Organometallics
ARTICLE
6.91 (t, 1 H, para-Xy, 3JHH = 7 Hz), 6.83 (d, 2 H, meta-Xy, 3JHH = 7 Hz),
1.60 (s, 6 H, 2 Me). 13C{1H} APT NMR (100.64 MHz, CDCl3): δ
180.77 (CdN), 155.94 (C), 145.58 (C), 145.52 (C), 134.42 (C, ortho-
Xy), 134.25 (d, CH, ortho-PPh3, 2JPC = 12.4 Hz), 132.64 (CH, C6H4),
2 Me), 2.14 (s, 6 H, 2 Me), 1.76 (s, 6 H, 2 Me). 13C{1H} APT NMR
(50.32 MHz, CDCl3): δ 174.8 (CdN), 171.8 (CdN), 167.6 (CdN),
150.7 (C), 148.0 (C), 146.5 (C), 144.7 (C), 144.0 (C), 137.2 (C), 134.7
(C), 131.1 (CH, C6H4), 130.8 (C), 130.4 (CH, C6H4), 129.6 (CH,
C6H4), 129.3 (CH, para-Xy), 129.2 (C), 128.2 (CH, meta-Xy), 127.9
(CH), 127.8 (CH, meta-Xy), 127.5 (2 CH, meta-Xy), 126.1 (C), 124.4
(CH, C3, C6H4NO2), 124.0 (CH, para-Xy), 123.9 (C), 123.8 (CH,
para-Xy), 19.4 (2 Me, XyNC), 18.8 (2 Me, XyNC), 18.7 (2 Me, XyNC),
18.6 (2 Me, XyNC). Anal. Calcd for C48H44BrN5O2PdS: C, 61.25; H,
4.71; N, 7.44; S, 3.41. Found: C, 60.91; H, 4.66; N, 7.22; S, 3.34.
