Paper
Dalton Transactions
1
4
a-major isomer. H NMR (CD
2
Cl
2
, 399.8 MHz, 293 K): 7.23 (td, 1H, 7.5 Hz, 14), 7.29 (dd, 2H, 8.4 Hz, 12, 16), 7.46 (dd,
δH 1.81 (m, 2H), 5.02 (m, 2H, 21 or 22), 6.91 (d, 1H, 9.6 Hz, 3), 2H, 7.1 Hz, 13, 15), 7.65 (dd, 1H, 8.1 Hz, 7), 7.76 (d, 1H,
7
2
.10 (d, 1H, 9.2 Hz, 6), 7.35 (dd, 2H, 8.3 Hz, 12, 16), 7.46 (dd, 9.2 Hz, 5), 7.88 (d, 1H, 8.6 Hz, 4), 7.93 (d, 1H, 8.6 Hz, 8), 9.08
3
13
1
H, 8.6 Hz, 13, 15), 7.64 (td, 1H, 7.8 Hz, 7), 7.72 (d, 1H, 8.2 Hz, (s, 1H,
2 2
JPt–H = 79.2 Hz, Pt–NvCH). C{ H} NMR: (CD Cl )
5
J
); 7.84 (d, 1H, 9.1 Hz, 4), 8.13 (d, 1H, 8.7 Hz, 8), 9.02 (s, 1H, δ 26.0 (23), 28.7 (19), 30.1 (20), 31.9 (24), 68.1 (17), 73.8 (18),
Pt–H = 76.2 Hz, Pt–NvCH). C{ H} NMR: (CD Cl ) δ 26.1 85.3 (21, 22), 110.6 (1), 119.5 (8), 123.3 (6), 123.3 (12, 16),
2 2
3
13
1
(
19), 28.6 (20), 31.5 (23), 32.4 (24), 68.2 (17), 73.8 (18), 75.8 (21, 125.9 (14), 128.0 (7), 128.2 (9), 129.2 (5), 129.8 (13, 15),
2
1
2), 111.9 (1), 119.3 (8), 123.5 (3), 124.3 (6), 124.9 (13, 15), 132.3 (10), 136.5 (4), 137.6 (11), 150.2 (3), 157.5 (#), 169.3 (2).
1
26.0 (9), 126.9 (12, 16), 127.8 (14), 128.6 (7), 129.1 (5), 135.3
4c-minor isomer. H NMR (CD
(s, 1H, JPt–H = 25.2 Hz, Pt–NvCH).
2
Cl
, 399.8 MHz, 293 K): 9.24
2
3
(
10), 138.4 (4), 140.3 (11), 153.2 (#), 169.7 (2).
1
4
a-minor isomer. H NMR (CD Cl , 399.8 MHz, 293 K): 9.21
LIFDI-MS, m/z 549.13 (calculated for C H NOPt [M]–OH =
2
2
25 24
3
(s, 1H, J
= 25.4 Hz, Pt–NvCH).
549.15); elemental analysis: for C H NO Pt Calc. C 53.00;
Pt–H
25 25
2
ESI-MS, positive ion: m/z 594.1329 (calculated for H 4.45; N 2.47; rest 40.08% Found C 53.19; H 4.48; N 2.72; rest
C H N O Pt [M]–O = 594.1353, Δ = 2.2 mDa); elemental ana- 39.61% IR (KBr)/cm− 1620 (CvN), 3498 (O–H), 1261 (C–O
1
2
5
23 2 3
lysis: for C H N O Pt calc. C 49.10, H 3.96, N 4.58, rest phenolic).
2
5
24 2 4
4
2.36%, found C 49.45; H 3.99; N 4.84, rest 41.72% IR (KBr)/
Synthesis of 4d. Dibromo(1,5-cyclooctadiene)platinum(II)
(50 mg, 0.108 mmol), N-(2-hydroxy-1-naphthalidene)-p-chloro-
−
1
cm 1579 (CvN), 3431 (O–H), 1262 (C–O phenolic).
