A.P. Mart´ınez et al. / Inorganica Chimica Acta 347 (2003) 86ꢂ
/
98
93
CH2). Data for 2: Orange; yield 95%. Anal. Calc. for
C23H18F7N2O4RhS: C, 42.22; H, 2.77; N, 4.28; S, 4.89.
Found: C, 42.06; H, 3.04; N, 4.23; S, 4.12%. MS (FAB)
11.4 Hz, 1H, H-8), 3.5 (s, 3H, NMe), 3.5 (s, 3H, NMe).
Data for 6: Green; yield 86%. Anal. Calc. for
C13H12F3IrN2O6S: C, 27.23; H, 2.11; N, 4.88; S, 5.59.
Found: C, 27.17; H 1.89; N 4.74; S 5.26%. IR (CH2Cl2,
cmꢃ1): n(CO): 2081 and 2006. MS (FAB) m/e 425 [Mꢁ,
m/e 505 [Mꢁ, 100]. LM (acetone, Cꢀ
/
5.0ꢄ
lꢃ1): 123 Vꢃ1 cm2 molꢃ1. H NMR (20 8C, CDCl3) d
ppm: 8.6 (d, 3JHꢂH 8.0 Hz, 1H, H-5), 8.2 (d, 3JHꢂH
11.4 Hz, 1H, H-9), 8.0 (m, H-4), 7.5 (2H, H-2ꢁ
/
10ꢃ4 mol
1
ꢀ
/
ꢀ
/
100], 395 [(Mꢃ
(acetone, Cꢀ5.0ꢄ
1H NMR (CDCl3) d ppm: 9.1 (d, JHꢂH
/
CO)ꢁ, 5], 365 [Mꢃ(CO)2ꢁ, 10]. LM
/
/H-3), 6.4
/
/
10ꢃ4 mol lꢃ1): 99 Vꢃ1 cm2 molꢃ1
.
8.1 Hz, 1H,
3
3
(d, JHꢂH
ꢀ
/
11.4 Hz, 1H, H-8), 5.7 (m, 2H, TFB), 4.0
ꢀ
/
(m, 4H, TFB), 3.4 (s, 3H, NMe), 3.3 (s, 3H, NMe). 19F
H-5), 8.7 (d, 3JHꢂH
ꢀ
/
5.4 Hz, 1H, H-2), 8.4 (d, 3JHꢂH
ꢀ
/
NMR (CDCl3) d ppm: ꢃ
/
80.6 (s, 1F, Otf), ꢃ
/
149.1 (m,
11.1 Hz, 1H, H-9), 8.3 (t, 3JHꢂH
ꢀ7.8 Hz, 1H, H-4), 7.7
/
3 3
(t, JHꢂH 6.3 Hz, 1H, H-3), 7.0 (d, JHꢂH
1H, H-8), 3.6 (s, 3H, NMe2), 3.6 (s, 3H, NMe2).
2F, TFB), ꢃ161.1 (m, 2F, TFB). Data for 3: Brown;
/
ꢀ
/
ꢀ11.4 Hz.
/
yield 92%. Anal. Calc. for C19H24F3IrN2O4S: C, 36.47;
H, 3.87; N, 4.48; S, 5.12. Found: C, 36.14; H, 3.23; N,
4.39; S, 5.03%. MS (FAB) m/e 477 [Mꢁ, 100], 626
3.3. Preparation of [M(CO)(PPh3)(N,O)]CF3SO3
1
(MOtf; 5). H NMR (20 8C, CDCl3) d ppm: 8.8 (d,
(Mꢀ
/
Rh, 7; MꢀIr, 8)
/
3
8.1Hz, 1H, H-5), 8.3 (d, JHꢂH
3JHꢂH
ꢀ
/
ꢀ11.4Hz, 1H,
/
3
3
H-9), 8.2 (t, JHꢂH
4.8Hz, 1H, H-2), 7.6 (t, 3JHꢂH
3JHꢂH
11.4Hz, 1H, H-8), 4.5 (br, 2H, Ä
2H, Ä
ꢀ
/
7.8Hz, 1H, H-4), 7.9 (d, JHꢂH
6.6Hz, 1H, H-3), 6.6 (d,
CH), 3.7 (br,
ꢀ
/
To CH2Cl2 (10 ml) suspensions of 5 (34 mg, 0.071
mmol) or 6 (42 mg, 0.073 mmol) PPh3 (20 mg, 0.076
mmol) was added and the solutions stirred for 10 min.