20: Yield: 77%. Mp: 139 °C. 1H NMR (400 MHz, CDCl3): δ 8.11 (d,
2 H, H3, C6H4NO2, 3JHH = 8 Hz), 7.45 (d, 2 H, C6H4, 3JHH = 8 Hz), 7.39
(d, 2 H, C6H4, 3JHH = 8 Hz), 7.37 (d, 2 H, C6H4, 3JHH = 8 Hz), 7.26 (d,
2 H, 3JHH = 8 Hz), 7.18 (d, 2 H, 3JHH = 8 Hz), 7.06 (m, 4 H), 6.99 (d, 2
1
132.12 (d, C, ipso-PPh3, JPC = 45.4 Hz), 131.44 (CH, C6H4), 130.81
(CH, C6H4), 130.25 (CH, Ph), 130.22 (CH, Ph), 129.52 (CH, para-
PPh3), 128.20 (d, CH, meta-PPh3, 3JPC = 10.8 Hz), 128.13 (CH, meta-
Xy), 127.36 (CH, Ph), 127.01 (CH, C6H4), 124.25 (CH, para-Xy),
18.85 (bs, 2 Me, XyNC). 31P NMR (121 MHz, CDCl3): δ 28.74 (s,
PPh3). Anal. Calcd for C39H33BrNPdPS: C, 61.23; H, 4.35; N, 1.83; S,
4.19. Found: C, 60.85; H, 4.50; N, 1.86; S, 3.86.
16: Yield: 90%. Mp: 230 °C. 1H NMR (300 MHz, CDCl3): δ 7.32 (s,
4 H), 7.23ꢀ6.81 (several m, 15 H), 6.34 (m, 2 H), 2.62 (s, 3 H, Me), 2.42
(s, 3 H, Me), 2.30 (s, 6 H, 2 Me), 2.19 (s, 3 H, Me), 2.13 (s, 6 H, 2 Me),
1.13 (s, 3 H, Me). 13C NMR (50.32 MHz, CDCl3): δ 174.28 (CdN),
172.87 (CdN), 168.79 (CdN), 150.83 (C), 147.83 (C), 143.58 (C),
135.12 (C), 134.62 (C), 133.89 (C), 132.16 (C), 130.99 (CH), 130.86
(CH), 130.65 (C), 129.45 (CH), 129.10 (CH), 128.87 (C), 128.65 (CH),
128.07 (CH), 127.95 (CH), 127.85 (CH), 127.71 (CH), 127.51 (CH),
127.41 (CH), 127.11 (C), 127.00 (CH), 126.80 (CH), 126.34 (CH),
125.38 (C), 123.76 (CH), 123.73 (CH), 121.86 (C), 20.22 (Me,
XyNC), 19.94 (Me, XyNC), 19.26 (Me, XyNC), 19.03 (Me, XyNC),
18.90 (Me, XyNC), 18.52 (2 Me, XyNC), 17.41 (Me, XyNC). Anal.
Calcd for C48H45BrN4PdS: C, 64.32; H, 5.06; N, 6.25; S, 3.58. Found: C,
64.02; H, 4.96; N, 5.75; S, 3.29. Single crystals were obtained by slow
diffusion of n-pentane into a solution of 16 in ClCH2CH2Cl.
H, 3JHH = 8 Hz), 6.94 (d, 2 H, 3JHH = 8 Hz), 6.89 (t, 1 H, XyNC, 3JHH
=
=
8 Hz), 6.59 (d, 2 H, XyNC, 3JHH = 8 Hz), 6.40 (t, 1 H, XyNC, 3JHH
8 Hz), 2.31 (s, 6 H, 2 Me), 2.21 (s, 6 H, 2 Me), 2.13 (s, 6 H, 2 Me), 1.73
(s, 6 H, 2 Me). 13C{1H} APT NMR (50.32 MHz, CDCl3): δ 176.2
(CdN), 171.5 (CdN), 167.6 (CdN), 150.3 (C), 148.0 (C), 147.0 (C),
146.1 (C), 145.9 (C), 140.9 (C), 135.1 (C), 135.0 (CH, C6H4), 134.9
(C), 133.5 (CH, C6H4), 131.6 (C), 130.3 (CH, C6H4), 129.2 (C), 129.0
(C), 128.3 (CH), 127.8 (CH), 127.7 (CH), 127.6 (CH), 127.5 (CH),
127.4 (CH), 126.3 (C), 124.3 (CH, C3, C6H4NO2), 124.1 (C), 124.0
(CH), 123.9 (CH), 19.7 (2 Me), 18.8 (2 Me), 18.7 (2 Me), 18.6 (2 Me).
Anal. Calcd for C54H48IN5O2PdS2: C, 59.15; H, 4.41; N, 5.85; S, 6.39.
Found: C, 59.46; H, 4.49; N, 5.67; S, 6.12.
Synthesis of [Pd{j2-C(dNXy)C(dNXy)C[C6H4SPh-2](dNXy)}-
(TfO)(CNXy)] (21). To a solution of 16 (80 mg, 0.08 mmol) in CH2Cl2
(15 mL) was added TlTfO (30 mg, 0.08 mmol), and the mixture was
stirred for 5 h. The suspension was filtered through Celite and the filtrate
concentrated (1 mL). Addition of pentane (15 mL) gave a suspension
that was filtered; the solid was washed with n-pentane (3 ꢁ 5 mL) to
give 21 as an orange-red solid. Yield: 62 mg, 72%. Mp: 131 °C. 1H NMR
(300 MHz, CDCl3): δ 7.33 (s, 5 H), 7.21ꢀ6.90 (several m, 14 H), 6.51
(m, 1 H), 6.24 (m, 1 H), 2.61 (s, 3 H, Me), 2.49 (s, 3 H, Me), 2.34 (s, 3 H,
Me), 2.28 (s, 3 H, Me), 2.18 (s, 3 H, Me), 2.14 (s, 6 H, 2 Me), 1.06 (s,
3 H, Me). 13C NMR (50.32 MHz, CDCl3): δ 174.43 (CdN), 166.66
(CdN), 162.76 (CdN), 149.10 (C), 147.66 (C), 141.07 (C), 135.66
(C), 135.56 (C), 133.36 (C), 131.50 (CH), 131.35 (CH), 131.10
(C), 130.78 (CH), 130.35 (C), 129.80 (CH), 129.66 (CH), 128.88
(C), 128.72 (CH), 128.63 (CH), 128.40 (CH), 128.25 (CH), 128.10
(CH), 127.92 (CH), 127.72 (CH), 127.67 (CH), 127.48 (CH), 127.34
(C), 127.05 (CH), 126.51 (CH), 125.21 (C), 124.44 (CH), 124.30
(CH), 121.65 (C), 20.07 (Me, XyNC), 19.37 (Me, XyNC), 19.31 (Me,
XyNC), 19.08 (Me, XyNC), 18.56 (Me, XyNC), 18.40 (2 Me, XyNC),
17.31 (Me, XyNC). Anal. Calcd for C49H45F3N4O3PdS2: C, 60.96; H,
4.70; N, 5.80; S, 6.64. Found: C, 60.82; H, 4.93; N, 5.81; S, 6.31. Single
crystals were obtained by slow diffusion of n-pentane into a solution of
21 in CH2Cl2.
