3530 Organometallics, Vol. 23, No. 14, 2004
Vicente et al.
C6F5), 138.06 (m, Cq C6F5), 137.78 (Ar), 136.39 (m, Cq C6F5),
111.88 (m, Cq C6F5), 109.90 (Ar), 107.15 (Ar), 62.37 (OMe),
62.32 (OMe), 61.96 (OMe), 61.64 (OMe), 61.35 (OMe). 13C{1H}
NMR (100.81 MHz, CDCl3, -50 °C): δ 162.97 (CO2), 156.37
(Ar), 154.61 (Ar), 152.79 (Ar), 151.09 (Ar), 147.05 (Ar), 146.29
(Ar), 145.30 (Ar), 144.86 (m, Cq C6F5), 143.33 (Ar), 142.34 (m,
Cq C6F5), 141.39 (Ar), 139.68 (m, Cq C6F5), 138.06 (m, Cq C6F5),
135.90 (Ar), 135.56 (m, Cq C6F5), 111.43 (m, Cq C6F5), 109.76
(Ar), 107.36 (Ar), 62.56 (OMe), 62.51 (OMe), 62.36 (OMe), 61.58
and deoxygenated toluene (10 mL). After 5 min stirring,
[HgAr2] (82 mg, 0.11 mmol) and toluene (5 mL) were added,
and the mixture was stirred for 6 h. The suspension was
concentrated to dryness, and the residue was treated with CH2-
Cl2 (10 mL) and filtrated though Celite. The filtrate was
concentrated (1 mL), and Et2O (15 mL) was added to give a
suspension, which was filtered and the solid air-dried to give
10 as a yellow solid. Yield: 97 mg, 61%. Mp: 135-137 °C. ΛM
(acetone, 5 × 10-4 M): 0.4 Ω-1 cm2 mol-1. 1H NMR (200 MHz,
CDCl3): δ 7.06-7.38 (m, 30 H, PPh3), 3.84 (s, 3 H, OMe), 3.83
(s, 6 H, OMe), 3.825 (s, 6 H, OMe), 3.75 (s, 3 H, OMe). 31P{1H}
NMR (81.01 MHz, CDCl3): δ 30.63 (d, Ptrans to Hg, 2J PP ) 16 Hz,
1J PPt ) 2529 Hz, 2J PHg ) 3325 Hz), 19.68 (d, Pcis to Hg, 2J PP ) 16
(OMe), 61.33 (OMe). 195Pt{1H} NMR (86.18 MHz, CDCl3): δ
1
-1497 (s, J PtHg ) 28026 Hz). Anal. Calcd for C50H36F10
-
HgN8O32Pt2: C, 29.42; H, 1.78; N, 5.49. Found: C, 29.37; H,
1.80; N, 5.46
1
2
Hz, J PPt ) 2647 Hz, J PHg ) 291 Hz). 13C{1H} NMR (75.45
Syn th esis of [Hg{P t(K2-Ar )2(O2CCF 3)}2] (9). To a solution
of 2 (from 0.08 mmol of 1) in CH2Cl2 (5 mL) was added [Hg(O2-
CCF3)2] (40 mg, 0.09 mmol). The resulting mixture was stirred
for 1 h and then filtered through dry Celite. The filtrate was
concentrated (1 mL), addition of n-hexane (10 mL) gave a
suspension, which was filtered, and the solid was air-dried to
give 9 as an orange solid. Yield: 62 mg, 75%. Mp: 183-187
°C. IR (cm-1): νasym(CO2) 1674. 1H NMR (200 MHz, CDCl3, 30
°C): δ 4.11 (s, 6 H, OMe, the most abundant, isomer 1), 4.10
(s, 3 H, OMe isomer 2), 4.08 (s, 6 H, OMe isomer 1), 4.07 (s, 9
H, OMe isomer 2), 4.01 (s, 6 H, OMe, isomer 1), 3.96 (s, 6 H,
OMe isomer 1), 3.92 (s, 3 H, OMe isomer 2), 3.90 (s, 6 H, OMe
isomer 1), 3.89 (s, 3 H, OMe isomer 2), 3.86 (s, 6 H, OMe isomer
3
MHz, CDCl3): δ 172.22 (dd, ArHg
,
3J PC ) 3.7 Hz, J PC ) 61
Hz), 150.18 (d, Cq, J PC ) 3.2 Hz, J PtC ) 18 Hz), 147.99 (dd, Cq,
J PC ) 2.6 Hz, J PC ) 6 Hz, J PtC ) 51 Hz), 145.93 (Cq), 144.74
(d, Cq, J PC ) 1.6 Hz), 142.42 (d, Cq, J PC ) 2.6 Hz), 140.54 (dd,
2
i-C ArPt
,
2J PC ) 9 Hz, J PC ) 99 Hz), 135.76 (dd, i-C PPh3,
3J PC ) 3.7 Hz, J PC ) 52 Hz, J PtC ) 29 Hz), 134.14 (d, o-C
1
2
PPh3, 2J PC ) 12 Hz, 3J PtC ) 24 Hz), 129.93 (s, p-C PPh3), 128.04
3
(d, m-C PPh3, J PC ) 11 Hz,), 62.00 (m-OMe), 61.79 (m-OMe),
61.36 (p-OMe), 61.02 (p-OMe). 195Pt{1H} NMR (86.18 MHz,
1
1
CDCl3): δ -4636 (dd, J PtP ) 2530 Hz, J PtP ) 2647 Hz,
1J PtHg ) 14945 Hz). Anal. Calcd for C54H48HgN4O14P2Pt: C,
45.21; H, 3.37; N, 3.90. Found: C, 45.43; H, 3.34; N, 3.81.
