Organometallics
Article
7
.6, 7.2, 1H, CHarom), 7.50 (dd, 3J
= 7.6, 7.2, 1H, CHarom), 7.13 (d,
for 3 h at room temperature. The volatiles were removed under
vacuum, and the residue was washed with diethyl ether (2 × 1 mL)
affording a dark red solid. Yield: 0.085 g (87%). A crystal suitable for
X-ray diffraction study was obtained from slow diffusion of pentane in
a concentrated solution of 11 in dichloromethane (11 contraion was
H−H
3
3
JH−H = 7.6, 1H, CHarom), 7.09 (d, J
= 7.6, 1H, CHarom), 2.66 (s,
H−H
3
2
H, py−CH ), 2.47 (s, 3H, py−CH ), 2.37−2.27 (m, 6H, PCH),
3
3
.27−2.18 (m, 6H, PCH), 1.18−1.09 (m, 36H, PCH(CH ) ), 1.05
3
2
3
(
dvt, N = 12.8, J
= 6.4, 18H, PCH(CH ) ), 0.98 (dvt, N = 12.8,
H−H
3
2
3
2
exchanged by BArF
JH−H = 6.8, 18H, PCH(CH ) ), −14.31 (t, J
−
= 20.0, Os−H, 1H),
4
in order to facilitate the crystallization; the same
procedure as the one used for 7). Anal. Calcd. for
C Cl H N OOs P : C, 44.84; H, 5.44; N, 5.81. Found: C, 45.10;
3
2
H−P
2
13
1
17.43 (t, J
= 18.8, Os−H, 1H). C{ H} NMR (100.6 MHz,
H−P
2 2
CD Cl , 298 K): δ 187.7 (t, J
= 9.8, CO), 185.8 (t, J = 9.4,
C−P
45
2
65
5
2 2
2
2
C−P
H, 5.51; N, 5.52. HRMS (electrospray, m/z): Calcd. for
CO), 171.0, 168.9, 167.3, 166.6, 158.2, 156.8 (all s, Carom), 140.0 (s,
CHarom), 139.5, 138.4 (both s, Carom), 137.8, 131.3, 130.3, 125.1, 124.9,
+
−1
C ClH N OOs P [M] : 1170.3544, found: 1170.3607. IR (cm ):
