1434
J.-H. Lee et al. / Journal of Organometallic Chemistry 693 (2008) 1426–1438
Table 1
Selected bond lengths (A) and angles (ꢁ)
1.11 (dd, JHP = 17.1 Hz, JHP = 6.9 Hz, 18H, P(CHMe2)3),
.26 (dd, JHP = 17.1 Hz, JHP = 6.6 Hz, 18H, P(CHMe ) ),
˚
1
2 3
F
Os1–O1
Os1–P2
Os1–H1OS
S1–O2
S1–O1
S1–Na1
S2–O5
2.103(3)
2.2744(9)
1.52(4)
Os1–O4
Os1–P1
Os1–H2OS
S1–O3
S1–C19
S2–O6
2.155(2)
2.2748(9)
1.44(4)
2.56 (m, 6H, P(CHMe ) ), 7.56 (s, 4H, BAr ), 7.66 (t,
2 3
4
F
JHH = 7.5 Hz, 2H, Ph), 7.72 (s, 8H, BAr ), 7.80 (t,
4
JHH = 7.2 Hz, 1H, Ph), 7.99 (d, JHH = 7.5 Hz, 2H, Ph),
1.416(3)
1.477(3)
3.3426(18)
1.434(3)
2.313(6)
2.399(3)
2.435(3)
87.34(9)
134.25(7)
93.73(7)
85.0(14)
67.5(14)
154.6(16)
75.0(17)
111(2)
1.436(3)
1.843(5)
1.428(3)
1.464(2)
2.379(3)
2.420(3)
4.176(3)
94.05(8)
138.78(9)
113.38(3)
157.6(14)
78.5(14)
84.6(16)
66.0(16)
1
4.22 (dt, J
= 3.3 Hz, JHP = 2.7 Hz, 1 H, PhCCH).
HH
3
1
1
19
P{ H} NMR (CD Cl , 25 ꢁC): 83.8 (s) ppm. F NMR
2
2
S2–O4
(CD Cl , 25 ꢁC): ꢀ63.8 (s) ppm.
2
2
Na1–O7
Na1–O6
0
0
Na1 –O5
Na1 –O2
Na1–Na1
6
.6. Reaction of Os(H) ClL (OTf) with MeCCPh,
2 2
0
Na1–O3
O1–Os1–O4
O4–Os1–P2
O4–Os1–P1
O1–Os1–H1Os
P2–Os1–H1Os
O1–Os1–H2Os
P2–Os1–H2Os
H1Os–Os1–H2Os
2
forming [Os(H) ClL (g -MeCCPh)][OTf]
O1–Os1–P2
O1–Os1–P1
P2–Os1–P1
O4–Os1–H1Os
P1–Os1–H1Os
O4–Os1–H2Os
P1–Os1–H2Os
2
2
Os(H) ClL (OTf) (10 mg, 14.3 lmol) in 0.5 mL CD Cl
2 2 2 2
was prepared in a J. Young tube. MeCCPh (18 lL,
4.3 lmol) was added to the solution. Formation of the
1
2
adduct, [Os(H) ClL (g -MeCCPh)][OTf] was complete in
2
2
1
30 min. H NMR (CD Cl , 25 ꢁC): ꢀ12.57 ppm (dt,
2
2
JHH = 3.3 Hz, J = 17.1 Hz, 1H, OsH), ꢀ0.55 (ddt,
HP
JHH = 3.3 Hz, JHP = 32.1 Hz, 1H, OsH), 1.10 (dd,
+
involving Os are longer than those involving Na , and the
Na/O distances to ether are shorter than to triflate.
JHP = 17.1 Hz, JHP = 7.2 Hz, 18H, P(CHMe ) ), 1.17 (dd,
2 3
JHP = 16.5 Hz, JHP = 6.9 Hz, 18H, P(CHMe ) ), 2.63 (m,
2 3
6
H, P(CHMe ) ), 4.36 (s, 3H, PhCCMe), 7.74 (t,
2 3
6
.4. Reaction of Os(H) ClL (OTf) with PhCCH;
2
JHH = 7.8 Hz, 2 H, Ph), 7.84 (t, J = 7.5 Hz, 1H, Ph),
HH
2
2
31
1
formation of [Os(H) ClL(g -PhCCH)][OTf], 2a
8.00 (d, JHH = 6.9 Hz, 2H, Ph). P{ H} NMR (CD Cl ,
2 2
2
1
9
2
5 ꢁC): 83.8 (s) ppm. F NMR (CD Cl , 25 ꢁC): ꢀ78.5
2
2
13 1
The CD Cl solution (0.5 mL) of 14.3 lmol Os(H) Cl-
(s) ppm. C{ H} NMR (CD Cl , ꢀ40 ꢁC): 225.6 ppm
2
2
2
2
2
L (OTf) (10 mg) was prepared in J. Young tube. PhCCH
(s), 193.4 (s), 135.8, (s), 132.2 (s), 131.0 (s), 128.2 (s).