Single crystals of 10 were obtained by slow diffusion of
n-hexane into a solution of 10 in CDCl3/ether.
1
1). H NMR (200 MHz, CDCl3, -33 °C): δ 4.13 (s, OMe), 4.10
(s, OMe), 4.07 (s, OMe), 4.01 (s, OMe), 3.92 (s, OMe), 3.88 (s,
OMe), 3.86 (s, OMe). 19F{1H} NMR (188.30 MHz, CDCl3, 30
°C): δ -72.81 (s, isomer 2), -72.89 (s, isomer 1). 13C{1H} NMR
Syn th esis of cis-[P t(K1-Ar ){Hg(K1-Ar )}(bp y)] (11). A
mixture of [Pt(dba)2] (102 mg, 0.15 mmol) and bpy (30 mg,
0.19 mmol) in dry and deoxygenated toluene (15 mL) was
stirred under nitrogen. After 10 min, [HgAr2] (87 mg, 0.12
mmol) was added and the mixture was stirred for 24 h. The
solvent was evaporated to dryness, and the residue was treated
with CH2Cl2 to give a suspension, which was filtered off though
Celite. The filtrate was concentrated (1 mL), addition of Et2O
(15 mL) gave a suspension, which was filtered, and the solid
was air-dried to give 11 as a yellow solid. Yield: 82 mg, 64%.
Mp: 170-174 °C. 1H NMR (200 MHz, CDCl3): δ 9.68 (m, 1
H, bpy), 8.44-8.46 (m, 1 H, bpy), 7.98-8.12 (m, 4 H, bpy),
7.46-7.52 (m, 2 H, bpy), 4.06 (s, 6 H, OMe), 4.02 (s, 6 H, OMe),
4.00 (s, 3 H, OMe), 3.89 (s, 3 H, OMe). 13C{1H} NMR (75.45
MHz, CDCl3): δ 168.78 (ArHg), 159.47 (CH bpy), 155.79 (Cq),
155.19 (Cq), 150.97 (Cq), 149.80 (Cq), 148.70 (CH bpy), 146.34
(Cq), 145.98 (Cq), 144.96 (Cq), 141.76 (Cq), 138.18 (CH bpy),
128.06 (CH bpy), 127.66 (CH bpy), 122.98 (CH bpy), 122.08
(CH bpy), 117.03 (Cq), 62.30 (OMe), 62.23 (OMe), 61.26 (OMe),
61.02 (OMe). 195Pt{1H} NMR (86.18 MHz, CDCl3): δ -3333
2
(150 MHz, CDCl3): δ 161.89 (q, CO, isomer 1, J CF ) 38 Hz),
2
161.28 (q, CO isomer 2, J CF ) 37.6 Hz), 156.30 (Ar, isomer
1), 155.95 (Ar, isomer 2), 154.53 (Ar, isomer 1), 153.56 (Ar,
isomer 2), 153.18 (Ar, isomer 1), 151.66 (Ar, isomer 2), 151.04
(Ar, isomer 1), 148.10 (Ar, isomer 1), 147.61 (Ar, isomer 2),
147.00 (Ar, isomer 2), 146.72 (Ar, isomer 1), 145.92 (Ar, isomer
2), 145.74 (Ar, isomer 1), 145.45 (Ar, isomer 1), 144.97 (Ar,
isomer 2), 141.62 (Ar, isomer 1), 141.53 (Ar, isomer 2), 137.42
(Ar, isomer 1), 137.28 (Ar, isomer 2), 115.60 (q, CF3 isomer 1,
1J CF ) 289 Hz), 109.01 (Ar, isomer 1), 108.53 (Ar, isomer 2),
106.47 (Ar, isomer 2), 104.75 (Ar, isomer 1), 62.74 (OMe), 62.45
(OMe), 62.41 (OMe), 62.25 (OMe), 62.10 (OMe), 61.68 (OMe),
61.66 (OMe), 61.55 (OMe), 61.43 (OMe). 13C{1H} NMR (100.81
2
MHz, CDCl3, - 50 °C): δ 161.56 (q, CO isomer 1, J CF ) 38
Hz), 161.03 (q, CO isomer 2, 2J CF ) 37.6 Hz), 156.74 (Ar, isomer
1), 156.23 (Ar, isomer 2), 154.69 (Ar, isomer 1), 154.23 (Ar,
isomer 2), 153.66 (Ar, isomer 2), 153.06 (Ar, isomer 1), 151.96
(Ar, isomer 2), 151.49 (Ar, isomer 1), 147.16 (Ar, isomer 1),
146.42 (Ar, isomer 2), 146.30 (Ar, isomer 2), 145.78 (Ar, isomer
1), 145.67 (Ar, isomer 2), 145.47 (Ar, isomer 1), 143.97 (Ar,
isomer 1), 143.50 (Ar, isomer 2), 141.16 (Ar, isomer 1), 140.91
(Ar, isomer 2), 135.91 (Ar, isomer 1), 135.73 (Ar, isomer 2),
115.32 (q, CF3 isomer 1, 1J CF ) 289 Hz), 115.16 (q, CF3 isomer
1
(s, J PtHg ) 25828 Hz). Anal. Calcd for C28H26HgN6O14Pt: C,
31.54; H, 2.46; N, 7.88. Found: C, 31.74; H, 2.35; N, 7.79.