Synthesis of 4b. Dibromo(1,5-cyclooctadiene)platinum(II) aniline (30 mg, 0.11 mmol) and sodium tert-butoxide (24 mg,
100 mg, 0.22 mmol), N-(2-hydroxy-1-naphthalidene)-p-ethoxy- 0.22 mmol) were stirred in THF (30 ml). The reaction mixture
(
aniline (63 mg, 0.22 mmol) and sodium tert-butoxide (50 mg, was left in a Schlenk tube under nitrogen and stirring over-
.43 mmol) were stirred in THF (30 ml). The reaction mixture night. The solution was then filtered under nitrogen, and
0
was left in a Schlenk tube under nitrogen and stirring over- dried under vacuum for 4 hours. The complex 4d was obtained
night. The solution was then filtered under nitrogen, and as yellow crystals (70 mg, 0.13 mmol, 60% yield).
1
dried under vacuum for 4 hours. The complex 4b was obtained
4d-major isomer. H NMR (CD
2
Cl
2
, 399.8 MHz, 293 K):
as yellow crystals (70 mg, 0.13 mmol, 60% yield).
H
δ 1.71 (m, 1H), 2.18 (m, 2H), 2.61 (m, 2H), 2.90 (m, 1H), 3.80
1
4
b-major isomer. H NMR (CD
2
Cl
2
, 399.8 MHz, 293 K): 1.43 (m, 1H), 4.05 (m, 1H), 4.98 (m, 2H, 21 and 22), 6.91 (d, 1H,
(t, 3H, 7.0 Hz, 26), 2.22 (m, 1H), 2.43 (m, 2H), 2.70 (m, 2H), 9.3 Hz, 3), 7.03 (dd, 1H, 8.6 Hz, 6), 7.25 (dd, 2H, 8.6 Hz, 12,
3
6
8
.61 (m, 1H), 4.08 (q, 2H, 7.2 Hz, 25), 4.96 (m, 2H, 21 and 22), 16), 7.44 (dd, 2H, 8.9 Hz, 13, 15), 7.65 (dd, 1H, 8.1 Hz, 7), 7.77
.88 (t, 2H, 7.2 Hz, 12, 16), 7.13 (d, 1H, 8.7 Hz, 3), 7.22 (td, 1H, (d, 1H, 9.4 Hz, 5), 7.86 (d, 1H, 8.5 Hz, 4), 7.91 (dd, 1H, 9.1 Hz,
3
13
1
.3 Hz, 6), 7.48 (m, 1H, 7.6 Hz, 7), 7.87 (d, 1H, 8.7 Hz, 5), 7.97 8), 9.03 (s, 1H, JPt–H = 69.4 Hz, Pt–NvCH). C{ H} NMR:
3
(d, 1H, 8.6 Hz, 4), 8.11 (d, 1H, 9.5 Hz, 8), 9.05 (s, 1H, JPt–H
=
(CD
2 2
Cl ) δ 27.6 (24), 28.4 (23), 31.3 (19), 33.8 (20), 68.2 (17),
1
3
1
7
2
7
1
1
1
7.8 Hz, Pt–NvCH). C{ H} NMR: (CD Cl ) δ 15.1 (26), 73.8 (18), 85.6 (21, 22), 110.2 (1), 119.5 (8), 123.1 (3), 123.1 (6),
2 2
6.0 (19), 27.5 (20), 28.6 (23), 31.5 (24), 64.3 (25), 68.3 (17), 125.1 (13, 15), 126.0 (12, 16), 126.4 (9), 127.3 (14), 128.0 (7),
3.9 (18), 84.6 (21, 22), 109.3 (1), 114.4 (12, 16), 119.4 (8), 129.2 (5), 132.3 (10), 136.7 (4), 137.6 (11), 157.6 (#), 169.4 (2).
1
21.6 (3), 125.3 (6), 126.9 (13, 15), 127.7 (9), 128.3 (7),
4d-minor isomer. H NMR (CD
2
Cl
2
, 399.8 MHz, 293 K): 9.21
3
29.1 (10), 129.7 (5), 135.8 (4), 137.0 (11), 155.0 (14), 157.8 (#), (s, 1H, JPt–H = 20.8 Hz, Pt–NvCH).
