3
250
L. Huang et al. / Journal of Organometallic Chemistry 694 (2009) 3247–3253
–
N(CH
2
)
2
), 7.37 (t, 2H, J = 6.6 Hz, d-CH, Py), 7.58 (d, 2H, J = 7.8 Hz,
= 7.8 Hz, J = 1.5 Hz, -CH, Py), 8.32 (s,
H, –NH), 8.85 (d, 2H, J = 6.0 Hz, -CH, Py); C NMR (CD
162.2 (2C, Py-
Py-dC), 153.4 (2C, Py-
H) 3319, (C@O) 2030,
Calc. for C41
aC), 127.3 (2C, Py-bC), 142.0 (2C, Py-cC), 124.9 (2C,
b-CH, Py), 7.95 (td, 2H, J
1
2
c
r
C), 197.5 (3C, fac-Re(CO)
(C@O) 1916,
Cl
3
); IR (KBr):
(C@O) 1650 cm ; Anal.
: C, 45.43; H, 5.31; N, 4.92.
m
(O–
13
ꢁ1
1
3
6
4
r
3
OD): d
m
m
m
7.21 (C1), 31.5 (C2), 73.2 (C3), 40.8 (C4), 43.3 (C5), 36.8 (C6),
9.9 (C7), 41.3 (C8), 28.2 (C9), 36.2 (C10), 29.9 (C11), 74.3 (C12),
7.8 (C13), 43.5 (C14), 24.5 (C15), 29.1 (C16), 48.4 (C17), 13.3
H
56
N
4
O
6
ReBrꢂ2CH
2
2
Found: C, 45.21; H, 5.51; N, 4.97%.
0
Analytical data for complex 1d : Yield: 75%, m.p. 137.6–138.3 °C;
1
(
C18), 23.5 (C19), 36.9 (C20), 18.1 (C21), 34.4 (C22), 33.5 (C23),
H NMR (CD
3
OD): d 0.71 (s, 3H, 18-CH
3
3
), 0.90 (s, 3H, 19-CH ), 0.92–
0
0
1
Py-
1
3
for C41
4
77.7 (C24), 43.3 (C1 ), 69.4 (C2 ), 68.9 (2C, PyCH
C), 127.3 (2C, Py-bC), 142.0 (2C, Py- C), 125.0 (2C, Py-dC),
53.4 (2C, Py- C), 197.4 (3C, fac-Re(CO) ); IR (KBr): (O–H)
316, (C@O) 2030, (C@O) 1920, (C@O) 1642 cm ; Anal. Calc.
ReBrꢂ0.5CH Cl : C, 48.61; H, 5.60; N, 5.46. Found: C,
8.46; H, 5.56; N, 5.61%.
Analytical data for complex 2d: Yield: 76%, m.p. 166.8–168.6 °C;
H NMR (CD OD): d 0.68 (s, 3H, 18-CH ), 0.92 (s, 3H, 19-CH ), 0.99
), 1.03–1.13 (m, 1H), 1.15–1.22(m, 2H),
2
), 162.2 (2C,
0.98 (m, 1H), 1.03 (d, 3H, J = 6.5 Hz, 21-CH
1.21–1.65 (m, 19H), 1.66–1.98 (m, 10H), 2.08–2.13 (m, 1H), 2.20–
2.30 (m, 3H), 3.20 (t, 2H, J = 6.7 Hz, 6 -CH
3
), 1.05–1.13 (m, 1H),
a
c
0
r
3
m
2
), 3.33–3.39 (m, 1H, 3-
ꢁ1
0
m
H
m
m
CH), 3.77–3.79 (m, 2H, 1 -CH
2
), 3.79–3.81 (m, 1H, 7-CH), 3.95 (br
), 7.37 (t, 2H,
= 6.6 Hz, d-CH , Py), 7.58 (d, 2H, J = 7.8 Hz , b-CH, Py), 7.94 (td,
56
N
4
O
7
2
2
2 2
s, 1H, 12-CH), 4.83–4.91 (m, 4H, –N(CH )
J
1
2H, J
1
= 7.8 Hz, J
2
= 1.5 Hz,
c
-CH, Py), 7.98 (br s, 1H, –NH), 8.85 (d,
1
13
3
3
3
2H, J = 5.5 Hz,
r
3
-CH, Py); C NMR (CD OD): d 37.2 (C1), 31.5
(
d, 3H, J = 6.5 Hz, 21-CH
3
(C2), 73.2 (C3), 40.8 (C4), 43.3 (C5), 36.8 (C6), 72.1 (C7), 41.3
(C8), 28.2 (C9), 36.2 (C10), 29.9 (C11), 74.3 (C12), 47.8 (C13),
43.5 (C14), 24.5 (C15), 29.0 (C16), 48.4 (C17), 13.3 (C18), 23.5
(C19),37.2 (C20), 18.1 (C21), 34.6 (C22), 33.8 (C23), 177.1
