1
was evaporated. The crude product was dried under vacuum for
H d (THF-d ) -14.23 (3H, br s, OsH), 1.02 (12H, dvt, JH,H 6.9, JH,P
8
◦
1
h at 50 C and then distilled (collecting all material distilling
13.8, CH
CH
d
3
), 1.07 (12H, dvt, JH,H 7.8, JH,P 14.4, CH
), 2.95 (4H, quint, JH,H 7.3, CH). H (hydride region) d (THF-
3
), 1.89 (8H, m,
◦
31
1
1
above 100 C, 0.01 mmHg). Yield: 11.4 g (94%). P{ H} d (C
6
D
6
)
2
1
31
◦
-
J
0.9. H{ P} d (C
6
D
6
) 0.98 (12H, d, JH,H 6.9, CH
3
), 1.02 (12H, d,
), 1.57
). An unknown impurity
8
, -90 C) -15.48 (2H, dt, JH,H 34.3, JH,P 10.5, OsH), -11.79 (1H,
1
3
1
H,H 7.2 Hz, CH
3
), 1.27 (1H, br s, NH), 1.51 (4H, m, CH
2
tt, JH,H 34.3, JH,P 8.0, OsH). C{ H} d (C
CH ), 20.1 (4C, t, JC,P 2.8, CH ), 27.8 (4C, t, JC,P 13.8, CH), 29.8
), 71.5 (2C, t, JC,P 6.6, NCH ).
6
D
6
) 18.8 (4C, t, JC,P 1.1,
(
4H, sep, JH,H 7.0, CH), 2.81 (4H, m, CH
2
1
3
3
3
1
was present in the distilled product, P{ H} d (C
6
D
6
) 3.5 (1.4%).
(2C, t, JC,P 9.0, PCH
2
2
i
OsH
3
Cl[HN(C
2
H
4
P Pr
2
)
2
] (1)
i
OsH
4
[HN(C
2
H
4
P Pr
2
)
2
] (3)
A 300 mL steel autoclave was taken into a nitrogen glovebox where
i
A mixture of OsH
3
Cl[HN(C
2
H
4
P Pr
2
)
2
] (1.11 g, 2.08 mmol) and
it was loaded with a stir bar, (NEt
4
)
2
OsCl
6
(3.73 g, 5.62 mmol),
(2.18 g, 16.87 mmol)
NaN(SiMe (0.39 g, 2.13 mmol) was stirred in 6 mL of diethyl
)
3 2
i
i
HN(C
2
H
4
P Pr
2
)
2
(1.9 g, 6.22 mmol), NEt Pr
2
ether for 3 h. The orange reaction solution was filtered, and the
flask and the fritted funnel were washed with 2 ¥ 1.5 mL of ether.
Then, 2-propanol (0.25 g, 4.16 mmol) was added and the mixture
and 2-propanol (125 mL). The autoclave was closed and removed
from the box; after tightening it was pressurized with hydrogen
gas under 120 psi, disconnected from the hydrogen line, and
◦
was left to crystallize in a freezer overnight, at -25 C. The mother
◦
placed into a preheated to 180 C oil bath. The reaction mixture
liquor was decanted and the remaining liquid was removed from
the colorless crystalline material with a pipette. The product was
dried under vacuum for 2 h. Yield: 0.876 g (84%). Found: C, 38.7;
was stirred for 24 h while maintaining the bath temperature at
◦
1
70–175 C with the use of a hotplate stirrer. The pressure in
the autoclave increased to 360 psi (ca. 25 bar), and continued
increasing, reaching 440 psi (ca. 30 bar) at the end of the reaction
time. When the autoclave was cooled to room temperature, the
residual pressure was 120 psi. The system was vented and opened
in air. All subsequent work was conducted in air. The reaction
solution was filtered into a 250 mL flask through a ca. 2 cm layer
of Celite. The autoclave and the fritted funnel were washed first
with 30 mL of THF and then with 20 mL of dichloromethane.
