100
J. Gimeno et al. / Inorganica Chimica Acta 347 (2003) 99Á106
/
LinBu, HBF4×
from Aldrich Chemical Co. Infrared spectra were
recorded on a PerkinÁElmer 1720-XFT spectrometer.
The C and H analyses were carried out with a PerkinÁ
/
OEt2 and AgBF4 were used as received
(C-2), 109.7 (C-3a,7a), 126.3 (Ind), 127.9Á
/140.4 (Ind,
Ph). Dd(C-3a,7a)ꢀ 21.0.
/
ꢂ
/
/
/
2.2.3. [Os(h5-C9H7)H(PPh3)2] (3)
Elmer 240-B microanalyzer. NMR spectra were re-
corded on a Bruker AC300 instrument at 300 (1H),
121.5 (31P) or 75.4 MHz (13C) and on a Bruker AC200
instrument at 200 (1H), 81.0 (31P) or 50.3 MHz (13C)
using SiMe4 or 85% H3PO4 as standards. The following
atom labels are used for the 1H and 13C{1H} NMR
spectroscopic data.
A solution of NaOMe prepared in situ stirring NaH
(0.192 g, 8 mmol) in MeOH (12 ml), was added to a
suspension of complex [OsCl(h5-C9H7)(PPh3)2] (343 mg,
0.40 mmol) in MeOH (50 ml) and the mixture was
refluxed for 1 hour. The solvent was evaporated and the
residue was extracted with diethyl ether and filtered with
Kieselguhr. The solvent was then removed in vacuo to
yield complex 3 (283 mg, 86%) as a yellow solid mixture
of two rotamers. Anal. Calc. for C45H38OsP2: C, 65.0;
H, 4.6. Found: C, 64.9; H, 4.5%. 31P{1H} NMR (C6D6):
1
d 17.21, 17.27; H NMR (C6D6): d ꢂ
/
17.83 (t, JHP
26.0 Hz, 1H, H), 4.57
(m, 4H, H-1,3), 5.77 (m, 2H, H-2), 6.01 (m, 4H, H-4,7 or
H-5,6), 6.87Á7.77 (m, 64H, H-4,7 or H-5,6 and Ph);
13C{1H} NMR (C6D6): d 67.6 (C-1,3), 67.7 (C-1,3), 82.2
(C-2), 106.5 (C-3a,7a), 123.4 (Ind), 123.8 (Ind), 127.8Á
142.7 (Ind, Ph). Dd(C-3a,7a)ꢀ
24.2. IR (KBr, cmꢂ1):
2158 (OsH).
ꢀ
/
26.0 Hz, 1H, H), ꢂ
/
17.82 (t, JHP
ꢀ
/
The parameter Dd(C-3a,7a) is defined as the differ-
ence between d(C-3a,7a) of the indenyl complex and
/
d(C-3a,7a) of sodium indenyl (dꢀ130.7 ppm). The term
/
/
‘Ind’ in the NMR data is used for the undefined signals
of the benzoid ring.
/
ꢂ
/
2.2.4. [Os(h5-C9H7)Br(PPh3)(PR3)] (PR3ꢀ
(4a), PMe2Ph (4b)
/PMe3
2.2. Synthesis
A solution of complex [OsBr(h5-C9H7)(PPh3)2] (100
mg, 0.11 mmol) and PR3 (0.48 mmol) in toluene (10 ml)
was heated at refluxing temperature for four hours. The
solvent was then evaporated and the residue was
extracted with diethyl ether and filtered through Kie-
selguhr. The solvent was then removed in vacuo and the
solid washed once with hexane (5 ml) and vacuum dried
2.2.1. [Os(h5-C9H7)Br(PPh3)2] (1)
A solution of [OsBr2(PPh3)3] (330 mg, 0.29 mmol) and
LiInd (70 mg, 0.58 mmol) in tetrahydrofuran (30 ml)
was stirred for 2 h at room temperature (r.t.). The
solvent was then evaporated and the residue was
extracted with diethyl ether, evaporated in vacuo and
the obtained solid washed once with hexane and vacuum
dried to yield complex 1 (209 mg, 79%) as an orange
solid. Anal. Calc. for C45H37BrOsP2: C, 59.4; H, 4.1.