17: Yield: 80%. Mp: 213 °C. 1H NMR (200 MHz, CDCl3): δ 7.37 (d,
3
2 H, C6H4OMe, JHH = 8 Hz), 7.09ꢀ6.83 (several m, 16 H, C6H4,
C6H4OMe + XyNC), 6.36 (m, 2 H, C6H4 and/or XyNC), 3.83 (s, 3 H,
OMe), 2.63 (s, 3 H, Me), 2.47 (s, 3 H, Me), 2.39 (s, 3 H, Me), 2.33 (s, 3
H, Me), 2.28 (s, 3 H, Me), 2.13 (s, 6 H, 2 Me), 1.11 (s, 3 H, Me).
13C{1H} APT NMR (50.32 MHz, CDCl3): δ 174.33 (CdN), 172.8
(CdN), 168.6 (CdN), 160.3 (COMe), 150.8 (C), 147.8 (C), 143.5
(C), 138.0 (C), 135.2 (CH, C6H4OMe), 134.6 (C), 130.8 (C), 130.8
(CH), 129.9 (C), 129.0 (CH), 128.8 (C), 128.3 (CH), 128.0 (CH),
127.9 (CH), 127.7 (CH), 127.6 (C), 127.5 (CH), 127.4 (CH), 127.1
(C), 126.9 (CH), 126.7 (CH), 125.4 (C), 125.1 (CH), 123.7 (CH),
122.3 (C), 121.8 (C), 115.2 (CH, C6H4OMe), 55.4 (OMe), 20.18 (Me,
XyNC), 20.05 (Me, XyNC), 19.37 (Me, XyNC), 19.07 (Me, XyNC),
18.88 (Me, XyNC), 18.49 (2 Me, XyNC), 17.32 (Me, XyNC). Anal.
Calcd for C49H47BrN4OPdS: C, 63.53; H, 5.11; N, 6.05; S, 3.46. Found:
C, 63.19; H, 5.26; N, 5.97; S, 3.17. Single crystals were obtained by slow
diffusion of n-pentane into a solution of 17 in CH2Cl2.
