Hughes et al.
1277
4
4
(10 mL) was added C3F7I (47 µL, 0.33 mmol) and the reac-
tion mixture was refluxed for 8 h. The solution was cooled
and the solvent removed in vacuo. Recrystallization from
hot hexane afforded the product as an orange
4JFF = 10 Hz, JPtF = 19 Hz, CF3), –93.51 (tq, 2F, JFF
=
=
2
3
10 Hz, JPtF = 410 Hz, PtCF2), –119.74 (t, 2F, JPtF
119 Hz, CF2CF3). Anal. calcd. for C24H27F7N2Pt (%): C
42.92, H 4.06; found (%): C 43.1, H 4.12.
1
microcrystalline solid (104 mg, 63%). H NMR (CDCl3) δ
3
[1,2-Bis(2,6-dimethylphenylimino)-1,2-dimethyl-
(ppm): 8.67 (t, 2H, JPtH = 26 Hz, N=CH), 7.45 (m, 4H,
ethane]methyl(1H-tetrafluoroethyl)platinum(II) (12)
To a solution of 8 (100 mg, 0.19 mmol) in ethyl acetate
(10 mL) was added C3F7I (42 µL, 0.29 mmol) and the reac-
tion mixture was heated under reflux in the absence of light
for 24 h. The solution was cooled and the solvent reduced to
5 mL in vacuo. Hexane was added. Filtration afforded the
product as a purple microcrystalline powder (100 mg, 85%).
1H NMR (CDCl3) δ (ppm): 7.30–7.17 (m, 6H, ArH), 5.63
ArH), 7.31 (m, 4H, ArH), 2.44 (s, 6H, ArCH3), 1.77 (t, 6H,
2JPtH = 74 Hz, PtCH3). 19F NMR (CDCl3) δ (ppm): –80.01 (t,
3F, 4JFF = 12 Hz, 4JPtF = 18 Hz, CF3), –91.93 (qt, 2F, 2JPtF
362 Hz, JFF = 12 Hz, JFF = 3 Hz, PtCF2), –121.79 (m, 2F,
CF2CF3). Anal. calcd. for C21H22F7IN2Pt (%): C 33.29, H
2.93; found (%): C 33.83, H 3.12.
=
4
3
[1,2-Bis(2,6-dimethylphenylimino)ethane](heptafluoro-
propyl)methylplatinum(II) (9)
2
3
2
(dq, 1H, JFH = 49 Hz, JFH = 13 Hz, JPtH = 52 Hz, CFH),
2.28 (s, ArCH3), 1.66 (s, 3H, N=C(CH3)), 1.35 (s, 3H,
To a solution of 7 (100 mg, 0.20 mmol) in hexane
(10 mL) was added C3F7I (44 µL, 0.31 mmol) and the reac-
tion mixture was heated at reflux for 18 h. The solution was
cooled. Filtration and washing with hexane afforded the
product as a maroon microcrystalline solid (146 mg, 91%).
2
N=C(CH3)), 1.10 (s, 3H, JPtH = 86 Hz, PtCH3). 19F NMR
3
3
(CDCl3) δ (ppm): –70.73 (dd, 3F, JFH = 13 Hz, JFF
=
2
3
14 Hz, CF3), –211.64 (dq, 1F, JFH = 49 Hz, JFF = 14 Hz,
CFH). Anal. calcd. for C23H28F4N2Pt (%): C 45.76, H 4.69;
found (%): C 45.77, H 4.53.
3
1H NMR (CDCl3) δ (ppm): 9.01 (t, 1H, JPt-H = 36 Hz,
3
N=CH), 8.93 (t, 1H, JPtH = 84 Hz, N=CH), 7.21 (s, 4H, m-
[1,2-Bis(2,6-dimethylphenylimino)ethane](heptafluoro-
propyl)iodoplatinum(II) (13)
ArH), 7.14 (m, 2H, p-ArH), 2.28 (s, 12H, CH3), 1.21 (t, 3H,
2JPtH = 88 Hz, PtCH3). 19F NMR (CDCl3) δ (ppm): –79.98 (t,
4
4
2
3F, JPtF = 36 Hz, JFF = 10 Hz, CF3), –94.74 (q, 2F, JPtF
=
=
Method 1:
4
3
420 Hz, JFF = 10 Hz, PtCF2), –120.33 (s, 2F, JPtF
To a solution of 9 (100 mg, 0.16 mmol) in CH2Cl2
(10 mL) was added iodine (39 mg, 0.16 mmol) and the reac-
tion mixture was stirred in the dark for 12 h. The solvent
was reduced in volume to approximately 5 mL in vacuo.
Hexane was added to precipitate the product as a brown
powder. Recrystallization from CH2Cl2–hexane at –30 °C af-
forded the product as an umber microcrystalline solid
116 Hz, CF2CF3). Anal. calcd. for C22H23F7N2Pt (%): C
41.06, H 3.61; found (%): C 41.04, H 3.69.