1
1
.28–1.39 (m, 7H), 1.41–1.56 (m, 6H), 1.57–1.67 (m, 2H), 1.71–
.78 (m, 1H), 1.82–1.89 (m, 4H), 1.90–2.01 (m, 3H), 2.18–2.36
0
(
m, 3H), 3.33–3.40 (m, 1H, 3-CH), 3.74 (t, 2H, J = 7.0 Hz, 2 -CH
2
),
0
0
0
0
0
0
3
.72–3.79 (s, 1H, 7-CH),3.94 (t, 2H, J = 7.1 Hz, 1 -CH
), 7.37 (t, 2H, J = 6.5 Hz, d-CH,Py), 7.56 (d, 2H,
J = 7.9 Hz, b-CH, Py), 7.94 (t, 2H, J = 7.8 Hz, -CH, Py), 8.85 (d, 2H,
OD): d 37.2(C1), 31.7 (C2),
3.2 (C3), 40.8 (C4), 43.5 (C5), 36.5 (C6), 69.9 (C7), 41.1 (C8),
6.2 (C9), 36.9 (C10), 22.1 (C11), 41.4 (C12), 44.0 (C13), 51.9
2
), 4.90–5.03
(C24),40.4 (C1 ), 30.5 (C2 ), 26.6 (C3 ), 27.7 (C4 ), 27.9 (C5 ), 69.3
0
(
m, 4H, –N(CH
2
)
2
(C6 ), 69.1 (2C, PyCH2), 162.5 (2C, Py-
a
C), 127.2 (2C, Py-bC),
C), 124.9 (2C, Py-dC), 153.4 (2C, Py- C), 197.6
); IR (KBr): (O–H) 3436, (C@O) 2026, (C@O)
(C@O) 1634 cm ; Anal. Calc. for C45 Cl
ReBrꢂ2CH
c
141.9 (2C, Py-
(3C, fac-Re(CO)
1916,
c
r
1
3
J = 5.5 Hz,
7
3
r
-CH, Py); C NMR (CD
3
3
m
m
H
m
ꢁ
1
m
64
N
4
O
7
2
2
:
C, 46.69; H, 5.66; N, 4.63. Found: C, 46.79; H, 5.26; N, 5.01%.
0
(
3
C14), 24.9 (C15), 29.6 (C16), 57.6 (C17), 12.5 (C18), 23.7 (C19),
7.2 (C20), 19.2 (C21), 34.4 (C22), 33.5 (C23), 177.6 (C24), 44.0
Analytical data for complex 2d : Yield: 78%, m.p. 213.2–215.4 °C;
1
H NMR (CD
3
OD): d 0.68 (s, 3H, 18-CH
3 3
), 0.91 (s, 3H, 19-CH ), 0.92–
0
0
(
C1 ), 69.3 (C2 ), 68.9 (2C, PyCH2), 162.2 (2C, Py-
Py-bC), 142.0 (2C, Py- C), 124.9 (2C, Py-dC), 153.4 (2C, Py-
97.4 (3C, fac-Re(CO) ); IR (KBr): (O–H) 3316, (C@O) 2030,
C@O) 1916, (C@O) 1646 cm ; Anal. Calc. for C41
aC), 127.3 (2C,
0.96 (m, 1H), 0.97 (d, 3H, J = 6.5 Hz, 21-CH
1.23–1.38 (m, 6H), 1.41–1.62 (m, 14H), 1.66–2.02 (m, 10H), 2.08–
2.14 (m, 1H), 2.20–2.29 (m, 2H), 3.19 (t, 2H, J = 6.5 Hz, 6 -CH
3.30–3.40 (m, 1H, 3-CH), 3.78–3.80 (m, 2H, 1 -CH
3
), 1.06–1.21 (m, 3H),
c
r
C),
0
1
(
3
m
m
m
R-
2
),
ꢁ1
0
m
H
56
N
4
O
6
2
), 3.81–3.83
eBrꢂ0.5CH
2
Cl
2
: C, 49.37; H, 5.69; N, 5.55. Found: C, 49.30; H,
(m, 1H, 7-CH),4.83–4.89 (m, 4H, –N(CH
d-CH, Py), 7.56 (d, 2H, J = 7.9 Hz, b-CH, Py), 7.94 (td, 2H, J
7.8 Hz, J = 1.4 Hz, -CH, Py), 8.85 (d, 2H, J = 5.4 Hz, -CH, Py);
C NMR (CD OD): d 37.2 (C1), 31.7(C2), 73.1 (C3), 40.4 (C4), 41.4
(C5), 36.2 (C6), 72.2 (C7), 40.8 (C8), 34.5 (C9), 36.8 (C10), 22.1
(C11), 41.1 (C12), 43.5(C13), 51.8 (C14), 24.9 (C15), 29.6 (C16),
57.7 (C17), 12.5 (C18), 23.7 (C19),36.5 (C20),19.2 (C21), 34.4
2 2
) ), 7.37 (t, 2H, J = 6.7 Hz,
6
.02; N, 5.53%.