The product solution was evaporated and the residue was dried
H, 8.1; N, 2.5. Calc. for C16
H
41NOsP : C, 38.5; H, 8.3; N, 2.8%.
2
3
1
1
1
31
P{ H} d (C
6
D
6
) 62.6 (s, JP,Os 202.1). H{ P} d (C
6
D
6
) -12.09,
), 1.15 (12H,
), 1.23 (6H, d, JH,H 7.2,
-
6.86 (4H, br, OsH), 0.94 (2H, td, JH,H 6.0, 14.3, PCH
2
d, JH,H 6.9, CH
3
), 1.22 (6H, d, JH,H 6.9, CH
3
CH ), 1.55–1.75 (8H, m, CH
3
2
+ CH), 2.42 (2H, m, NCH
2
), 2.83
1
◦
(
(
1H, br t, NH). H (hydride region) d (THF-d
8
, -50 C) -14.14
1H, dt, JH,H 14.4, JH,P 4.3, OsH), -14.05 (1H, dt, JH,H 14.4, JH,P
4
.2, OsH), -7.31 (1H, dt, JH,H 10.5, JH,P 3.9, OsH), -7.19 (1H, dt,
13 1
J
H,H 10.5, JH,P 4.3, OsH). C{ H} d (C
), 20.19 (2C, t, JC,P 1.5, CH ), 20.72 (2C, t, JC,P 3.4, CH
0.94 (2C, t, JC,P 2.5, CH ), 26.63 (2C, t, JC,P 13.1, CH), 28.30 (2C,
t, JC,P 13.3, CH), 32.29 (2C, t, JC,P 8.9, PCH ), 59.50 (2C, t, JC,P
.5, NCH ).
6
D
6
) 20.08 (2C, t, JC,P 1.7,
◦
for 30 min at 50 C. Then, THF (80 mL) was added into the
CH
2
3
3
3
),
flask, followed by addition of 20 mL of deionized water. The
mixture was stirred rapidly. Upon standing it formed two layers,
and the aqueous layer was removed with a pipette. Further 50 mL
of water was added and the product started to crystallize from the
homogeneous aqueous THF solution. The flask was placed in an
ice bath for 1 h. The snow-white solid was isolated by filtration,
washed with 3 ¥ 6 mL of 2-propanol, and dried under vacuum for
3
2
4
2
i
Trans-OsH
2
(PMe
3
)[HN(C
2
H
4
P Pr
2
)
2
] (4)
] (200 mg, 0.37 mmol) and
i
5
h. Yield: 2.28 g (76%). Found: C, 35.8; H, 7.3; N, 2.4. Calc. for
A mixture of OsH
3
Cl[HN(C
2
H
4
P Pr
2 2
)
3
1
1
C
16
H
40ClNOsP
2
1
: C, 36.0; H, 7.55; N, 2.6%. P{ H} d (C
) -15.73 (1H, br s, OsH), -10.32
2H, br s, OsH), 0.78 (6H, d, JH,H 7.4, CH ), 0.98 (6H, d, JH,H 6.9,
), 1.09 (6H, d, JH,H 7.4, CH ), 1.54 (6H, d, JH,H 7.2, CH ), 1.45
2H, td, JH,H 6.0, 14.4, PCH ), 1.60 (2H, quint, JH,H 6.9, CH), 1.76
2H, dd, JH,H 3.6, 14.4, PCH ), 1.92 (2H, m, NCH ), 2.75 (2H,
6
D
6
) 53.1
tBuOK (44 mg, 0.39 mmol) was stirred in 6 mL of toluene for
3 h. The reaction solution was filtered and the flask and the fritted
funnel were washed with 2 ¥ 1.5 mL of toluene affording a clear
orange solution. Then, trimethylphosphine (28 mg, 0.37 mmol)
was added and the reaction solution was evaporated to dryness.
