Organometallics
Article
3
and PhCCMe (40 μL, 0.32 mmol). 5a′ is soluble in CH Cl ,
1H, H13 bpy), 8.36 (t, 3JHH = 8 Hz, 1H, H14′ bpy), 8.15 (t, J = 8
2
2
HH
3
CHCl , and acetone. Yield: raw product, 90 mg; crystallized product,
Hz, 1H, H14 bpy), 7.86 (t, J = 6 Hz, 1H, H15′ bpy), 7.58 (s, 1H,
3
HH
−1
2
−1
1
III
IV
3
9 mg (33%). Mp: 286 °C. ΛM (acetone): 257 Ω cm mol . H
H9), 7.57−7.51 (m, 5H, o,p-H Ph + o-H Ph ), 7.52 (s, 1H, H6),
3 3
3
NMR (600 MHz, CDCl ): 8.89 (d, J = 6 Hz, 2H, H16′ tbbpy),
7.50 (d, J = 5 Hz, 1H, H16 bpy), 7.38 (t, J = 8 Hz, 2H, m-H
HH HH
3
HH
3
3
III
3
IV
3
8
.19 (d, J = 6 Hz, 2H, H16 tbbpy), 8.06 (d, J = 2, 2H, H13′
Ph ), 7.36 (t, J = 8 Hz, 2H, m-H Ph ), 7.34 (d, J = 16 Hz, 1H,
HH
HH
HH HH
3
3
4
II
IV
tbbpy), 8.03 (d, J = 2, 2H, H13 tbbpy), 8.00 (dd, J = 6, J =
Hα), 7.34−7.27 (m, 4H, m,p-H Ph + p-H Ph ), 7.26−7.20 (m, 3H,
II I 3
HH
HH
HH
3
4
2
7
, 2H, H15′ tbbpy), 7.59 (dd, J = 6, J = 2, 2H, H15 tbbpy),
.36−7−32 (m, 4H, o-H Ph ), 7.30−7.27 (m, 6H, m,p-H Ph ), 7.27
H15 bpy + o-H Ph ), 7.18−7.13 (m, 3H, m,p-H Ph ), 7.01 (d, JHH =
I
HH
HH
II
II
16 Hz, 1H, Hβ), 6.99−6.95 (m, 2H, o-H Ph ), 3.80 y 3.76 (AB system,
I 13 1
I
2
(
s, 2H, H6), 7.06−7.03 (m, 4H, o-H Ph ), 6.94−6.88 (m, 6H, m,p-H
JHH = 14 Hz, 2H, CH Ph ). C{ H} NMR (150.9 MHz, CDCl ):
2 3
I
2
I
Ph ), 4.09 and 3.50 (AB system, J = 14 Hz, 4H, CH Ph ), 1.72 (s,
154.0 (C12 bpy), 153.8 (C12′ bpy), 152.3 (CH16′ bpy), 151.4 (CH16
HH
2
6
H, Me-3), 1.47 (s, 18H, tBu′), 1.46 (s, 18H, tBu). Anal. Calcd for
bpy), 142.2 (CH14′ bpy), 141.8 (CH14 bpy), 137.5 (C8), 136.8 (i-C
IV
I
C H Cl N O Pd : C, 62.47; H, 5.52; N, 3.83. Found: C, 62.42; H,
Ph ), 136.0 (C5), 134.4 (i-C Ph ), 134.2 (C4), 132.1 (CHβ), 131.2
7
6
80
2
4
8
2
II
II
III
5
.71; N, 3.81. Single crystals of 5a′·8CH Cl were grown by liquid
(C2), 131.0 (2C, o-CH Ph ), 130.8 (i-C Ph ), 130.0 (p-CH Ph ),
2
2
III
III
III
diffusion of Et O into a solution of 5a′ in CH Cl .
129.9 (2C, o-CH Ph ), 129.7 (2C, m-CH Ph ), 129.7 (i-C Ph ),
129.2 (p-CH Ph ), 129.15 y 129.09 (4C, m-CH Ph ,Ph ), 129.0 (2C,
2
2
2
II
I
IV
Synthesis of [(μ-η,η-C H Bn -1,5-Ph -2,6-Me -3,7){Pd-
1
2
2
2
2
2
I
IV
I
(tmeda)} ](OTf) (5b). The brownish complex 5b was similarly
m-CH Ph ), 128.7 (p-CH Ph ), 128.7 (2C, o-CH Ph ), 128.3 (CH15′
2
2
I
prepared from 1b (60 mg, 0.067 mmol), TlOTf (47 mg, 0.13 mmol),
and PhCCMe (68 μL, 0.54 mmol). 5b is soluble in CH Cl , CHCl ,
bpy), 127.6 (CHα), 127.4 (p-CH Ph ), 127.2 (CH15 bpy), 127.1
IV
2
2
3
(2C, o-CH Ph ), 125.7 (CH13′ bpy), 125.1 (CH13 bpy), 124.1 (C7),
I
and acetone. Yield: raw product, 63 mg; crystallized product, 38 mg
122.8 (CH6), 114.7 (CH9), 94.1 (C3), 93.1 (C1), 31.2 (CH Ph ).