2
(
1.6 lL, 14.3 lmol) was added to the NMR tube. The pale
t
6.7. Reaction of Os(H) ClL (OTf) with BuCCH;
orange solution color changed to red in 30 min. Complete
formation of [Os(H) ClL(g -PhCCH)][OTf] was observed
2
2
2
2 t
2
formation of [Os(H) ClL (g - BuCCH)][OTf] (3a)
2 2
1
by NMR. H NMR (CD Cl , 25 ꢁC): ꢀ12.50 ppm (dt,
2
2
JHH = 4.5 Hz, J = 17.1 Hz, 1 H, OsH), ꢀ0.76 (ddt,
HP
Os(H) ClL (OTf) (10 mg, 14.3 lmol) was dissolved in
2 2
t
JHH = 3.3 Hz, JHH = 4.2 Hz, J = 33 Hz, 1H, OsH),
0.5 mL of CD Cl in a J. Young tube. BuCCH (1.8 lL,
2 2
HP
1
1
2
.14 (dd, JHP = 17.1 Hz, JHP = 6.6 Hz, 18H, P(CHMe2)3),
.28 (dd, JHP = 17.1 Hz, JHP = 6.6 Hz, 18H, P(CHMe2)3),
.64 (m, 6H, P(CHMe ) ), 7.72 (t, J = 7.2 Hz, 2H,
14.3 lmol) was added to the solution. Reaction was com-
2
t
plete in 30 min to form [Os(H) ClL (g - BuCCH)][OTf].
2
2
1
2
3
HH
H NMR (CD Cl , 25 ꢁC): ꢀ13.00 ppm (dt, J = 4.8 Hz,
2
2
HH
Ph), 7.83 (t, JHH = 7.2 Hz, 1 H, Ph), 8.08 (d, JHH = 7.2 Hz,
H, Ph), 14.13 (dt, J = 3.3 Hz, JHP = 2.7 Hz, 1H,
J
= 16.6 Hz, 1H, OsH), ꢀ0.76 (ddt, J = 2.7 Hz,
HH
HP
2
JHH = 4.8 Hz,
J
= 34.5 Hz, 1H, OsH), 1.25 (dd,
HP
HH
3
1
1
PhCCH). P{ H} NMR (CD Cl , 25 ꢁC): 84.6 (s) ppm.
JHP = 16.4 Hz, JHP = 6.0 Hz, 18H, P(CHMe ) ), 1.33 (dd,
2
2
2 3
1
9
13
1
F NMR (CD Cl , 25 ꢁC): ꢀ78.3 (s) ppm. C{ H}
JHP = 16.0 Hz, J = 6.0 Hz, 18H, P(CHMe ) ), 1.40 (s,
2
2
HP
2 3
t
NMR (CD Cl , ꢀ40 ꢁC): 199.5 ppm (br s), 185.7 (s),
9H, HCC Bu), 2.53 (m, 6H, P(CHMe ) ), 13.40 (dt,
2 3
2
2
1
36.3, (s), 135.3 (s), 131.0 (s), 129.9 (s).
J
= 2.7 Hz, triplet was not completely resolved, 1H,
HH
t
31
1
BuCCH). P{ H} NMR (CD Cl , 25 ꢁC): 85.3 (s) ppm.
2
2
F
19
13
1
6
.5. Reaction of [Os(H) ClL ][BAr ] with PhCCH;
F NMR (CD Cl , 25 ꢁC): ꢀ78.5 (s) ppm. C{ H}
2
2
2
4
2
2
F
formation of [Os(H) ClL (g -PhCCH)][BAr ], 2b
NMR (CD Cl , ꢀ40 ꢁC): 199.1 ppm (s), 192.2 (s).
2
2
4
2
2
F
t
Compound A: 1.6 lL (14.3 lmol) of PhCCH was added
6.8. Reaction of [Os(H) ClL ][BAr ] with BuCCH;
4
2 t
2
2
F
F
to 14.3 lmol [Os(H) ClL ][BAr ] dissolved in 0.5 ml of
formation of [Os(H) ClL(g - BuCCH)][BAr ] (3b)
2
2
4
2
4
CD Cl in a J. Young tube. Formation of the adduct,
2
2
2
F
t
[
Os(H) ClL (g -PhCCH)][BAr ] was complete in 30 min.
Compound
Compound A: 1.8 lL (14.3 lmol) of BuCCH was added
to 14.3 lmol [Os(H) ClL ][BAr ] dissolved in 0.5 ml of
2
2
4
2
F
B:
14.3 lmol
of
[Os(H) ClL (g -
2
2
2
2
4
PhCCH)][OTf] in 0.5 mL CD Cl was prepared in a J.
Young tube. NaBAr 4 (12.7 mg, 14.3 lmol) was added to
CD Cl in J. Young tube. Formation of the adduct,
2 2
2
2
F
2 t
F
[Os(H) ClL (g - BuCCH)][BAr ] was complete in 30 min.
2 2
4
t
2
the solution. The anion exchange was complete in
Compound B: 14.3 lmol of [Os(H) ClL (g - BuC-
2 2
1
3
0 min. H NMR (CD Cl , 25 ꢁC): ꢀ12.56 ppm (dt,
CH)][OTf] in 0.5 mL CD Cl was prepared in a J. Young
2 2
2
2
F
JHH = 4.5 Hz, J = 16.8 Hz, 1H, OsH), ꢀ0.89 (ddt,
HP
tube. NaBAr (12.7 mg, 14.3 lmol) was added to the solu-
4
1
JHH = 3.3 Hz, JHH = 4.2 Hz, J = 32.7 Hz, 1H, OsH),
HP
tion. The anion exchange was complete in 30 min. H