Evaporation to 2 ml and addition of diethyl ether (10
ml) led to orange solids, 7 and 8, which were separated
by filtration, washed with diethyl ether and vacuum
dried. Data for 7: Orange; yield 81%. Anal. Calc. for
C30H27F3N2O5PRhS: C, 50.15; H, 3.79; N, 3.90; S, 4.46.
Found: C, 50.50; H, 3.24; N, 3.94; S, 3.78%. IR
(CH2Cl2, cmꢃ1): n(CO): 1983. MS (FAB) m/e 569
ꢀ
/
ꢀ
/
/
/
CH), 3.4 (s, 3H, NMe), 3.4 (s, 3H, NMe), 2.3(m,
4H, CH2), 1.7 (m, 4H, CH2). 13C {H} NMR (CDCl3) d
ppm: 187.9 (s, C-7), 160.9 (s, C-9), 158.2 (s, C-6), 147.9
(s, C-2), 141.3 (s, C-4), 128.8 (s, C-3), 126.6 (s, C-5),
1
120.8 (q, JCꢂF
ꢀ324.5 Hz, Otf), 93.1 (s, C-8), 47.6 (s,
/
Me), 39.7 (s, NMe), 31.1 (s, CH2). Data for 4: Brown;
yield 69%. Anal. Calc. for C23H18F7IrN2O4S: C, 37.15;
H, 2.44; N, 3.77; S, 4.30. Found: C, 37.53; H, 2.08; N,
3.70; S, 4.12%. MS (FAB) m/e 505 [Mꢁ, 100]. LM
[Mꢁ, 100], 541 [(Mꢃ
5.0ꢄ
10ꢃ4 mol lꢃ1): 106 Vꢃ1 cm2 molꢃ1. H NMR
(CDCl3) d ppm: 8.7 (d, JHꢂHꢀ6.3 Hz, 1H, H-2), 8.7
/
CO)ꢁ, 10].]. LM (acetone, Cꢀ
/
1
/
3
(acetone, Cꢀ
/
5.0ꢄ
/
10ꢃ4 mol lꢃ1): 101 Vꢃ1 cm2 molꢃ1
.
8.0
/
1H NMR (20 8C, CDCl3) d ppm: 8.7 (d, JHꢂH
ꢀ
/
(d, JHꢂH
ꢀ
/
8.4 Hz, 1H, H-5), 8.2 (t, JHꢂH
ꢀ7.8 Hz,
/
3
3
3
3
Hz, 1H, H-5), 8.7 (d, JHꢂH
3
H-3), 7.1 (d, JHꢂH
ꢀ
/
11.0 Hz, 1H, H-9), 8.4 (t,
1H, H-4), 7.7ꢂ
/
7.4 (16H, PPh3ꢁ
/
ꢀ
/
3
8.0 Hz, 1H, H-4), 8.0 (d, JHꢂH
3
11.4 Hz, 1H, H-9), 6.4 (d, JHꢂH
3JHꢂH
H-2), 7.8 (t, JHꢂH
11.4 Hz, H-8), 5.8 (br, 2H, TFB), 3.7 (s, 3H, NMe), 3.5
ꢀ
/
ꢀ
/
5.5 Hz, 1H,
ꢀ11.4 Hz, 1H, H-8),
/
3
3
ꢀ
/
6.6 Hz, 1H, H-3), 6.6 (d, JHꢂH
ꢀ
/
3.3 (s, 3H, NMe), 3.3 (s, 3H, NMe). 31P{1H} NMR
1
(CDCl3) d ppm: 46.2 (d, JRhꢂP
ꢀ
156.8 Hz). 13C {H}
/
(s, 3H, NMe), 3.4 (br, 4H, TFB). 19F NMR (CDCl3) d
ꢀ76.0 Hz, 1H,
/
2
NMR (CDCl3) d ppm: 189.6 (d, JCꢂRh
ppm: ꢃ
(m, 2F, TFB).
