. After the addition of pentane (2 mL) the
product slowly precipitated as a microcrystalline material which was
further washed with pentane (2 × 1 mL). The product was obtained as
a white solid after drying under vacuum (33 mg, 88% yield). Single
crystals suitable for X-ray diffraction analysis were obtained by slow
(
on a rotary evaporator. After the crude product was filtered through a
pad of silica gel (glass pipet: one-third filled) and the pad was rinsed
with dichloromethane (3 × 1.5 mL), the filtrate was evaporated to
dryness. Slow vapor diffusion of pentane (2.5 mL) into a solution of
the crude product in CHCl provided DiPP-2 as colorless plates (80
mg, 68% yield) which were suitable for X-ray diffraction analysis. Anal.
Calcd for C H AuClN (651.00 g/mol): C, 55.35; H, 4.64; N, 4.30.
Found: C, 55.23; H, 4.62; N, 4.36. H NMR (500.13 MHz, CDCl ):
7
3
30
30
2
1
vapor diffusion of pentane into a solution of Me-3 in CHCl . Anal.
3
3
benz quart Ar
.83 (ps-d, J = 7.5 Hz, 2H, C
C
C H), 7.56−7.51 (m, 2H,
Calcd for C H AuF N O S (749.45 g/mol): C, 33.66; H, 2.15; N,
HH
21 16
6
3
4 2
Ar
Ar
3
1
C H), 7.50−7.47 (m, 4H, C H), 7.37 (t, J = 7.8 Hz, 1H, p-
C
6
5.61. Found: C, 33.74; H, 1.97; N, 5.68. H NMR (500.13 MHz,
HH
DiPP
3
DiPP
olef
3
benz quart Ar
H), 7.14 (d, J = 7.8 Hz, 2H, m-C H), 6.97 (s, 2H, C H),
CDCl ): 7.81 (ps-d, J = 7.4 Hz, 2H, C
C
C H), 7.54−7.49
HH
3
HH
benz
3
Imi
3
Ar
Ar
olef
.78 (s, 1H, C H), 6.63 (d, J = 2.0 Hz, 1H, C H), 6.61 (d, J
(m, 2H, C H), 7.48−7.44 (m, 4H, C H), 6.98 (s, 2H, C H), 6.77
H,H
H,H
Imi
3
benz 3
=
2.0 Hz, 1H, C H), 2.23 (sept, J = 6.9 Hz, 2H, CH(CH ) ), 1.17
(s, 1H, C H), 6.70 (d, J = 2.1 Hz, 1H, MeNCHCHN), 6.68 (d,
H,H
HH
3
2
3
a
b
3
3
13
1
(
d, J = 6.8 Hz, 6H, 2 × CH(CH ) (CH ) ), 1.04 (d, J = 6.9 Hz,
JHH = 2.1 Hz, 1H, MeNCHCHN), 3.71 (s, 3H, MeN). C{ H}
HH
3
3
HH
a
b
13
1
6
H, 2 × CH(CH ) (CH ) ). C{ H} DEPTQ NMR (125.76 MHz,
DEPTQ NMR (125.76 MHz, CDCl ): 163.27 (NCN), 134.37
3
3
3
DiPP
quart trop
quart trop
olef
quart trop
benz quart Ar
CDCl ): 173.43 (NCN), 145.53 (C -N), 134.94 (C
C
1
1
+ o-
(C
), 134.11 (C
), 131.66 (C
C
C H), 131.21
3
DiPP
quart trop
), 131.21 (CbenzC C H), 130.79 (C H),
quart Ar
olef
Ar
Ar
Ar
), 134.32 (C
(C H), 130.65 (C H), 130.10 (C H), 129.42 (C H), 121.77 (s,
MeNCHCHN), 120.67 (s, MeNCHCHN), 119.56 (q, J = 321.1
Hz, CF ), 71.54 (C H), 39.09 ((H C)N).
DiPP
Ar
Ar
Ar
1
30.44 (p-C H), 130.27 (C H), 129.93 (C H), 129.20 (C H),
24.14 (m-C H), 121.11 (s, C H), 120.96 (s, C H), 70.60
CF
DiPP
Imi
Imi
benz
3
3
benz
a
b
(
(
C
H), 28.33 (CH(CH ) ), 24.40 (CH(CH ) (CH ) ), 24.29
Preparation of [(DiPP-NHC-Trop)Au(NTf )] (DiPP-3). Gold
3
2
3
3
2
a
b
CH(CH ) (CH ) ).
