1
Yield = 1.09 g, 72%. H NMR (300 MHz, CDCl
3
) 1.71 (18 H, s,
),
mixture was filtered and the volatiles removed from the filtrate
3
CH
3
) 2.99 (4 H, t, JH–H = 6.8, CH
2
CH
2
), 3.71 (2 H, s, PhCH
2
under reduced pressure to give 12 as a yellow solid. Yield =
3
3
1
4
.19 (4 H, t, JH–H = 6.8, CH
2
CH
2
), 7.06 (2 H, d, JHH = 1.8,
, CH=CH); C{ H} NMR
), 49.8 (CH CH ), 55.2 (CH CH ),
156 mg, 65%. H NMR (500 MHz, CDCl
3
, 233 K) 1.93 (18 H, s,
1
3
1
2
CH=CH), 7.14–7.30 (7 H, m, C
75.5 MHz, CDCl ) 38.9 (CH
), 59.4 (C(CH
), 128.8 (C
H
CH
13.6, PhCH
m, N(Bn)CH
N(Bn)CH
), 3.29 (2 H, m, (N(Bn)CH
CH
), 3.95 (1 H, d, JH–H = 13.6, PhCH
), 4.62 (2 H, m, N(Bn)CH CH ) 5.36 (2 H, m,
), 3.77 (1 H, d, JH–H
=
6
5
3
2
2
2
(
3
3
2
2
2
2
2
2
), 3.96 (2 H,
5
1
(
2
6.4 (PhCH
28.5 (C
2
3
)
3
), 121.8 (CH=CH), 122.0 (CH=CH),
2
2
2
ipso
3
H
5
6
H
5
), 129.1 (C
6
H
5
), 138.0 (
C
6
H
5
), 181.1
2
) 6.94 (2 H, d, JH–H = 1.9, CH=CH) 7.02 (2 H, d,
6
+
3
13
CAg); MS (TOF ES ) m/z 694.3 ([M] 5%), 514.2 (100, [M − Ag −
J
H–H = 1.9, CH=CH), 7.28–7.42 (5 H, m, CHaryl); C NMR
+
Cl] ). Anal. [found (calc.)] C25
.69 (5.36), N 9.87 (10.07).
H
39Ag
2
Cl
2
N
5
: C 43.19 (43.19), H
(100.5 MHz, CDCl
3
) 31.9 (CH
3
), 47.2 (CH
2
CH
2
), 49.8 (CH
2
CH ),
2
5
58.2 (C(CH )), 59.0 (PhCH
3
2
), 117.8 (CH=CH), 125.2 (CH=CH),
ipso
1
(
[
27.2 (CHaryl), 128.1 (CHaryl), 128.4 (CHaryl), 138.1 (
Caryl), 165.6
Mes
Mes
[
C(AgCl)N(Bn)C(AgCl) ] (9). Compound 9 was prepared
as a light brown solid following an analogous procedure as for 8
using dichloromethane (15 mL), 3 (488 mg, 0.81 mmol) and Ag
0.21 g, 0.88 mmol). Yield = 415 mg, 67%. H NMR (270 MHz,
CDCl ) d 1.96 (12 H, s, CH ), 2.30 (6 H, s, CH ), 3.07 (4 H, t,
), 3.78 (2 H, s, PhCH ), 4.25 (4 H, t, JH–H
+
+
CPd). MS (TOF ES ) m/z 548 ([M − Cl ] 38%) 512 (100,
+
M − 2Cl − H] ). HRMS calc. for C18
H
30
N
5
Pd: 546.1777, found
2
O
5
46.1770. Anal. [found (calc.)] for C25
H
37
N
5
PdCl
2
(+0.5 CHCl
3
1
(
(
(
analysis performed on NMR sample)): C 48.18 (47.51), H 5.43
5.86), N 10.08 (10.86).