to yield complexes 4a, b as brown solids. PR3ꢀ
(4a): 15% yield; 31P{1H} NMR (C6D6): d Á
42.40 (d,
JPP 15.0 Hz, PMe3), 5.82 (d, JPP
15.0 Hz, PPh3); 1H
NMR (C6D6): d 1.34 (d, JHP 9.4 Hz, PMe3), 3.87 (m,,
1H, H-2), 4.92 (m, 1H, H-1 or H-3), 4.97 (m, 1H, H-1 or
H-3), 6.66Á7.69 (m, 19H, H-4,7, H-5,6 and Ph);
13C{1H} NMR (C6D6): d 20.2 (d, JCP
37.2 Hz,
/PMe3
/
ꢀ
/
ꢀ
/
Found: C, 59.9; H, 4.3%. 31P{1H} NMR (C6D6): d ꢂ
2.23; 1H NMR (C6D6): d 4.53 (d, JHH
1.9 Hz, 2H, H-
7.93 (m,
/
ꢀ
/
ꢀ
/
1,3), 5.11 (t, JHH
ꢀ
/
1.9 Hz, 1H, H-2), 6.90Á
/
/
34H, H-4,7, H-5,6 and Ph); 13C{1H} NMR (C6D6): d
ꢀ
/
62.3 (C-1,3), 84.3 (C-2), 110.1 (C-3a,7a), 125.0 (Ind),
PMe3), 58.9 (C-1 or C-3), 61.8 (C-1 or C-3), 81.9 (C-
2), 110.2 (C-3a,7a), 110.3 (C-3a,7a), 125.5 (Ind), 127.2
127.4Á
/
139.3 (Ind, Ph). Dd(C-3a,7a)ꢀ
/
ꢂ20.6.
/
(Ind), 132.3-140.4 (Ind, Ph). Dd(C-3a,7a)ꢀ
PR3ꢀ
PMe2Ph (4b): 21% yield; 31P{1H} NMR (C6D6):
d ꢂ31.97 (d, JPP 13.1 Hz, PMe2Ph), 3.90 (d, JPP
13.1 Hz, PPh3); H NMR (C6D6): d 1.26 (d, JHP 9.9
Hz, PMe2Ph), 3.66 (m,, 1H, H-2), 4.51 (m, 1H, H-1 or
H-3), 4.70 (m, 1H, H-1 or H-3), 6.50Á7.74 (m, 24H, H-
4,7, H-5,6 and Ph).
/
ꢂ
/
20.5;
2.2.2. [Os(h5-C9H7)I(PPh3)2] (2)
/
A suspension of complex [Os(h5-C9H7)Cl(PPh3)2] (50
mg, 0.06 mmol) and NaI (17 mg, 0.12 mmol) in MeOH
(1 ml) was refluxed for three hours. The solvent was then
evaporated and the residue was extracted with diethyl
ether and filtered with Kieselguhr. The solvent was
removed in vacuo and the resulting solid washed with
hexane (2x 10 ml) and vacuum dried to yield complex 2
(57 mg, 61%) as an orange solid. Anal. Calc. for
C45H37IOsP2: C, 56.5; H, 3.9. Found: C, 56.1; H,
/
ꢀ
/
ꢀ
/
1
ꢀ
/
/
2.2.5. [Os(h5-C9H7)H2(PPh3)2][BF4] (5)
To a solution of complex [OsH(h5-C9H7)(PPh3)2] (3)
(100 mg, 0.12 mmol) in diethyl ether (20 ml), HBF4×
/
4.0%. 31P{1H} NMR (C6D6): d ꢂ
(C6D6): d 4.51 (d, JHH 2.2 Hz, 2H, H-1,3), 4.93 (t,
JHH 2.2 Hz, 1H, H-2), 6.22Á7.41 (m, 34H, H-4,7, H-
5,6 and Ph); 13C{1H} NMR (C6D6): d 63.8 (C-1,3), 85.9
/
4.26; 1H NMR
OEt2 (0.12 mmol) in diethyl ether (20 ml) was added
dropwise at ꢂ80 8C and the mixture was stirred until
r.t. was reached. Solvents were then decanted and the
solid residue washed with diethyl ether (2ꢃ10 ml) and
ꢀ
/
/
ꢀ
/
/
/