complex DiPP-2 (35.0 mg, 53.8 μmol) and AgNTf (20.9 mg, 53.8
3
3
2
Preparation of [(Ad-NHC-Trop)AuCl] (Ad-2). Ad-1 (85.8 mg,
μmol) were dried under vacuum for 10 min. Under an atmosphere of
argon, dichloromethane (3 mL) was quickly added and the mixture
was stirred in the dark for 20 min. The suspension was filtered through
a pad of Celite (glass pipet: one-third filled), which was subsequently
rinsed with dichloromethane (3 × 1 mL), and the filtrate was
concentrated to approximately 0.3 mL. The slow addition of pentane
(∼2 mL) led to the precipitation of the product as colorless needles
which were further washed with pentane (2 × 1 mL) and dried under
vacuum (41 mg, 85% yield). Single crystals suitable for X-ray
diffraction analysis were obtained by slow vapor diffusion of pentane
2
4
6
00 μmol), [(DMS)AuCl] (58.9 mg, 200 μmol) and K CO (55.3 mg,
2
3
00 μmol) were suspended in dry acetone (3 mL) and were stirred at
0 °C for 7 h. The mixture was filtered through a pad of Celite (glass
pipet: one-third filled) and the filtrate was evaporated to dryness on a
rotary evaporator. After the crude product was filtered quickly through
a pad of silica gel (glass pipet: one-third filled) and the pad was rinsed
with dichloromethane (3 × 1.5 mL), the filtrate was evaporated to
dryness. Trituration of the residue with pentane (2 × 2 mL) and
drying under vacuum gave Ad-2 as a white solid (85 mg, 68% yield).
Anal. Calcd for C H AuClN (624.96 g/mol): C, 53.81; H, 4.52; N,
2
8
28
2
into a solution of DiPP-3 in CHCl . Anal. Calcd for
3
1
4
.48. Found: C, 53.68; H, 4.61; N, 4.51. H NMR (300.06 MHz,
C H AuF N O S (895.68 g/mol): C, 42.91; H, 3.38; N, 4.69.
3
2
30
6
3
4 2
benz quart Ar
1
CDCl ): 7.90 (ps-d, J = 7.3 Hz, 2H, C
C
C H), 7.52−7.44
Found: C, 43.02; H, 3.41; N, 4.75. H NMR (500.13 MHz, CDCl ):
3
HH
3
Ar
Ar
benz
benz quart Ar
(
(
m, 2H, C H), 7.44−7.41 (m, 4H, C H), 7.15 (s, 1H, C H), 6.97
7.81 (ps-d, J = 7.6 Hz, 2H, C
C
C H), 7.57−7.52 (m, 2H,
HH
olef
3
Imi
3
Ar
Ar
3
s, 2H, C H), 6.79 (d, J = 2.2 Hz, 1H, C H), 6.74 (d, J = 2.0
C H), 7.51−7.47 (m, 4H, C H), 7.42 (t, J = 7.8 Hz, 1H, p-
H,H
H,H
HH
Imi
3
Ad
Ad
DiPP 3 DiPP olef
Hz, 1H, C H), 2.39 (d, J = 3.1 Hz, 6H, C H ), 2.18 (s, C H),
C
H), 7.18 (d, J = 7.6 Hz, 2H, m-C H), 6.96 (s, 2H, C H),
HH
2
HH
Ad
13
1
3
Imi
benz
3
1
.69 (t, JHH = 2.9 Hz, 6H, C H ). C{ H} DEPTQ NMR (75.45
6.73 (d, J = 2.0 Hz, 1H, C H), 6.72 (s, 1H, C H), 6.63 (d, J
= 2.0 Hz, 1H, C H), 2.17 (sept, J = 6.9 Hz, 2H, CH(CH ) ), 1.14
HH 3 2
2
H,H H,H
quart trop
quart trop
Imi
3
MHz, CDCl ): 168.11 (NCN), 134.83 (C
), 134.48 (C
),
3
benz quart Ar
olef
Ar
3
a
b
3
1
32.99 (C
C
C H), 131.27 (C H), 130.57 (C H), 129.93
(d, J = 6.5 Hz, 6H, 2 × CH(CH ) (CH ) ), 1.04 (d, J = 6.9 Hz,
HH 3 3 HH
a b 13 1
Ar
Ar
Imi
Imi
(
(
(
C H), 129.06 (C H), 118.68 (s, C H), 116.42 (s, C H), 72.26
C
C H).