3
3
3
3
3
J
H–H = 6.7, CH
2
CH
2
2
=
3
6
.7, CH
2
CH
2
), 6.89 (2 H, d, JH–H = 1.5, CH=CH), 6.92 (2 H, s,
Mes
Mes
[
(
CN(H)C )PdCl ] (13). Compound 13 was prepared as
2
3
CHmes), 7.25 (5 H, m, C
6
H
5
), 7.33 (2 H, d, J = 1.5 Hz, CH=CH);
an off white powder following an analogous procedure as for 12
using PdCl (MeCN) (28 mg, 0.110 mmol) and 11 (20 mL, 80 mg,
.110 mmol). Yield = 40 mg, 59%. H NMR (270 MHz, CDCl
.01 (6 H, s, CH ), 2.55 (6 H, s, CH ), 2.56 (6 H, s, CH ), 2.57 (2 H,
), 3.82 (2 H, m, CH ), 4.33 (2 H, m, CH ), 4.40 (2 H, m,
1
3
1
C{ H} NMR (67.9 MHz, CD
3
CN) d 17.8 (CH
3
), 21.6 (CH
3
),
2
2
5
1
1
1.0 (CH CH ), 56.0 (CH CH ), 60.2 (PhCH
2
2
2
2
2
), 123.5 (CH=CH),
1
0
2
3
), d
24.0 (CH=CH), 128.6 (CHaryl), 129.0 (CHaryl), 129.8 (CHaryl),
ipso
ipso
ipso
3
3
3
30.4 (CHaryl), 136.4 (
C
aryl), 137.3 (
C
aryl), 139.5 (
Caryl), 140.7
m, CH
CH
2
2
2
ipso
+
(
C
aryl) (CAg) not detected; MS (TOF ES ) m/z 638 (100, [M −
3
), 6.73 (2 H, d, JH–H = 1.9 Hz, CH=CH), 6.83 (2 H, s, CHaryl),
+
2
Ag − 2Cl] ).
3
6
.86 (2 H, s, CHaryl), 7.09 (2 H, d, JH–H = 1.9 Hz, CH=CH),
tBu
tBu
13
[
C(AgCl)N(H)C(AgCl) ] (10). Compound 10 was pre-
pared as a light brown solid following an analogous procedure
as for 8 using dichloromethane (60 mL), 4 (2.15 g, 5.5 mmol) and
7.58 (1 H, broad s, NH). C NMR (67.9 MHz, CDCl
3
), 18.4
CH ),
), 129.0
), 166.8 (CPd). MS (ESI), m/z
(CH
121.2 (CH=CH), 123.5 (CH=CH), 128.5 (C
(C (CH ), 138.3 (C (CH
584 ([M − Cl] , 100%), 548 ([M − 2Cl] , 85%).
3
), 19.7 (CH
3
), 21.0 (CH
3
), 49.7 (CH
2
CH
2
), 51.3 (CH
(CH
2
2
6
H
2
)
3 3
1
Ag
CDCl
4
2
O (1.53 g, 6.6 mmol). Yield = 2.57 g, 64%. H NMR (300 MHz,
6
H
2
3
)
3
6
H
2
)
3 3
3
+
+
3
) 1.71 (18 H, s, CH
3
), 3.02 (4 H, t, JH–H = 5.9, CH
2
CH ),
2
3
3
.23 (4 H, t, JH–H = 5.9, CH
2
CH
2
), 7.18 (2 H, d, JH–H = 6.0,
3
13
1
tBu
tBu
CH=CH), 7.19 (2 H, d, JH–H = 6.0, CH=CH); C{ H} NMR
75.5 MHz, CDCl ), 32.2 (CH ), 50.6 (CH CH ), 53.5 (CH CH ),
8.1 (C(CH
), 119.3 (CH=CH), 120.8 (CH=CH), 178.0 (CAg);
MS (TOF ES ) m/z 644.5 ([M + K] , 7%), 318.2 (M − 2Cl −
[( CN(Bn)C )Pd(NCMe)
][BF
2
] (15). An acetonitrile solu-
2
2
(
3
3
2
2
2
2
tion (2 mL) of AgBF (27 mg, 0.14 mmol) was added to an
4
5
3
)
3
acetonitrile solution (5 mL) of 12 (41 mg, 0.07 mmol) immediately
giving a white precipitate and the mixture stirred in the dark for 1 h.
The mixture was filtered and the volatiles removed from the filtrate
+
+
+
+
2
Ag − H] , 76%), 354.2 (100, [M − Cl − 2Ag − H] ). Anal.
[
found (calc.)] for C18 Cl : C 35.76 (35.79), H 5.32 (5.17),
H
33Ag
2
2
N
5
under reduced pressure to give 15 as a pink solid. Yield = 43 mg,
1
N 11.42 (11.59).