95.5 (2).
ESI-MS, positive ion, m/z 584.1181 (calculated for
b-minor isomer. H NMR (CD 23ClNOPt [M]–OH = 584.1191, Δ = 0.7 mDa). Elemental
analysis: for C H NO ClPt Calc. C 49.96; H 4.03; N 2.33; rest
1
4
2
Cl
= 25.8 Hz, Pt–NvCH).
2
, 399.8 MHz, 293 K): 9.24
25
C H
3
(s, 1H, J
Pt–H
25 24
2
ESI-MS, positive ion: m/z 593.1767 (calculated for 43.68% Found C 50.08; H 4.08; N 2.42; rest 43.42%; IR (KBr)/
−
1
C
27
H
28NO
2
Pt [M]–OH = 593.1765, Δ = −0.2 mDa); elemental cm 1580 (CvN), 3473 (O–H), 1261 (C–O phenolic).
Synthesis of 4e. Dibromo(1,5-cyclooctadiene)platinum(II)
9.81% Found C 53.57; H 4.81; N 2.75; rest 38.87% IR (KBr)/ (50 mg, 0.11 mmol), N-(2-hydroxy-1-naphthalidene)-p-methoxy-
analysis: for C H NO Pt Calc. C 53.11; H 4.79; N 2.29; rest
3
2
7
29
3
−
1
cm 1580 (CvN), 3433 (O–H), 1427 (C–O ether aromatic), aniline (30 mg, 0.11 mmol) and sodium tert-butoxide (24 mg,
261 (C–O phenolic). 22 mmol) in THF (30 ml). The reaction mixture was left in a
Synthesis of 4c. Dibromo(1,5-cyclooctadiene)platinum(II) Schlenk tube under nitrogen and stirring overnight. The solu-
1
(
(
50 mg, 0.11 mmol), N-(2-hydroxy-1-naphthalidene)aniline tion was then filtered under nitrogen, and dried under
26 mg, 0.11 mmol) and sodium tert-butoxide (10 mg, vacuum for 4 hours. Complex 4e was obtained as yellow crys-
0
.22 mmol) were stirred in THF (30 ml). The reaction mixture tals (70 mg, 0.13 mmol, 60% yield).
1
was left in a Schlenk tube under nitrogen and stirring over-
night. The solution was then filtered under nitrogen, and
4e-major isomer. H NMR (CD
2 2
Cl , 399.8 MHz, 293 K):
δ
H
1.81 (m, 1H), 2.15 (m, 2H), 2.60 (m, 2H), 2.90 (m, 2H), 3.84
dried under vacuum for 4 hours. The complex 4c was obtained (s, 3H, 27), 4.05 (m, 1H), 4.98 (m, 2H, 21 and 22), 6.91 (d, 1H,
as yellow crystals (70 mg, 0.13 mmol, 60% yield).
9.4 Hz, 3), 7.03 (dd, 1H, 8.5 Hz, 6), 7.25 (dd, 2H, 8.6 Hz, 12,
, 399.8 MHz, 293 K): 16), 7.44 (dd, 2H, 8.9 Hz, 13, 15), 7.65 (dd, 1H, 8.1 Hz, 7), 7.77
δH 1.69 (m, 2H), 3.84 (m, 1H), 4.08 (td, 1H, 8.8 Hz), 4.98 (m, (d, 1H, 9.3 Hz, 5), 7.86 (d, 1H, 8.5 Hz, 4), 7.91 (d, 1H, 8.9 Hz,
1
4
2 2
c-major isomer. H NMR (CD Cl
3
2
H, 21 and 22), 6.92 (d, 1H, 9.2 Hz, 3), 7.07 (dd, 1H, 8.4 Hz, 6), 8), 9.06 (s, 1H, JPt–H = 78.4
Dalton Trans.
This journal is © The Royal Society of Chemistry 2015