1
=
Analytical data for complex 3d: Yield: 73%, m.p. 226.7–228.3 °C;
H NMR (CD OD): d 0.70 (s, 3H, 18-CH ), 0.96 (s, 3H, 19-CH ), 0.99
), 1.01–1.05 (m, 1H), 1.08–1.38 (m, 10H),
2
c
r
1
13
3
3
3
3
(
d, 3H, J = 6.5 Hz, 21-CH
3
1
2
.39–1.49 (m, 6H), 1.50–1.61 (m, 4H), 1.77–1.90 (m, 5H), 2.01–
.07 (m, 1H), 2.15–2.22 (m, 1H), 2.31–2.37 (m, 1H), 3.40–3.50
0
0
0
0
(
m, 2H, 3-CH and 7-CH), 3.74 (t, 2H, J = 7.0 Hz, 2 -CH
2
), 3.94 (t,
(C22), 33.7 (C23), 177.6 (C24), 44.0 (C1 ), 30.6 (C2 ), 26.5 (C3 ),
0
0
0
0
2
H, J = 7.1 Hz, 1 -CH
2
), 4.90–5.05 (m, 4H, –N(CH
2
)
2
), 7.37 (t, 2H,
27.7 (C4 ), 27.9 (C5 ), 69.3 (C6 ), 69.1 (2C, PyCH2), 162.5 (2C, Py-
C), 127.2 (2C, Py-bC), 141.9 (2C, Py- C), 124.9 (2C, Py-dC), 153.5
(2C, Py- C), 197.5 (3C, fac-Re(CO) ); IR (KBr): (O–H) 3419,
(C@O) 2026, (C@O) 1916, (C = O) 1650 cm ; Anal. Calc. for
ReBrꢂ1.5CH
48.16; H, 5.69; N, 5.21%.
J = 6.6 Hz, d-CH, Py), 7.57 (d, 2H, J = 8.0 Hz, b-CH, Py), 7.94 (td,
H, J = 7.8 Hz, J = 1.4 Hz, -CH, Py, 8.85 (d, 2H, J = 5.4 Hz, -CH,
Py); C NMR (CD OD): d 38.3 (C1), 31.3 (C2), 72.4 (C3), 38.9
a
c
2
1
1
2
c
r
r
3
m
m
3
ꢁ1
3
m
m
(
(
C4), 44.3 (C5), 36.4 (C6), 72.3 (C7), 41.0 (C8), 35.5 (C9), 36.8
C10), 22.7 (C11), 41.9 (C12), 44.8 (C13), 56.9 (C14), 28.2 (C15),
C H
45 64
N
4
O
6
2
Cl
2
: C, 48.54; H, 5.86; N, 4.87. Found: C,
0
3
0.0 (C16), 57.8 (C17), 12.9 (C18), 24.2 (C19), 37.1 (C20), 19.3
Analytical data for complex 3d : Yield: 65%, m.p. 225.6–226.5 °C;
0
0
1
(
6
C21), 34.4 (C22), 33.5 (C23), 177.6 (C24), 45.1 (C1 ), 69.9 (C2 ),
8.9 (2C, PyCH ), 162.2 (2C, Py- C), 127.3 (2C, Py-bC), 141.9 (2C,
Py- C), 124.9 (2C, Py-dC), 153.4 (2C, Py- C), 197.3 (3C, fac-
Re(CO) ); IR (KBr): (O–H) 3319, (C@O) 2026, (C@O) 1920,
C@O) 1650 cm ; Anal. Calc. for C41 Cl : C,
ReBrꢂ1.5CH
6.64; H, 5.43; N, 5.11. Found: C, 46.32; H, 5.80; N, 5.01%.