[1,2-Bis(2,6-dimethylphenylimino)ethane](1H-tetrafluoro-
ethyl)methylplatinum(II) (10)
To a solution of 7 (100 mg, 0.20 mmol) in ethyl acetate
(10 mL) was added iodo-1H-tetrafluoroethane (70 mg,
0.31 mmol) and the reaction mixture was heated at reflux for
12 h in the absence of light. The solvent was removed in
vacuo and the residue was washed with hexane until no col-
our persisted in the washings. The product was obtained as
purple needles after recrystallization from chloroform–hex-
1
(94 mg, 80%). H NMR (CDCl3) δ (ppm): 9.00 (t, 1H,
3
3JPtH = 102 Hz, N=CH), 8.62 (t, 1H, JPtH = 40 Hz, N=CH),
7.23–7.15 (m, 6H, ArH), 2.33 (s, 6H, CH3), 2.30 (s, 6H,
4
CH3). 19F NMR (CDCl3) δ (ppm): –80.08 (t, 3F, JFF
=
2
4
11 Hz, CF3), –80.83 (tqd, 2F, JPtF = 288 Hz, JFF = 11 Hz,
5JFH = 4 Hz, PtCF2), –114.69 (t, 2F, JPtF = 72 Hz, CF2CF3).
5
1
ane (50 mg, 45%). H NMR (CDCl33) δ (ppm): 9.20 (s, 1H,
Anal. calcd. for C21H20F7IN2Pt (%): C 33.39, H 2.67; found
(%): C 32.65, H 2.57.
3JPtH = 37 Hz, N=CH), 9.06 (s, 1H, JPtH = 42 Hz, N=CH),
2
3
7.24–7.15 (m, 6H, ArH), 6.03 (dq, 1H, JFH = 50 Hz, JFH
=
2
11 Hz, JPtF = 61 Hz, CFH), 2.36 (s, 3H, ArCH3), 2.29 (s,
3H, ArCH3), 2.27 (s, 3H, ArCH3), 2.20 (s, 3H, ArCH3), 1.36
Method 2:
To a solution of 9 (100 mg, 0.16 mmol) in toluene
(10 mL) was added hydriodic acid (57% w/w, 20 µL,
0.16 mmol) and the reaction mixture was stirred at room
temperature for 4 h. The solvent was removed in vacuo and
the residue recrystallized from CH2Cl2–hexane to afford the
product as an umber microcrystalline powder (83 mg, 78%).
(s, 3H, JPtH = 86 Hz, PtCH3). 19F NMR (CDCl3) δ (ppm):
2
3
3
3
–70.69 (dd, 3F, JFH = 14 Hz, JFF = 14 Hz, JPtF = 141 Hz,
2
3
2
CF3), –212.28 (dq, 1F, JFH = 50 Hz, JFF = 14 Hz, JPtF
=
327 Hz, CFH). Anal. calcd. for C21H24F4N2PtC0.5CHCl3
(%): C 40.65, H 3.90; found (%): C 41.37, H 3.74.
[1,2-Bis(2,6-dimethylphenylimino)-1,2-dimethyl-
ethane](heptafluoropropyl)methylplatinum(II) (11)
[1,2-Bis(2,6-dimethylphenylimino)ethane](1H-tetrafluoro-
ethyl)iodoplatinum(II) (14)
To a solution of 8 (100 mg, 0.19 mmol) in ethyl acetate
(10 mL) was added C3F7I (42 µL, 0.29 mmol) and the reac-
tion mixture was heated under reflux in the absence of light
for 2 h. The solution was cooled and the solvent removed in
vacuo. The residue was recrystallized from CH2Cl2–hexane.
Filtration afforded the complex as a purple powder (66 mg,
51%). 1H NMR (CDCl3) δ (ppm): 7.19 (m, 4H, p-ArH), 7.12
To a solution of 10 (100 mg, 0.19 mmol) in toluene
(10 mL) was added HI (57% w/w, 33 µL, 0.29 mmol) and
the reaction mixture was stirred at room temperature for 4 h.
The solvent was removed in vacuo and the residue recrystal-
lized from CH2Cl2–hexane to afford the product as a black
1
powder (86 mg, 74%). H NMR (CDCl3) δ (ppm): 9.16 (s,
3
3
1H, JPtH = 100 Hz, N=CH), 8.68 (s, 1H, JPtH = 38 Hz,
2
(s, 2H, p-ArH), 2.21 (s, 12H, o-ArCH3), 1.73 (s, 3H,
N=CH), 7.25–7.15 (m, 6H, ArH), 6.09 (dq, 1H, JFH =
50 Hz, JFH = 11 Hz, JPtH = 61 Hz, Hz, CFH), 2.39 (s, 3H,
ArCH3), 2.36 (s, 3H, ArCH3), 2.29 (s, 3H, ArCH3), 2.25 (s,
2
3
2
N=C(CH3)), 1.63 ((s, 3H, N=C(CH3)), 0.70 (t, 3H, JPtH
=
86 Hz, PtCH3). 19F NMR (CDCl3) δ (ppm): –80.01 (tt, 3F,
© 2003 NRC Canada