45
65
5
2 2
1
ν (CO) 1888 (s). H NMR (400 MHz, CD Cl , 298 K) δ 8.98 (d,
1
22.1, 122.0, 117.5, 116.0 (all s, CHarom), 28.1 (vt, N = 24.9, PCH),
2
2
3
3
JH−H = 7.5, 1H, CHarom), 8.43 (d, J
= 8.3, 1H, CHarom), 8.29 (d,
2
8.0 (vt, N = 24.5, PCH), 25.2 (s, py−CH ), 25.1 (s, py−CH ), 20.2
H−H
3
3
31
1
3JH−H = 7.5, 1H, CHarom), 7.85−7.74 (m, 3H, CHarom), 7.68 (dd, 3JH−H
and 20.1 (both s, PCH(CH ) ). P{ H} NMR (162 MHz, CD Cl ,
3
2
2
2
3
298 K): δ 20.6 and 20.2 (both s).
= 7.5, 7.5, 1H, CH ), 7.54 (dd, J
= 7.5, 7.5 1H, CHarom), 7.16
= 7.3, 1H, CHarom), 6.29
H−H
arom
H−H
6
2
3
3
trans-[{OsCl(η -C H )} {μ-(κ -N ,N
) -BMePI}]Cl ([9a]Cl). A
py imine 2
(d, J
= 7.7, 1H, CHarom), 7.12 (d, J
6
6
2
H−H
6
6
solution of [(η -C H )OsCl ] (8) (0.100 g, 0.147 mmol) in methanol
(s, 6H, η -C H ) 2.75 (s, 3H, py−CH ), 2.65 (s, 3H, py−CH ), 2.43−
6
6
2
2
6
6
3
3
(
5 mL) was treated with HBPI (0.058 g, 0.177 mmol) and stirred for
2.33 (m, 3H, PCH), 2.33−2.22 (m, 3H, PCH), 1.93−0.99 (m, 36H,
2
13
1
4
8 h at room temperature in the absence of light. After this time, a red
PCH(CH ) ), −14.39 (t, J
= 20.0, Os−H, 1H). C{ H} NMR
H−P
2
3
2
solid had precipitated, and the solution was removed. The volatiles
were removed under vacuum, and the red solid was washed with
diethyl ether (3 × 2 mL) and dried under vacuum. Yield: 0.085 g
(100.6 MHz, CD Cl , 298 K): δ 185.6 (t, J
= 9.6, CO), 170.7,
C−P
2
2
169.6, 166.8, 166.0, 158.2, 157.4 (all s, Carom), 140.8 (s, CHarom), 138.7
(s, Carom), 138.2 (s, CHarom), 137.7 (s, Carom), 132.4, 131.0, 125.5,
6
(
59%). A crystal suitable for X-ray diffraction study was obtained from
124.1, 123.3, 121.1, 117.0, 115.3 (all s, CHarom), 76.1 (s, η -C H ),
6
6
a concentrated solution of 9a in dichloromethane. It was not possible
to measure 13C spectrum due to low solubility of the complex. Isomer
trans was obtained. Anal. Calcd. for C Cl H N Os : C, 39.65; H,
28.3−27.7 (m, PCH), 25.1 (s, py−CH ), 23.6 (s, py−CH ), 20.0 and
3
3
31 1
19.9 (both s, PCH(CH ) ). P{ H} NMR (162 MHz, CD Cl , 298
3
2
2
2
2
K): δ 20.5 (AB spin system, Δν = 169.5, J = 229.4).
32
3
28
5
2
A‑B
1
i
2
6
2
.91; N, 7.22. Found: C, 39.82; H, 2.79; N, 7.03. H NMR (300 MHz,
[(P Pr ) (CO)HOs{μ-(κ -N ,N
) -BMePI}OsCl(η -pCy)]Cl
3
2
py imine 2
3
4
CD Cl , 298 K): δ 8.36 (dd, J
7
= 5.6, J = 3.1, 2H, CHarom),
(12). A solution of 4 (0.066 g, 0.076 mmol) in methanol (5 mL) was
2
2
H−H
H−H
3
3
6
.81 (dd, J
arom
= 8.4, 7.7, 2H, CH ), 7.72 (d, J = 8.4, 2H,
treated with [(η -p-cymene)OsCl ] (7) (0.030 g, 0.038 mmol) and
2 2
H−H
arom
H−H
3
4
CH ), 7.68 (dd, J
= 5.6, J = 3.1, 2H, CHarom), 7.13 (d,
stirred for 3 h at room temperature. The volatiles were removed under
vacuum, and the residue was washed with diethyl ether (3 × 1.5 mL)
affording a reddish-purple solid. Yield: 0.080 g (92%). Anal. Calcd. for
H−H
H−H
3
6
JH−H = 7.7, 2H, CHarom), 6.32 (s, 12H, η -C H ) 2.69 (s, 6H, py−
6
6
CH3).
{OsCl(η -C H )} {μ-(κ -N ,N
6
2
F
F
C Cl H N OOs P : C, 46.66; H, 5.83; N, 5.55. Found: C, 46.85; H,
[
) -BMePI}](BAr ) ([9a]BAr
4
49
2
73
5
2 2
6
6
2
py imine 2
4
F
+
[9b]BAr ). A suspension of [9a]Cl (0.085g, 0.088 mmol) in
5.87; N, 5.67. HRMS (electrospray, m/z): Calcd. for
4
F
+
−1
methanol (5 mL) was treated with NaBAr 4 (0.093 g, 0.105 mmol)
and stirred for 3 h, at room temperature under light. The volatiles of
the resulting red solution were removed under vacuum, and 10 mL of
dichloromethane was added. The solution was filtered through Celite
and dried under vacuum. The residue was washed with pentane (3 × 2
mL) at approximately 203 K affording an orange solid, which was a
C
49ClH73
N
5
OOs
2 2
P [M] : 1226.4171, found: 1226.4235. IR (cm ):
1
ν (CO) 1897 (s). H NMR (300 MHz, CD
H−H = 7.5, 1H, CHarom), 8.42 (d, JH−H = 8.2, 1H, CHarom), 8.25 (d,
= 7.4, 1H, CHarom), 7.86−7.74 (m, 3H, CH ), 7.68 (dd, J
= 7.5, 7.4, 1H, CH ), 7.57 (dd, J
Cl , 298 K) δ 9.06 (d,
2
2
3
3
J
3J
3
H−H
arom
H−H
3
= 7.5, 7.5, 1H, CHarom), 7.17
arom
H−H
3
3
(d, J
= 7.2, 1H, CHarom), 7.15 (d, J
= 7.2, 1H, CHarom), 6.32
H−H
H−H
F
−
(d, 3JH−H = 5.5, 1H, CHarom(pCy)), 6.01 (d, JH−H = 5.6, 1H,
3
mixture of [BAr ] salts of the cations 9a and 9b in about a 1:1 ratio.
