4714 Organometallics, Vol. 23, No. 20, 2004
Vicente et al.
cm-1): ν 2124, 2101 (NdCdN). 1H NMR (200 MHz, CDCl3):
δ 7.7-7.5 (m, 13 H, ortho H’s PPh3 + H6, C6H3), 7.4-7.2 (m,
19 H, meta H’s PPh3 + para H’s PPh3 + H4, C6H3), 7.11 (d, 2
mixture was stirred for a further 5 h. The suspension was
concentrated to dryness, the residue was extracted with CH2-
Cl2 (10 mL), without the protective nitrogen atmosphere, and
the extract was filtered over anhydrous MgSO4. The filtrate
was concentrated (ca. 1 mL) and Et2O (5 mL) added, causing
the precipitation of a solid, which was collected by filtration,
washed with Et2O (5 × 3 mL), and air-dried to give orange 6.
Yield: 210 mg, 76%. Mp: 184-186 °C. IR (KBr, cm-1): ν 2146,
3
3
H, To, J HH ) 8 Hz), 6.90 (d, 2 H, To, J HH ) 8 Hz), 6.12 (d, 1
3
H, H4, C6H3, J H,H ) 8 Hz), 2.37 (s, 3 H, Me). 13C{1H} NMR
2
(100 MHz, CDCl3): δ 158.42 (t, CPd, J PC ) 4.5 Hz), 148.49
(C2, C6H3), 143.19 (C5, C6H3), 135.51 (C, To), 134.91 (C, To),
2
134.64 (“t”, CH, ortho C’s PPh3, | J PC + 4J PC| ) 13 Hz), 131.90
3
1
(t, C6H, C6H3, J PC ) 4 Hz), 131.70 (s, C), 130.60 (“t”, ipso C’s
2100 (SCN). H NMR (400 MHz, CDCl3): δ 7.62-7.55 (m, 12
1
PPh3, | J PC + 3J PC| ) 46 Hz), 130.16 (para CH’s PPh3), 130.13
H, ortho H’s, PPh3), 7.35-7.31 (m, 6 H, para H’s, PPh3), 7.29-
7.24 (m, 12 H, meta H’s, PPh3), 6.97-6.94 (m, 1 H, C6H4),
6.40-6.35 (m, 2 H, C6H4), 6.00-6.35 (m, 1 H, C6H4). 13C{1H}
NMR (100 MHz, CDCl3): δ 160.51 (t, C1, C6H4, 2J PC ) 4.5 Hz),
3
(C2H and C6H, To), 127.98 (“t”, meta CH’s PPh3, | J PC + 5J PC
|
) 10 Hz), 124.08 (C3H and C5H, To), 122.97 (C3H, C6H3),
119.23 (C4H, C6H3), 21.03 (Me). 31P{1H} NMR (81 MHz,
CDCl3): δ 24.03 (s, PPh3). Anal. Calcd for C50H40BrN3O2P2Pd:
C, 62.35; H, 4.19; N, 4.36. Found: C, 62.36; H, 4.24; N, 4.16.
Syn th esis of tr a n s-[P d (C6H3NdCdNTo-2-Me-5)Br (P -
P h 3)2] (4c). Pd(dba)2 (1.48 g, 2.55 mmol) and PPh3 (1.67 g,
6.38 mmol) were mixed in dry degassed toluene (10 mL) under
nitrogen and stirred for 10 min. The compound 2c (1.00 g, 3.32
mmol) was added to the mixture, which was slowly heated to
reflux temperature and then refluxed for 40 min (whereby
black palladium started to form). Working up as described for
4a ,b gave colorless 4c. Yield: 1.36 g, 57%. Mp: 140-142 °C
135.53 (t, C6H, C6H4, 3J PC ) 4.2 Hz), 134.96 (C2, C6H4), 134.83
1
(“t”, ortho CH’s, PPh3, | J PC
+
3J PC| ) 12.2 Hz), 131.48 (“t”,
1
ipso C’s, PPh3, | J PC
+
3J PC| ) 47.2 Hz), 129.96 (para CH’s,
1
3
PPh3), 127.82 (“t”, meta CH’s, PPh3, | J PC + J PC| ) 10.8 Hz),
126.45 (CH, C6H4), 125.50 (CH, C6H4), 123.41 (CH, C6H4). 31P-
{1H} NMR (161 MHz, CDCl3): δ 22.04 (s, PPh3). Anal. Calcd
for
C43H34INP2PdS: C, 57.90; H, 3.84; N, 1.57; S, 3.59.
Found: C, 57.54; H, 3.92; N, 1.60; S, 3.24. Single crystals were
obtained by slow diffusion of Et2O into solutions of 6 in CDCl3.