The product was extracted with 6 mL of hexane, then evaporated
and dried under vacuum for 5 h. Yield: 0.16 g (74%). Found: C,
31
(
(
s, JP,Os 201.6). H{ P} d (C
6
D
6
3
CH
(
(
3
3
3
2
2
2
quint, JH,H 7.4, CH), 2.82 (2H, m, NCH
2
), 3.89 (1H, br t, JH,H
1
◦
1
0.9, NH). H (hydride region) d (CD
2
Cl
2
, -80 C) -15.88 (1H, tt,
39.7; H, 8.1; N, 2.2. Calc. for C19
H
48NOsP
) -55.5 (1P, t, JP,P 16.1, PMe
31
3
: C, 39.8; H, 8.4; N,
), 59.5 (2P,
) -11.18 (1H, d, JH,H 15.8,
),
), 1.34 (6H, d,
), 1.38 (2H, m, PCH ), 1.69–1.82
3
1
1
J
H,H 6.8, JH,P 13.0, OsH), -11.16 (2H, dt, JH,H 6.8, JH,P 8.5, OsH).
2.4%. P{ H} d (THF-d
8
3
1
3
1
i
1
C{ H} d (C
6
D
6
) 17.2 (2C, br, CH
), 22.1 (2C, JC,P 3.5, CH
3.6, CH), 24.9 (2C, t, JC,P 12.6, CH), 33.5 (2C, t, JC,P 9.9, PCH
3
), 19.9 (2C, t, JC,P 1.1, CH
3
),
d, JP,P 16.1, P Pr
2
). H{ P} d (THF-d
8
2
1
5
1.9 (2C, t, JC,P 4.1, CH
3
3
), 23.8 (2C, t, JC,P
OsH), -10.47 (1H, d, JH,H 15.8, OsH), 1.11 (6H, d, JH,H 7.2, CH
1.18 (6H, d, JH,H 6.9, CH ), 1.21 (6H, d, JH,H 6.9, CH
H,H 7.2, CH ), 1.44 (9H, s, PMe
3
2
),
3
3
8.1 (2C, t, JC,P 3.7, NCH
2
).
J
3
3
2
(
4H, m, CH
2
), 1.97 (2H, quint, JH,H 7.2, CH), 2.05 (2H, quint, JH,H
1
i
6.9, CH), 2.96 (2H, m, NCH
region) d (THF-d
-10.47 (1H, dq, JH,H 15.8, JH,P 15.5, OsH). C{ H} d (THF-d
17.1 (2C, t, JC,P 1.4, CH ), 20.1 (2C, t, JC,P 1.3, CH ), 20.5 (2C, t,
C,P 3.3, CH ), 21.6 (2C, t, JC,P 3.4, CH ), 24.7 (2C, td, JC,P 1.3,
11.3, CH), 27.6 (2C, td, JC,P 0.8, 12.6, CH), 29.4 (2C, td, JC,P 3.4,
9.3, PCH ), 32.4 (3C, dt, JC,P 2.4, 28.1, PMe ), 58.7 (2C, td, JC,P
1.2, 4.6, NCH ).
2
), 4.43 (1H, br t, NH). H (hydride
OsH
3
[N(C
2
H
4
P Pr
2
)
2
] (2)
8
) -11.18 (1H, dq, JH,H 15.8, JH,P 15.5, OsH),
13 1
This complex was obtained and characterized in solu-
tion without isolation. 23–25 mg (0.043–0.047 mmol) of
8
)
3
3
i
OsH
mg of NaN(SiMe
tube. The product complex formed upon addition of the chosen
3
Cl[HN(C
2
H
4
P Pr
)
2
)
2
] and 5 mg of tBuOK (0.045 mmol) or
J
3
3
9
3 2
(0.049 mmol) were combined in an NMR
2
3
3
1
1
solvent (THF-d
8
, MCH-d14, C
6
D
6
). P{ H} d (THF-d
8
) 80.7 (s).
2
This journal is © The Royal Society of Chemistry 2011
Dalton Trans., 2011, 40, 8941–8949 | 8947