4
3
3
Yield: 0.126 g (80%). A crystal of 9b suitable for X-ray diffraction
study was obtained from slow diffusion of pentane in a concentrated
solution of the mixture in dichloromethane. Anal. Calcd. for
BC Cl F H N Os : C, 42.77; H, 2.24; N, 3.90. Found: C, 42.88;
CHarom(pCy)), 5.86 (d, J
= 5.5, 1H, CHarom(pCy)), 5.68 (d, J
H−H H−H
= 5.6, 1H, CHarom(pCy)), 2.71 (s, 3H, py−CH ), 2.68 (s, 3H, py−
3
3
CH ), 2.54 (sept, J
= 6.9, 1H, pCy−CH(CH ) ), 2.43 (s, 3H,
3
H−H
3
2
3
64
2
24 40
5
2
CH −pCy), 2.42−2.27 (m, 6H, PCH), 1.31 (d, J
3
H−H
= 6.9, 3H, pCy−
H, 2.60; N, 3.51. HRMS (electrospray, m/z): Calcd. for
CH(CH ) ), 1.20−1.04 (m, 36H, PCH(CH ) ), 1.20−1.04 (3H,
3
2
3 2
+
C Cl H N Os [M] : 934.0900, found: 934.0947. Isomer trans
pCy−CH(CH ) , overlapped with PCH(CH ) signals), −14.50 (t,
32
2
28
5
2
3
2
3 2
1
3
2 13 1
(
9a): H NMR (300 MHz, CD Cl , 298 K) δ 8.39 (dd, J
= 5.6,
J
= 19.9 Os−H, 1H). C{ H} NMR (75.5 MHz, CD Cl , 298 K):
H−P
2
2
2
H−H
2
2
4
F
JH−H = 3.1, 2H, CHarom), 7.81−7.67 (m, 14H, CH
(BPI + BAr )),
arom
4
δ 185.7 (t, J
= 9.6, CO), 170.9, 169.5, 166.7, 166.1, 158.4, 157.4
C−P
F
3
7
(
.56 (s, 4H, CH
(BAr )), 7.06 (d, J
= 8.0, 2H, CHarom), 6.16
(all s, Carom), 140.9 (s, CHarom), 138.9 (s, Carom), 138.3 (s, CHarom),
137.9 (s, Carom), 132.5, 131.3, 125.7, 124.4, 123.4, 121.3, 117.0, 115.6
(all s, CHarom), 95.9 (s, Cipso(pCy)), 95.2 (s, Cipso(pCy)), 74.1, 73.6,
72.5, 71.3 (both s, CHarom(pCy)), 32.6 (s, pCy−CH(CH ) ), 28.2 (vt,
arom
4
H−H
6
13
1
s, 12H, η -C H ) 2.64 (s, 6H, py−CH ). C{ H} NMR (75.5 MHz,
CD Cl , 298 K): δ 171.7, 166.3 (both s, C ), 162.3 (q, J = 49.8,
C(BAr )), 157.2 (s, Carom), 141.3 (s, CHarom), 139.0 (s, C ), 135.4
s, CHarom (BAr )), 133.0 (s, CH ), 129.4 (qq, J
6
6
3
1
2
2
arom
B−C
F
4
arom
3 2
F
2
3
(
=
1
(
= 31.5, J
N = 17.1, PCH), 28.0 (vt, N = 17.8, PCH), 25.2 (s, py−CH ), 23.6 (s,
4
arom
C−F
C−B
3
F
1
F
2.8, C−CF (BAr )), 125.2 (q, J
= 272.5, CF3 (BAr )), 125.0,
py−CH ), 23.0 (s, pCy−CH(CH ) ), 22.6 (s, pCy−CH(CH ) ), 20.0
3
4
C−F
4
3
3
2
3 2
3
F
31
1
22.1 (both s, CH ), 118.1 (spt, J
= 3.9, CHarom (BAr )), 116.1