/
79.2(s, 1F, Otf), ꢃ
/
148.2 (m, 2F, TFB), ꢃ
/
160.2
CO), 185.9 (s, C-7), 159.7 (s, C-9), 155.4 (s, C-6), 151.3
(s, C-2), 140.2 (s, C-4), 134.2 (d, 3JCꢂP
ꢀ11.5Hz, Cortho),
/
3
131.2 (d, JHꢂH
ꢀ
/
48.8Hz, 1C, Cipso), 131.0 (s, Cpara),
3
128.7 (d, JCꢂP
3.2. Preparation of [M(CO)2(N,O)]CF3SO3 (Mꢀ
/Rh,
ꢀ
/
10.1 Hz, Cmeta), 128.0 (s, C-3), 126.7
1
(s, C-5), 120.9 (q, JCꢂF
5; MꢀIr, 6)
/
ꢀ321.5 Hz, Otf), 92.9 (s, C-8),
/
46.8 (s, NMe), 39.1 (s, NMe). Data for 8: Orange; yield
68%. Anal. Calc. for C30H27F3IrN2O5PS: C, 44.61; H,
3.37; N, 3.47; S, 3.97. Found: C, 44.75; H, 2.93; N, 3.23;
S, 3.33%. IR (CH2Cl2, cmꢃ1): n(CO): 1967. MS (FAB)
Through CH2Cl2 (15 ml) solutions of 1 or 3 (0.14
mmol) CO (1 atm, r.t.) was bubbled for 1 h; complexes 5
and 6 were formed as green solids, which were separated
by filtration, washed with diethyl ether and vacuum
dried. Both complexes are scarcely soluble in most
solvents and they have to be store under argon to avoid
decomposition. Data for 5: Green; yield 67%. Anal.
Calc. for C13H12F3N2O6RhS: C, 32.25; H, 2.50; N, 5.80;
S, 6.61. Found: C, 31.35; H, 2.12; N, 5.66; S, 6.36%. IR
(CH2Cl2, cmꢃ1): n(CO): 2095 and 2025. MS (FAB) m/e
m/e 659 [Mꢁ, 100], 629 [(MꢃCO)ꢁ, 10]. LM (acetone,
/
Cꢀ
/
5.0ꢄ
/
10ꢃ4 mol lꢃ1): 112 Vꢃ1 cm2 molꢃ1
.
1H
ꢀ5.4 Hz, 1H, H-
3
NMR (CDCl3) d ppm: 8.8 (d, JHꢂH
/
3
3
2), 8.7 (d, JHꢂH
7.8 Hz, 4JHꢂH
3), 7.1 (d, JHꢂH
ꢀ
/
8.1 Hz, 1H, H-5), 8.2 (td, JHꢂH
1.5, 1H, H-4), 7.7ꢂ7.3 (16H, PPh3ꢁ
11.1 Hz, 1H, H-9), 6.5 (d, JHꢂH
ꢀ
/
ꢀ
/
/
/H-
3
3
ꢀ
/
ꢀ
/
11.7 Hz, 1H, H-8), 3.3 (s, 3H, NMe), 3.2 (s, 3H, NMe).
31P{1H} NMR (CDCl3) d ppm: 20.2 s. 13C {H} NMR
335 [Mꢁ, 100], 307 [(Mꢃ
5.0ꢄ
10ꢃ4 mol lꢃ1): 106 Vꢃ1 cm2 molꢃ1. H NMR
(CDCl3) d ppm: 9.0 (d, JHꢂH
/
CO)ꢁ, 55]. LM (acetone, Cꢀ
/
1
/
(CDCl3) d ppm: 186.9 (s, Cꢂ
CꢂO), 161.0 (s, C-9), 155.1 (s, C-6), 150.9 (s, C-2), 140.5
(s, C-4), 134.5 (d, JC-P
1JCꢂP
60.4 Hz, Cipso), 131.1 (s, Cpara), 129.4 (s, C-3),
/
O or C-7), 173.5 (br, C-7 or
3
ꢀ
/
8.1 Hz, 1H, H-5), 8.5
/
3
3
2
(d, JHꢂH
ꢀ
/
4.8 Hz, 1H, H-2), 8.3 (d, JHꢂH
1H, H-9), 8.3 (t, H-4), 7.6 (m, 1H, H-3), 6.8 (d, 3JHꢂH
ꢀ/11.4 Hz,
ꢀ11.5 Hz, Cortho), 131.2 (d,
/
ꢀ
/
ꢀ
/