Analytical data for complex 4d: Yield: 68%, m.p. 220.4–222.1 °C;
H NMR (CD OD): d 0.68 (s, 3H, 18-CH ), 0.92 (s, 3H, 19-CH ), 0.99
), 1.02–1.26 (m, 7H), 1.27–1.50 (m, 10H),
.56–1.65 (m, 4H), 1.73–1.92 (m, 4H), 1.94–2.03 (m, 1H), 2.18–2.28
H NMR (CD
3
OD): d 0.71 (s, 3H, 18-CH
3 3
), 0.95 (s, 3H, 19-CH ), 0.97
2
a
(d, 3H, J = 6.6 Hz, 21-CH
3
), 1.01–1.08 (m, 2H), 1.10–1.33 (m, 7H),
c
r
1.36–1.44 (m, 11H), 1.51–1.62 (m, 6H), 1.78–2.10 (m, 10H), 2.21–
0
3
m
m
m
m
2.25 (m, 1H), 3.20 (t, 2H, J = 6.8 Hz, 6 -CH
2
), 3.42–3.51 (m, 2H, 3-
), 4.83–4.87 (m, 4H,
ꢁ1
0
(
4
H
56
N
4
O
6
2
2
CH and 7-CH), 3.73–3.82 (m, 2H, 1 -CH
2
–N(CH
7.9 Hz, J
2
)
2
), 7.36 (t, 2H, J = 6.5 Hz, d-CH, Py), 7.55 (dd, 2H, J
= 2.5 Hz, b-CH, Py), 7.93 (td, 2H, J = 7.8 Hz, J = 1.4 Hz,
-CH, Py); C NMR (CD OD): d
1
=
2
1
2
1
13
3
3
3
c-CH, Py), 8.85 (d, 2H, J = 5.4 Hz,
r
3
(
1
d, 3H, J = 6.4 Hz, 21-CH
3
38.9 (C1), 31.4 (C2), 72.4 (C3), 40.4 (C4), 44.3 (C5), 36.4 (C6),
72.3 (C7), 41.0 (C8), 35.5 (C9), 37.2 (C10), 22.7 (C11), 41.9 (C12),
44.8 (C13), 56.9 (C14), 28.3 (C15), 30.0 (C16), 57.8 (C17), 12.9
(C18), 24.2 (C19), 38.3 (C20), 19.3 (C21), 34.5 (C22), 33.8(C23),
(
7
m, 1H), 2.30–2.38 (m, 1H), 3.49–3.53 (m, 1H, 3-CH), 3.75 (t, 2H, J =
0
0
.1 Hz, 2 -CH
2
), 3.94 (t, 2H, J = 6.7 Hz, 1 -CH
), 7.37 (t, 2H, J = 6.6 Hz, d-CH,Py),
.56 (t, 2H, J = 7.7 Hz, b-CH, Py), 7.94 (td, 2H, J = 7.8 Hz, J
.5 Hz, -CH, Py), 8.85 (d, 2H, J = 5.5 Hz, -CH, Py; C NMR
OD): d 36.8 (C1), 30.3 (C2), 72.7 (C3), 35.9 (C4), 44.3 (C5),
2
), 3.97–4.02 (m, 1H, 6-
0
0
0
0
CH),4.90–5.05 (m, 4H, –N(CH
7
1
2
)
2
177.1 (C24), 45.1 (C1 ), 30.6 (C2 ), 26.5 (C3 ), 27.7 (C4 ), 27.9
0
0
1
2
=
(C5 ), 72.2 (C6 ), 69.1 (2C, PyCH
Py-bC), 141.9 (2C, Py- C), 124.9 (2C, Py-dC), 153.5 (2C, Py-
197.9 (3C, fac-Re(CO) ); IR (KBr): (O–H) 3416, (C@O) 2026,
(C@O) 1920, (C@O) 1642 cm ; Anal. Calc. for C45 ReBr:
2
), 162.5 (2C, Py-
a
C), 127.2 (2C,
13
c
r
c
r
C),
(
CD
3
3
m
m
m
ꢁ1
6
3
9.9 (C6), 36.5 (C7), 33.4 (C8), 34.3 (C9), 37.1 (C10), 22.2 (C11),
7.2 (C12), 41.6 (C13), 50.2 (C14), 24.4 (C15), 25.6 (C16), 57.7
m
64 4 6
H N O
C, 52.82; H, 6.31; N, 5.47. Found: C, 52.44; H, 6.17; N, 5.56%.
0
(
C17), 12.8 (C18), 19.3 (C19), 36.8 (C20), 19.2 (C21), 29.6 (C22),
Analytical data for complex 4d : Yield: 73%, m.p. 214.8–215.6 °C;
H NMR (CD OD): d 0.67 (s, 3H, 18-CH ), 0.91 (s, 3H, 19-CH ), 0.95
3 3 3
0
0
1
3
1.4 (C23), 177.6 (C24), 44.3 (C1 ), 57.9 (C2 ), 68.9 (2C, PyCH
2
),