2
−
1
2
−1 1
(
(
45%). Mp: 185 °C. Λ (acetone): 237 Ω cm mol . H NMR
Anal. Calcd for C H BrClN O Pd: C, 61.35; H, 3.81; N, 3.11.
M
46 34
2
4
II
600 MHz, CDCl ): 7.49−7.45 (m, 4H, m-H Ph ), 7.45−7.40 (m, 6H,
Found: C, 61.73; H, 3.77; N, 3.15.
3
II
I
o,p-H Ph ), 7.15−7.13 (m, 6H, p,m-H Ph ), 6.97−6.95 (m, 4H, o-H
Synthesis of [Pd(η-C H Bn-1-Me -2,3-((E)-CHCHPh)-5-Br-
9
2
2
I
2
Ph ), 6.90 (s, 2H, H6), 3.54 and 3.29 (AB system, J = 15 Hz, 4H,
6)(bpy)]OTf (7). The brownish complex 7 was similarly prepared
from 2 (80 mg, 0.11 mmol), TlOTf (39 mg, 0.11 mmol), and MeC
CMe (69 μL, 0.88 mmol). 7 is soluble in CH Cl , CHCl , and acetone.
2 2 3
HH
I
CH Ph ), 3.35−3.24 (m, 4H, NCH tmeda), 3.00, 2.90, 2.82, and 2.53
2
2
(
s, 6H, MeN tmeda), 2.78−2.70 (m, 4H, NCH tmeda), 1.36 (s, 6H,
2
13
1
−1
2
−1
Me-3). C{ H} NMR (150.9 MHz, CDCl ): 138.3 (2C, C4), 136.7
Yield: 45 mg (50%). Mp: 208 °C. Λ (acetone): 154 Ω cm mol .
3
M
3
I
II
1
(
1
2C, C5), 135.7 (2C, i-C Ph ), 132.4 (2C, C2), 131.6 (2C, i-C Ph ),
30.5 (4C, o-CH Ph ), 129.3 (4C, m-CH Ph ), 129.1 (2C, p-CH
Ph ), 128.9 (4C, o-CH Ph ), 128.7 (4C, m-CH Ph ), 126.9 (2C, p-CH
Ph ), 105.6 (2C, CH6), 91.4 (2C, C3), 88.5 (2C, C1), 61.9 and 61.8
H NMR (600 MHz, CDCl
): 8.61 and 8.59 (d, JHH = 8 Hz, 1H,
3
II
II
3
H13,13′ bpy), 8.53 and 8.49 (d, J = 5 Hz, 1H, H16,16′ bpy), 8.25
HH
II
I
I
3
3
and 8.32 (t, J = 8 Hz, 1H, H14,14′ bpy), 7.74 and 7.71 (t, J = 6
HH
HH
II
3 IV
Hz, 1H, H15,15′ bpy), 7.54 (d, J = 8 Hz, 2H, o-H Ph ), 7.38−7.30
HH
I IV 3
(
(
2C, CH N tmeda), 52.8, 52.3, 52.2, and 51.7 (2C, MeN tmeda), 31.1
(m, 7H, Ph , m-H Ph ), 7.33 (s, 1H, H9), 7.31 (d, J = 16 Hz, 1H,
2
HH
I
IV
3
2C, CH Ph ), 11.3 (2C, Me-3). Anal. Calcd for C H F N O Pd S :
Hα), 7.28−7.24 (m, 1H, p-H Ph ), 7.19 (s, 1H, H6), 7.12 (d, J
=
HH
2
54 64
6
4
6
2
2
2
I
C, 51.64; H, 5.14; N, 4.46; S, 5.11. Found: C, 50.32; H, 4.93; N, 4.61;
S, 4.95. With respect to the deviation of the C percentage see the
Results and Discussion. HR ESI+ TOF MS: calcd for
C H F N O Pd S m/z 1107.2746, found 1107.2753, Δ = 0.6 ppm.