and 20.0 (both s, PCH(CH ) ), 19.3 (s, CH −pCy) . P{ H} NMR
arom
C−F
4
3
2
3
6
1
2
s, CHarom), 76.1 (s, η -C H ), 23.3 (s, py−CH ). Isomer cis (9b): H
(121 MHz, CD Cl , 298 K): δ 20.5 (AB spin system, Δν = 69.0, J
6
6
3
2
2
A‑B
3
4
NMR (300 MHz, CD Cl , 298 K) δ 8.34 (dd, J
= 5.6, J = 3.1,
= 229.1).
2
2
H−H
H−H
3
2
H, CHarom), 8.06 (d, J
= 8.5, 2H, CHarom), 7.81−7.67 (m, 12H,
General Procedure for the Os-Catalyzed Dehydrogenation
Reactions of Alcohols. A solution of the catalyst (0.0178 mmol) and
the corresponding substrate (0.254 mmol) in toluene (1 mL) was
placed in a Schlenk flask equipped with a condenser. The mixture was
stirred at 100 °C for 24 h. After this time the solution was cooled at
room temperature, and the progress of the reaction was monitored by
GC (Agilent 6890N gas chromatograph with a flame ionization
detector, using an Agilent 19091N-133 polyethylene glycol column
(30 m × 250 μm × 0.25 μm thickness)). The oven conditions used are
as follows: 80 °C (hold 5 min) to 200 °C at 15 °C/min (hold 7 min),
except the reaction of dehydrogenation of diphenylmethanol: 150 °C
(hold 5 min) to 240 °C at 15 °C/min. For the reactions of
dehydrogenation of primary alcohols, yields and molar ratio of
H−H
F
F
3
CHarom (BPI + BAr )), 7.56 (s, 4H, CH
.9, 2H, CH ), 6.16 (s, 12H, η -C H ) 2.67 (s, 6H, py−CH ).
C{ H} NMR (75.5 MHz, CD Cl , 298 K): δ 171.7, 166.7 (both s,
(BAr )), 7.12 (d, J
=
4
arom
4
H−H
6
8
arom
6
6
3
1
3
1
2
2
1
F
Carom), 162.3 (q, J
= 49.8, C(BAr )), 157.0 (s, Carom), 141.2 (s,
B−C
4
F
CHarom), 138.7 (s, C ), 135.4 (s, CH
(BAr )), 132.6 (s,
4
arom
arom
2
3
F
CH ), 129.4 (qq, J
= 31.5, J
= 2.8, C−CF (BAr )), 125.2
arom
C−F
C−B
3
4
1
F
(
(
q, J
spt, J
= 272.5, CF (BAr )), 124.6, 122.0 (both s, CH ), 118.1
= 3.9, CHarom (BAr )), 116.5 (s, CH ), 76.1 (s, η -
C−F
3
4
arom
3
F
6
C−F
4 arom
C H ), 23.2 (s, py−CH ).
6
6
3
i
2
6
[
(P Pr ) (CO)HOs{μ-(κ -N ,N
) -BMePI}OsCl(η -C H )]Cl
3
2
py imine 2 6 6
(
11). A solution of 4 (0.070 g, 0.081 mmol) in methanol (5 mL) was
6
treated with [(η -C H )OsCl ] (8) (0.027 g, 0.040 mmol) and stirred
6
6
2 2
L
Organometallics XXXX, XXX, XXX−XXX