18: Yield: 76%. Mp: 222 °C. 1H NMR (400 MHz, CDCl3): δ 8.07 (d,
2 H, C6H4NO2, 3JHH = 8 Hz), 7.49ꢀ7.34 (several m, 4 H, C6H4 and
XyNC), 7.02 (d, 2 H, C6H4NO2, 3JHH = 8 Hz), 7.08ꢀ6.79 (several m,
10 H, C6H4 and XyNC), 6.37 (m, 2 H, C6H4 or XyNC), 2.59 (s, 3 H,
Me), 2.21 (s, 3 H, Me), 2.19 (s, 3 H, Me), 2.16 (s, 3 H, Me), 2.12 (s, 6 H,
2 Me), 2.04 (s, 3 H, Me), 1.30 (s, 3 H, Me). 13C{1H} APT NMR
(50.32 MHz, CDCl3): δ 174.5 (CdN), 173.7 (CdN), 168.3 (CdN),
152.3 (C), 147.7 (C), 146.1 (C), 145.9 (C), 143.8 (C), 135.6 (C), 134.9
(CH), 134.6 (C), 131.5 (CH), 130.2 (C), 129.9 (C), 129.4 (CH), 129.2
(CH), 128.9 (CH), 128.7 (C), 128.1 (CH), 127.8 (CH), 127.7 (CH),
127.6 (CH), 127.5 (CH), 127.4 (CH), 127.3 (CH), 127.2 (CH), 127.0
(CH), 126.7 (C), 125.8 (C), 125.3 (C), 124.1 (CH), 123.9 (CH), 123.8
(CH), 122.2 (C), 20.17 (Me, XyNC), 19.44 (Me, XyNC), 19.04 (Me,
XyNC), 18.89 (Me, XyNC), 18.71 (Me, XyNC), 18.47 (2 Me, XyNC),
17.71 (Me, XyNC). Anal. Calcd for C48H44BrN5O2PdS: C, 61.25; H,
4.71; N, 7.44; S, 3.41. Found: C, 61.61; H, 4.87; N, 7.16; S, 3.10.
19: Yield: 87%. Mp: 213 °C. 1H NMR (200 MHz, CDCl3): δ 8.10 (d,
2 H, H3, C6H4NO2, 3JHH = 8 Hz), 7.48 (d, 2 H, C6H4, 3JHH = 8 Hz), 7.33
Synthesis of [Pd{j2-C,S-C(dNXy)C6H4SPh-2}(PPh3)(CNXy)]-
TfO (22). A mixture of 1 (80 mg, 0.09 mmol), XyNC (23 mg, 0.18 mmol),
and TlTfO (31 mg, 0.09 mmol) in acetone (15 mL) was stirred for 1 h.
The suspension was filtered through Celite, and the filtrate was
concentrated to dryness. The residue was washed with Et2O (3 ꢁ
5 mL) to give 22 as a yellow solid. Yield: 56 mg, 60%. Mp: 155 °C.
ΛM (acetone, 4.84 ꢁ 10ꢀ4 mol Lꢀ1): 136 Ωꢀ1 cm2 molꢀ1. 1H NMR
3
(400 MHz, CDCl3): δ 8.28 (d, 1 H, H3 or H6, C6H4, JHH = 9 Hz),
7.56ꢀ7.50 (m, 3 H, C6H4 and/or Ph), 7.45 (m, 4 H, C6H4 and/or Ph
and/or XyNC), 7.32 (td, 6 H, meta-PPh3, 3JHH = 9 Hz, 4JHH = 3 Hz),
7.26 (m, 3 H, para-PPh3), 7.18 (m, 6 H, ortho-PPh3), 6.90 (m, 2 H, Ph +
2 H, meta-Xy(i) + 2 H, meta-Xy(c)), 6.79 (m, 1 H, para-Xy(i)), 2.19 (s, 6
H, 2 Me), 1.68 (s, 6 H, 2 Me). 13C{1H} APT NMR (50.32 MHz,
CDCl3): δ 152.2 (C), 151.2 (C), 150.8 (C), 134.2 (C), 133.5 (d, CH,
3
3
(d, 2 H, C6H4, JHH = 8 Hz), 7.29 (d, 2 H, C6H4, JHH = 8 Hz),
7.10ꢀ6.92 (several m, 9 H, XyNC), 6.62 (d, 2 H, XyNC, 3JHH = 8 Hz),
3
2
6.43 (t, 1 H, XyNC, JHH = 8 Hz), 2.36 (s, 6 H, 2 Me), 2.22 (s, 6 H,
ortho-PPh3, JPC = 12.4 Hz), 133.5 (CH, C6H4 or Ph), 131.8 (CH),
4993
dx.doi.org/10.1021/om200607h |Organometallics 2011, 30, 4983–4998