Syn th esis of tr a n s-[P d (C6H4NdCdNTo-2)(p y)(P P h 3)2]-
TfO (7a ). Pyridine (py; 43 µL, 0.52 mmol) and Tl(TfO) (TfO )
triflate, CF3SO3; 91 mg, 0.26 mmol) were added to a suspension
of 4a (250 mg, 0.26 mmol) in a CH2Cl2 (5 mL)/Me2CO (5 mL)
mixture. The mixture was stirred for 10 min, and the suspen-
sion was filtered through Celite; the filtrate was concentrated
to dryness and the residue triturated with Et2O (10 mL). The
suspension was filtered, and the solid was washed with Et2O
(3 × 3 mL) and dried in vacuo overnight to give colorless 7a .
1
dec. IR (Nujol, cm-1): ν 2122 (NdCdN). H NMR (300 MHz,
CDCl3): δ 7.6-7.45 (m, 12 H, ortho H’s, PPh3), 7.4-7.29 (m,
6 H, para H’s, PPh3), 7.25-7.18 (m, 12 H, meta H’s, PPh3),
3
7.06 (d, 2 H, H3 and H5, To, J HH ) 8 Hz), 6.86 (d, 2 H, H2
3
4
and H6, To, J HH ) 8 Hz), 6.52 (d, 1 H, H6, C6H3, J H,H ) 2
3
Hz), 6.22 (d, 1 H, H4, C6H3, J H,H ) 8 Hz), 5.99 (d, 1 H, H3,
3
C6H3, J H,H ) 8 Hz), 2.34 (s, 3 H, Me, To), 1.74 (s, 3 H, Me).
13C{1H} NMR (75 MHz, CDCl3): δ 153.8 (NCN), 138.7 (C2,
Yield: 223 mg, 81%. Mp: 131 °C dec. ΛM ) 134 Ω-1 cm2 mol-1
.
C6H3), 137.3 (NC, To), 137.1 (C6H, C6H3), 134.8 (“t”, ortho CH’s,
2
PPh3, | J PC + 4J PC| ) 12.5 Hz), 134.2 (C, CMe), 133.5 (C, C1 or
IR (Nujol, cm-1): ν 2132, 2114 (NdCdN), 1030 (OTf). 1H NMR
3
4
C5, C6H3), 133.3 (C, C1 or C5, C6H3), 131.1 (“t”, C, ipso C’s,
(400 MHz, CDCl3): δ 8.04 (dd, 2 H, py, J HH ) 6 Hz, J HH ) 1
1
PPh3, | J PC + 3J PC| ) 46 Hz), 129.9 (C3H and C5H, To), 129.7
Hz), 7.41-7.36 (m, 6 H, PPh3), 7.30 (t, 1 H, 3J HH ) 8 Hz), 7.27-
3
5
3
(para C’s, PPh3), 127.7 (“t”, meta CH’s, PPh3, | J PC + J PC| )
10.5 Hz), 124.8 (C3H, C6H3), 124.3 (C4H, C6H3), 123.8 (C2H
and C6H, To), 21.0 (Me, To), 20.8 (Me). 31P{1H} NMR (121
MHz, CDCl3): δ 24.10 (s, PPh3). Anal. Calcd for C51H43BrN2P2-
Pd: C, 65.71; H, 4.65; N, 3.01. Found: C, 65.32; H, 4.80; N,
2.95.
7.18 (m, 24 H, PPh3), 7.14 (d, 2 H, To, J HH ) 13.5 Hz), 6.96
3
4
3
(dd, 1 H, J HH ) 8 Hz, J HH ) 1 Hz), 6.82 (d, 2 H, To, J HH
)
13.5 Hz), 6.78-6.72 (m, 3 H), 6.45 (t, 1 H, 3J HH ) 7.5 Hz), 6.43
(dd, 1 H, J HH ) 7.5 Hz, J HH ) 1 Hz), 2.37 (s, 3 H, Me). 13C-
{1H} NMR (100 MHz, CDCl3): δ 150.75 (CH py), 142.20 (C),
141.69 (C), 137.86 (CH), 137.28 (CH), 136.03 (C), 135.48 (C),
3
4
2
4
133.58 (“t”, ortho CH’s, PPh3, | J PC + J PC| ) 12 Hz), 130.97
Syn th esis of [P d (C6H4NdCdNTo-2)I(bp y)] (5a ; bp y )
2,2′-Bip yr id in e). Pd(dba)2 (1.48 g, 2.55 mmol) and bpy (0.61
g, 3.9 mmol) were mixed in dry degassed toluene (10 mL)
under nitrogen and stirred for 10 min at 0 °C. Then, 2a (1.14
g, 3.4 mmol) and toluene (20 mL) were added and the resulting
mixture was stirred, allowing the temperature to rise to room
temperature for 16 h. The residue was treated with CH2Cl2
(40 mL), without the protective nitrogen atmosphere, and the
new suspension filtered through MgSO4. The resulting solution
was concentrated to dryness, leaving a residue that was
triturated with Et2O (20 mL) and then filtered, washed with
Et2O (2 × 5 mL), and dried to give orange 5a . Yield: 1.07 g,
70%. Mp: 102-104 °C dec. IR (Nujol, cm-1): ν 2088 (NdCd
(para CH’s, PPh3), 130.26 (CH, To), 128.81 (“t”, meta CH’s,
3
PPh3, | J PC
+
5J PC| ) 10 Hz), 127.94 (“t”, C, ipso C’s, PPh3,
| J PC + 3J PC| ) 46 Hz), 125.75 (CH), 125.28 (CH), 125.15 (CH),
124.90 (CH), 123.82 (CH, To), 20.99 (Me). 31P{1H} NMR (121
MHz, CDCl3): δ 19.77 (s, PPh3). Anal. Calcd for C56H46F3-
IN3O3P2PdS: C, 63.07; H, 4.35; N, 3.94; S, 3.01. Found: C,
62.99; H, 4.27; N, 4.07; S, 2.73.