16 Hz, 1H, Hβ), 3.90 y 3.53 (AB system, JHH = 14 Hz, 2H, CH
2
Ph ),
2.42 (s, 3H, Me-2), 1.82 (s, 3H, Me-3). 13C{ H} NMR (150.9 MHz,
CDCl ): 153.7 and 153.5 (1C, C12,12′ bpy), 152.1 and 151.7 (1C,
CH16,16′ bpy), 141.6 (2C, CH14,14′ bpy), 137.6 (1C, C4), 137.4
1
3
5
3
64
3
4
3
2
IV
I
Synthesis of [Pd(η-C H Bn-1-Ph -2,3-((E)-CHCHPh)-5-Br-
suspension of 2 (80 mg, 0.11 mmol) and TlOTf (39 mg, 0.11 mmol)
(1C, C5), 137.0 (1C, i-C Ph ), 136.1 (1C, C8), 134.5 (1C, i-C Ph ),
9
2
2
I
IV
6
)(bpy)]OTf (6). PhCCPh (157 mg, 0.88 mmol) was added to a
131.8 (1C, CHβ), 129.4 (2C, m-CH Ph ), 129.0 (2C, m-CH Ph ),
IV
I
128.5 (1C, p-CH Ph ), 128.3 (2C, o-CH Ph ), 128.0 and 127.7 (1C,
I
in CH Cl (15 mL) under N . The mixture was stirred for 24 h at
CH15,15′ bpy), 127.7 (1C, p-CH Ph ), 127.6 (1C, C2), 127.1 (2C, o-
2
2
2
IV
room temperature (color changed from yellow to brown) and filtered
over Celite. The resulting brownish solution was evaporated to
CH Ph ), 127.0 (1C, CHα), 124.93 and 124.87 (1C, CH13,13′
bpy), 124.1 (1C, C7), 120.3 (1C, CH6), 113.6 (1C, CH9), 91.3 (1C,
I
dryness. Et O (20 mL) was added to precipitate a brownish solid,
C3), 90.1 (1C, C1), 31.4 (1C, CH Ph ), 13.2 (1C, Me-2), 10.8 (1C,
2
2
which was filtered off, thoroughly washed with Et O (3 × 5 mL), and
Me-3). Anal. Calcd for C H BrF N O PdS: C, 53.80; H, 3.66; N,
3.39; S, 3.88. Found: C, 53.52; H, 3.94; N, 3.48; S, 3.59.
2
37 30
3
2
3
dried in vacuo to give 6 as a brown solid, which is soluble in CH Cl ,
2
2
CHCl , and acetone. Yield: 73 mg (70%). Mp: 186 °C. Λ (acetone):
Synthesis of [Pd(η-C H Bn-1-Ph-2-Me-3-((E)-CHCHPh)-5-
3
M
9
2
−1
2
−1
1
3
1
50 Ω cm mol . H NMR (600 MHz, CDCl ): 8.88 (d, J = 8
Br-6)(bpy)]OTf (8). The brownish complex 8 was similarly prepared
from 2 (80 mg, 0.11 mmol), TlOTf (39 mg, 0.11 mmol), and PhC
CMe (110 μL, 0.88 mmol). 8 is soluble in CH Cl , CHCl , and
2 2 3
3
HH
3
3
Hz, 1H, H13′ bpy), 8.77 (d, J = 8 Hz, 1H, H13 bpy), 8.69 (d, J
HH
HH
3
=
J
(
5 Hz, 1H, H16′ bpy), 8.39 (t, J = 8 Hz, 1H, H14′ bpy), 8.16 (t,
HH
−
1
3
3
acetone. Yield: 79 mg (81%). Mp: 192 °C. Λ (acetone): 165 Ω
= 8 Hz, 1H, H14 bpy), 7.84 (t, J = 6 Hz, 1H, H15′ bpy), 7.58
M
HH
HH
2
−1
1
3
III
IV
cm mol . H NMR (600 MHz, CDCl ): 8.77 (d, J = 8 Hz, 1H,
s, 1H, H9), 7.56−7.51 (m, 5H, o,p-H Ph + o-H Ph ), 7.51 (s, 1H,
3 HH
3
3
3
3
H13′ bpy), 8.72 (d, J = 8 Hz, 1H, H13 bpy), 8.59 (dd, J = 5,
H6), 7.49 (d, J = 5, 1H, H16 bpy), 7.38 (t, J = 8 Hz, 2H, m-H
HH
HH
HH
HH
4
3
4
III
3
IV
3
J