6H, 2 × CH(CH ) (CH ) ). C{ H} DEPTQ NMR (125.76 MHz,
3 3
DiPP DiPP
benz
Ad
quart
Ad
Ad
H), 59.41 (C -N), 44.21 (C H ), 35.84 (C H ), 29.93
CDCl ): 166.28 (NCN), 145.45 (C -N), 134.62 (o-C H), 134.56
3
2
2
quart trop
olef
quart trop
benz quart Ar
(C
), 134.17 (C
), 131.13 (C
C
C H), 130.77
DiPP
Ar
Ar
Preparation of (Trop-NHC-Trop)AuCl (Trop-2). Trop-1 (91.0
(C H), 130.64 (p-C H), 130.38 (C H), 129.97 (C H), 129.41
(C H), 124.14 (m-C H), 121.78 (s, C H), 121.50 (s, C H),
119.21 (q, J = 323.2 Hz, CF ), 70.78 (C H), 28.41 (CH(CH ) ),
24.62 (CH(CH ) (CH ) ), 24.58 (CH(CH ) (CH ) ).
Ar
DiPP
Imi
Imi
mg, 200 μmol), [(DMS)AuCl] (58.9 mg, 200 μmol) and K CO (55.3
2
3
1
benz
mg, 400 μmol) were suspended in dry acetone (3 mL) and were
stirred at 60 °C for 7 h. The mixture was filtered through a pad of
Celite (glass pipet: one-third filled), and the filtrate was evaporated to
dryness on a rotary evaporator. After the crude product was filtered
through a pad of silica gel (glass pipet: one-third filled) and the pad
was rinsed with dichloromethane (3 × 1.5 mL), the solvent was
removed and the product was triturated with pentane (2 × 2 mL). A
white powder was obtained after drying under vacuum (83 mg, 65%
yield). Colorless needles of Trop-1 suitable for X-ray diffraction
analysis were grown by slow vapor diffusion of pentane into a
CF 3 3 2
a
b
a
b
3
3
3
3
Preparation of [(Ad-NHC-Trop)Au(NTf )] (Ad-3). Gold complex
2
Ad-2 (25.0 mg, 40.0 μmol) and AgNTf (15.5 mg, 40.0 μmol) were
2
dried under vacuum for 10 min. Under an atmosphere of argon,
dichloromethane (2 mL) was quickly added and the mixture was
stirred in the dark for 10 min. The suspension was filtered through a
pad of Celite (glass pipet: one-third filled), which was subsequently
rinsed with dichloromethane (3 × 1 mL), and the filtrate was
evaporated to dryness. The crude product was filtered once again
through Celite and was concentrated to approximately 0.5 mL. The
product was precipitated by the addition of pentane (∼3 mL), washed
with pentane (2 mL), and dried under vacuum (32 mg, 92% yield).
Single crystals suitable for X-ray diffraction analysis were obtained by
slow vapor diffusion of pentane into a solution of Ad-3 in CHCl3.
Anal. Calcd for C H AuF N O S (869.65 g/mol): C, 41.43; H,
concentrated solution of the compound in CHCl . Anal. Calcd for
C H AuClN (680.99 g/mol): C, 58.20; H, 3.55; N, 4.11. Found: C,
5
3
3
3
24
2
1
8.05; H, 3.49; N, 4.02. H NMR (500.13 MHz, CDCl ): 7.75 (ps-d,
3
benz quart Ar
JHH = 7.4 Hz, 4H, C
C
C H), 7.43 (dt, J = 10.8 Hz, J = 1.9 Hz,
Ar
Ar
olef
4
H, C H), 7.40−7.35 (m, 8H, C H), 6.86 (s, 4H, C H), 6.82 (d,
H,H
3
benz Imi 13 1
J
= 2.2 Hz, 2H, C H), 6.39 (s, 2H, C H). C{ H} DEPTQ
30 28
6
3
4 2
quart trop
1
NMR (125.76 MHz, CDCl ): 169.68 (NCN), 134.48 (C
),
3.25; N, 4.83. Found: C, 41.52; H, 3.34; N, 4.86. H NMR (500.13
MHz, CDCl ): 7.87 (ps-d, J = 7.5 Hz, 2H, C
3
quart trop
benz quart Ar
olef
Imi
benz quart Ar
1
34.39 (C
), 131.80 (C
C
C H), 131.13 (C H), 130.43
C
C H), 7.52−
3
HH
Ar
Ar
Ar
Ar
Ar
benz
(C H), 129.85 (C H), 129.05 (C H), 119.31 (s, C H), 71.29
7.47 (m, 2H, C H), 7.47−7.42 (m, 4H, C H), 7.19 (s, 1H, C H),
benz
olef 3
(C
H).
7.01 (d, J = 1.0 Hz, 2H, C H), 6.99 (t, J
= 2.1 Hz, 1H,
HH
H,H
dx.doi.org/10.1021/om501093s | Organometallics XXXX, XXX, XXX−XXX
I