1
Syn th esis of [P d (C6H4NdCdNTo-2)(tBu p y)(bp y)]TfO
t
(8a ; Bu p y ) 4-ter t-Bu tylp yr id in e). The colorless complex
8a was similarly prepared as for 7a from 5a (100 mg, 0.17
t
mmol), Bupy (50 µL, 0.34 mmol), and Tl(TfO) (60 mg, 0.17
mmol) in Me2CO (10 mL). Yield: 115 mg, 90%. Mp: 172 °C.
1
3
ΛM ) 132 Ω-1 cm2 mol-1. IR (Nujol, cm-1): ν 2108, 2090 (Nd
N). H NMR (300 MHz, CDCl3): δ 9.29 (d, 1 H, bpy, J HH ) 5
3
4
1
Hz), 7.97 (td, 1 H, H4 or H5, C6H4, J HH ) 8 Hz, J HH ) 1.5
Hz), 7.9-7.75 (m, 3 H), 7.65-7.60 (m, 1 H), 7.57-7.50 (m, 1
H), 7.37-7.27 (m, 2 H), 6.97-6.85 (m, 3 H), 6.61-6.54 (m, 4
H, To), 2.14 (s, 3 H, Me).13C{1H} NMR (75 MHz, CDCl3): δ
155.76 (C), 155.39 (C), 152.60 (CH), 149.61 (CH), 144.14 (C),
143.66 (C), 138.76 (CH), 138.62 (CH), 138.02 (CH), 136.55 (C),
136.23 (C), 133.46 (C), 129.11 (CH, To), 126.59 (CH), 126.25
(CH), 124.25 (CH), 124.15 (CH), 123.84 (CH), 123.70 (CH, To),
CdN), 1030 (OTf). H NMR (300 MHz, CDCl3): δ 8.85 (dd, 2
t
3
4
H, H2 and H6, Bupy, J HH ) 5.5 Hz, J HH ) 1.5 Hz), 8.28 (d,
3
3
1 H, J HH ) 7.5 Hz), 8.22 (d, 1 H, J HH ) 8 Hz), 8.13 (td, 1 H,
3J HH ) 7.5 Hz, 4J ) 1.5 Hz), 8.09 (td, 1 H, J HH ) 7.5 Hz, J )
3
4
1.5 Hz), 7.61-7.55 (m, 4 H, H3 and H5, tBupy and other
3
aromatic protons), 7.52 (m, 1 H), 7.39 (dd, 1 H, J ) 5.5 Hz,
4J HH ) 1 Hz), 7.33 (m, 1 H), 7.08 (td, 1 H, J HH ) 7.5 Hz, J HH
3
4
) 1.5 Hz), 7.01-6.95 (m, 2 H), 6.56 (d, 2 H, H3 and H5, To,
3J HH ) 8 Hz), 6.30 (d, 2 H, H2 and H6, To, J HH ) 8 Hz), 2.18
3
122.12 (CH), 121.30 (CH), 20.86 (Me). Anal. Calcd for C24H19
-
(s, 3 H, Me), 1.37 (s, 9 H, tBu). 13C{1H} NMR (50 MHz,
IN4Pd: C, 48.31; H, 3.21; N, 9.39. Found: C, 48.61; H, 3.46;
N, 9.08.
t
CDCl3): δ 164.5 (C4, Bupy), 156.4 (C), 153.2(C), 151.4 (C2H
Syn th esis of tr a n s-[P d (C6H4NdCdS-2)I(P P h 3)2] (6). Pd-
(dba)2 (179 mg, 0.31 mmol) and PPh3 (204 mg, 0.78 mmol) were
mixed in dry degassed toluene (10 mL) under nitrogen and
stirred for 15 min. 2-Iodophenyl isothiocyanate (135 mg,
approximately 0.47 mmol) was added, and the resulting
and C6H, tBupy), 150.8 (C), 150.7 (CH), 147.0 (CH), 142.9 (C),
140.8 (CH), 140.5 (CH), 137.2 (C), 135.1 (C4 or C1, To), 135.0
(C4 or C1, To), 133.6 (CH), 129.8 (C3H and C5H, To), 127.5
t
(CH), 127.0 (CH), 125.8 (CH), 125.4 (C3H and C5H, Bupy),
124.7 (CH), 124.2 (C2H and C6H, To), 123.6 (CH), 122.4 (CH),