80%. H NMR (500 MHz, CD
3
CN, 238 K) 1.82 (18 H, s, CH ),
3
2
.96 (2 H, m, CH
2
CH
2
), 3.16 (2 H, m, CH
CH ), 4.83 (2 H, m, CH
.45 (9 H, CH=CH, Ph); C NMR (67.9 MHz, CD
2.3 (CH ), 52.2 (CH CH ), 56.4 (C(CH )), 66.1 (CH
2
CH
2
), 4.02 (2 H, s,
CH ), 7.33–
CN, 300 K)
CH ), 73.0
Mes
Mes
[
C(AgCl)N(H)C(AgCl) ] (11). Compound 11 was pre-
PhCH ), 4.33 (2 H, m, CH
7
3
2
2
3
2
2
2
pared as a white powder solid following an analogous procedure
as for 8 using dichloromethane (15 mL), 5 (157 mg, 0.31 mmol)
and Ag
270 MHz, CDCl
1
3
1
3
2
2
3
2
2
2
O (156 mg, 0.67 mmol). Yield = 155 mg, 70%. H NMR
(
(
(
PhCH
2
), 123.0 (CH=CH), 124.0 (CH=CH), 129.8 (CHaryl), 130.0
(
(
6
3
) d 1.93 (12 H, s, CH
3
), 2.31 (6 H, s, CH
3
), 3.13
CH ),
ipso
CHaryl), 133.5 (CHaryl), 140.1 (
calc.)] for C29
Caryl), 158.8 (CPd). Anal. [found
3
3
4 H, t, JH–H = 6.3, CH
2
CH
2
), 4.29 (4 H, t, JH–H = 6.3, CH
2
2
H
43
N
7
B
2
8
F Pd: C 45.35 (45.25), H 6.00 (5.63), N
3
.92 (4 H, s, CHaryl), 7.24 (2 H, d, JH–H = 1.5, CH=CH), 7.45 (2 H,
1
2.43 (12.74).
3
13
1
d, JH–H = 1.5, CH=CH); C{ H} NMR (67.9 MHz, CDCl
) d
), 122.0
3
1
(
(
7.7 (CH
3
), 21.0 (CH
3
), 50.2 (CH
2
CH
2
), 51.9 (CH
2
ipso
CH
C
2
Mes
Mes
[
(
CN(H)C )Pd(NCMe)
2
][BF
2
2
] (16). Compound 16 was
CH=CH), 122.6 (CH=CH), 129.3 (CHaryl), 134.6 (
aryl), 135.3
prepared as a white solid following an analogous procedure as
for 15 using AgBF
ipso
ipso
+
Caryl), 139.4 (
C
aryl) (CAg) not detected; MS (TOF ES ) m/z
−
5
(9.5 mg, 4.8 × 10 mol) and 13 (15 mg,
CN), d 2.27 (6 H, s,
), 3.21 (2 H, m, CH ), 3.30 (2 H, m,
), 4.36 (2 H, m, CH ), 5.27 (1 H, broad s,
+
+
4
6
18 ([M − Ag − H] , 43%), 548 (100, [M − 2Cl − Ag − H] ).
−
5
1
2
CH
CH
.4 × 10 mol). H NMR (270 MHz, CD
3
Anal. [found (calc.)] for C28 Cl : C 45.35 (46.16), H 4.91
H
35Ag
2
2
N
5
3
), 2.34 (12 H, s, CH
), 4.31 (2 H, m, CH
3
2
(
4.84), N 9.27 (9.62).
2
2
2
tBu
tBu
[
(
CN(Bn)C )PdCl
2
]
(12). Dichloromethane solutions
] (107 mg, 0.41 mmol) and 8 (10 mL,
85 mg, 0.41 mmol) were added simultaneously to dichloro-
NH), 6.97 (2 H, s, CHaryl), 7.08 (2 H, s, CHaryl), 7.12 (2 H, d,
3
3
(
2
10 mL) of [PdCl
2
(CH
3
CN)
2
J = 1.8 Hz, CH=CH), 7.44 (2 H, d, J = 1.8 Hz, CH=CH).
1
3
C NMR (67.9 MHz, CD
3
CN), d 19.4 (CH
3
), 20.8 (CH ), 49.0
3
◦
methane (20 mL) and stirred at −80 C for 10 min in the absence
of light. A precipitate formed immediately. The solution was
warmed to room temperature and stirred for a further 1 h. The
(CH
125.5 (C
140.9 (C
2
CH
2
), 52.3 (CH
(CH ), 130.5 (C
(CH ), CPd not detected.
2
CH
2
), 123.6 (CH=CH), 124.4 (CH=CH),
6
H
2
3
)
3 3
)
3
6
H
2
(CH ), 130.9 (C (CH ),
3
)
3
6
H
2
)
3 3
6
H
2
This journal is © The Royal Society of Chemistry 2007
Dalton Trans., 2007, 3065–3073 | 3071