Syn th esis of [P t(K1-Ar ){Hg(K1-Ar )}(CNXy)(P P h 3)] (12).
To a solution of 10 (64 mg, 0.045 mmol) in CH2Cl2 (4 mL) was
added XyNC (5.9 mg, 0.045 mmol), and a yellow solution was
obtained. After 15 h the solvent was evaporated almost to
dryness, addition of Et2O (10 mL) gave a suspension, which
was filtered, and the solid was air-dried to give 12 as a pale
yellow solid. Yield: 38 mg, 65%. Mp: 196-198 °C. IR (cm-1):
1
2, J CF ) 290 Hz), 109.09 (Ar, isomer 1), 108.81 (Ar, isomer
2), 105.95 (Ar, isomer 2), 104.64 (Ar, isomer 1), 62.84 (OMe),
62.71 (OMe), 62.61 (OMe), 62.57 (OMe), 62.51 (OMe), 62.39
(OMe), 61.60 (OMe), 61.42 (OMe). 195Pt{1H} NMR (128.81
MHz, CDCl3): δ -1470 (s, isomer 1, 1J PtHg ) 28040 Hz), -1471
(s, isomer 2). Anal. Calcd for C40H36F6HgN8O32Pt2: C, 26.03;
H, 1.97; N, 6.07. Found: C, 25.81; H, 2.00; N, 5.96. Single
crystals of 9‚CHCl3‚CH2Cl2 were obtained by slow diffusion of
n-hexane into a CDCl3 solution of 9.
1
ν(NtC) 2144. H NMR (200 MHz, CDCl3): δ 7.55-7.45 (m, 6
H, PPh3), 7.34-7.31 (m, 9 H, PPh3), 7.15-7.07 (m, 1 H, p-H
XyNC), 6.96-6.92 (m, 2 H, m-H XyNC), 3.98 (s, 6 H, OMe),
3.86 (s, 3 H, OMe), 3.84 (s, 3 H, OMe), 3.83 (s, 6 H, OMe),
1.94 (s, 6 H, Me). 31P{1H} NMR (81.01 MHz, CDCl3): δ 25.70
Syn t h esis of cis-[P t (K1-Ar ){H g(K1-Ar )}(P P h 3)2] (10).
Meth od a . A suspension of [HgAr2] (255 mg, 0.36 mmol) and
[Pt(PPh3)3] (346 mg, 0.35 mmol) was refluxed under nitrogen
for 1 h in dry and deoxygenated toluene (6 mL). Addition of
n-hexane gave a suspension, which was filtered, and the solid
was recrystallized from CH2Cl2/n-hexane to give 10 as a yellow
solid. Yield: 457 mg, 90%.
1
2
(s, J PPt ) 2373 Hz, J PHg ) 3195 Hz). 13C{1H} NMR (75.45
3
MHz, CDCl3): δ 175.33 (d, i-C ArHg, J PC ) 60 Hz), 151.24 (d,
Ar, J PC ) 3.6 Hz), 147.94 (d, Ar, J PC ) 2.5 Hz, J PtC ) 50 Hz),
146.44 (Ar), 146.37 (Ar), 144.51 (Ar), 142.53 (d, Ar, J PC ) 2.6
Hz), 136.61 (d, Ar, J PC ) 9.4 Hz), 135.18 (o-C Xy), 134.36 (d,
2
3
o-CH PPh3, J PC ) 12 Hz, J PtC ) 16 Hz), 130.93 (d, i-C PPh3,
1J PC ) 47 Hz, 2J PtC ) 25 Hz), 130.39 (p-C PPh3), 128.69 (p-CH
Xy), 128.11 (d, m-C PPh3, J PC ) 11 Hz), 127.73 (m-C Xy),
127.43 (i-C Xy), 62.19 (m-OMe), 61.93 (m-OMe), 61.43 (p-OMe),
3
Meth od b. PPh3 (114 mg, 0.43 mmol) was added under
nitrogen to a solution of [Pt(dba)2] (102 mg, 0.15 mmol) in dry