= 1, 1H, H16′ bpy), 8.41 (d, J = 5 Hz, J = 1 Hz, 1H, H16
Ph ), 7.36 (t, J = 8 Hz, 2H, m-H Ph ), 7.34 (d, J = 16 Hz, 1H,
HH
HH
HH
HH
HH
3
4
3
II
IV
bpy), 8.33 (td, J = 8 Hz, J = 1 Hz, 1H, H14′ bpy), 8.25 (td, J
Hα), 7.34−7.27 (m, 4H, m,p-H Ph + p-H Ph ), 7.26−7.20 (m, 3H,
HH
HH
HH
4
3
3
II
I
3
=
8 Hz, J = 1 Hz, 1H, H14 bpy), 7.74 (ddd, J = 8 Hz, J = 5
H15 bpy + o-H Ph ), 7.19−7.14 (m, 3H, m,p-H Ph ), 7.01 (d, J
=
HH HH HH
HH
4
3
3
I
Hz, J = 1 Hz, 1H, H15′ bpy), 7.69 (ddd, J = 8 Hz, J = 5 Hz,
1
6 Hz, 1H, Hβ), 6.98−6.95 (m, 2H, o-H Ph ), 3.79 and 3.73 (AB
HH
HH
HH
4
IV
2
I
JHH = 1 Hz, 1H, H15 bpy), 7.55−7.52 (m, 2H, o-H Ph ), 7.42 (s, 1H,
system,
J
= 14 Hz, 2H, CH Ph ). Anal. Calcd for
HH 2
II
3
IV
C H BrF N O SPd: C, 59.41; H, 3.61; N, 2.95; S, 3.37. Found: C,
H9), 7.39 (s, 5H, Ph ), 7.35 (t, JHH = 8 Hz, 2H, m-H Ph ), 7.33 (d,
4
7
34
3
2
3
3
5
8.90; H, 3.65; N, 2.92; S, 3.36. With respect to the deviation of the C
J
HH = 16 Hz, 1H, CHα), 7.31 (s, 1H, H6), 7.30−7.28 (m, 1H, p-H
IV
I
3
percentage see the Results and Discussion. HR ESI+ TOF MS: calcd
Ph ), 7.22−7.19 (m, 3H, m,p-H Ph ), 7.14 (d, JHH = 16 Hz, 1H,
I
2
for C H BrN Pd m/z 801.0944, found 801.0944, Δ = 0.00 ppm.
CHβ), 7.00−6.98 (m, 2H, o-H Ph ), 3.72 y 3.53 (AB system, JHH = 14
I 13 1
46
34
2
Single crystals of 6 were grown by liquid diffusion of Et O into a
Hz, 2H, CH
Ph ), 1.76 (s, 3H, Me-3). C{ H} NMR (150.9 MHz,
2
2
solution of 6 in CH Cl .
CDCl ): 154.0 (1C, C12′ bpy), 153.6 (1C, C12 bpy), 151.8 (1C,
3
2
2
Synthesis of [Pd(η-C H Bn-1-Ph -2,3-((E)-CHCHPh)-5-Br-
CH16′ bpy), 151.4 (1C, CH16 bpy), 142.0 (1C, CH14′ bpy), 141.9
9
2
2
IV
6
)(bpy)]ClO (6′). The brownish complex 6′ was similarly prepared
(1C, CH14 bpy), 137.0 (1C, i-C Ph ), 136.9 (1C, C4), 136.9 (1C,
4
I
from 2 (80 mg, 0.11 mmol), AgClO (23 mg, 0.11 mmol), and PhC
C8), 136.4 (1C, C5), 134.7 (1C, i-C Ph ), 132.2 (1C, CHβ), 132.1
4
II
II
CPh (157 mg, 0.88 mmol). 6′ is soluble in CH Cl , CHCl , and
(1C, C2), 130.7 (2C, o-CH Ph ), 130.5 (1C, i-C Ph ), 129.5 (1C, p-
2
2
3
−1
II
II
I
IV
acetone. Yield: 58 mg (58%). Mp: 194 °C. Λ (acetone): 144 Ω
CH Ph ), 129.2 (2C, m-CH Ph ), 129.1 (4C, m-CH Ph ,Ph ), 128.6
M
2
−1
1
3
IV
I
cm mol . H NMR (600 MHz, CDCl ): 8.75 (d, J = 8 Hz, 1H,
(1C, p-CH Ph ), 128.5 (2C, o-CH Ph ), 128.0 (1C, CH15 bpy), 127.8
(1C, CH15′ bpy), 127.5 (1C, p-CH Ph ), 127.1 (2C, o-CH Ph ),
3
HH
3
3
I
IV
H13′ bpy), 8.73 (d, J = 5 Hz, 1H, H16′ bpy), 8.64 (d, J = 8 Hz,
HH
HH
K
dx.doi.org/10.1021/om5010034 | Organometallics XXXX, XXX, XXX−XXX