2894
S. Dilsky / Journal of Organometallic Chemistry 692 (2007) 2887–2896
C, 28.18; H, 1.82; N, 15.17. Found: C, 27.86; H, 2.19; N,
15.38%.
change of the reaction mixture. After 1 h, pentane (6 mL)
was added, the precipitate was filtered off, washed twice
with pentane (5 mL), and dried under vacuum.
5.10. Halogen addition to [MeC(CH2 PPh2)3M(CO)3]
(5, 6)
5.15. [HC(pz)3W(CO)3H]BF4 (11)
The appropriate tricarbonyl complex (5 175 mg, 6
157 mg, 0.196 mmol) was suspended in dichloromethane
(5 mL). At 20 ꢁC, two equivalents of elemental halogen
(I2 100 mg, Br2 20.2 lL, 63 mg, 0.394 mmol) were added,
resulting in a change of color of the reaction mixture. After
2 h, diethyl ether (10 mL) was added, the precipitate was
filtered off, washed twice with diethyl ether (5 mL), and
dried under vacuum.
Yield 222 mg (0.390 mmol, quant.) blue powder, m.p.
138 ꢁC (dec.). 1H NMR (400 MHz, CD2Cl2, 20 ꢁC):
1
d = À2.50 (s, JW,H = 10.4 Hz, 1H, WH), 6.56 (dd,
3
3JH,H = 2.4 Hz, JH,H = 2.4 Hz, 3H, pyrazole-H4), 8.24
3
4
(dt, JH,H = 2.4 Hz, JH,H = 0.7 Hz, 3H, pyrazole-H3,5),
3
4
8.45 (dd, JH,H = 2.4 Hz, JH,H = 0.6 Hz, 3 H, pyrazole-
H3,5), 9.57 (s, 1H, HC(pz)3). 13C NMR (100 MHz,
CD2Cl2, 20 ꢁC) d = 76.3 (s, HC(pz)3), 109.7 (s), 135.3 (s),
1
149.6 (s), 214.3 (s, J(W,C) = 137 Hz, CO). IR (CH2Cl2):
5.11. [MeC(CH2PPh2)3 W(CO)3I]I3 (9a)
m (CO) = 2023 (s) cmÀ1, 1936 (s) cmÀ1, 1913 (m) cmÀ1
.
Anal. Calc. for C13H11BF4N6O3W (569.92): C, 27.40; H,
1.95; N, 14.75. Found: C, 23.29; H, 2.20; N, 13.27%.
Yield 275 mg (0.196 mmol, quant.) orange-yellow pow-
der, m.p. 108 ꢁC (dec.). 1H NMR (400 MHz, CD2Cl2,
4
20 ꢁC): d = 2.11 (q, JP,H = 3.1 Hz, 3H, CH3), 3.06–3.12
5.16. [HC(pz)3Mo(CO)3H]BF4 (12)
(m, 6 H, PCH2), 7.13–7.35 (m, 30H, C6H5). 13C NMR
(100 MHz, CD2Cl2, 20 ꢁC) d = 34.2–34.8 (m, PCH2),
38.8–39.0 (m, CH2CCH3), 40.4–41.1 (m, CH3), 129.0–
133.0 (m, C6H5). 31P NMR (162 MHz, CD2Cl2, 20 ꢁC):
Yield 188 mg (0.390 mmol, quant.) brown powder, m.p.
124 ꢁC (dec.). 1H NMR (400 MHz, CD2Cl2, 20 ꢁC):
d = À3.12 (s, 1H, MoH), 6.54 (vt, 3JH,H = 2.4 Hz, 3H, pyr-
1
3
d = À23.5 (s, JW,P = 157 Hz). IR (CH2Cl2): m (CO) =
azole-H4), 8.14 (d, JH,H = 2.4 Hz, 3H, pyrazole-H3,5),
3
2030 (s) cmÀ1, 1973 (s) cmÀ1, 1928 (m) cmÀ1. Anal. Calc.
for C44H39I4O3P3W (1400.16): C, 37.74; H, 2.81. Found:
C, 36.87; H, 2.92%.
8.42 (d, JH,H = 2.4 Hz, 3H, pyrazole-H3,5), 9.47 (s, 1H,
HC(pz)3). 13C NMR (100 MHz, CD2Cl2, 20 ꢁC) d = 75.8
(s, HC(pz)3), 109.1 (s), 135.1 (s), 148.5 (s), 219.1 (s, CO).
IR (CH2Cl2): m (CO) = 2030 (s) cmÀ1, 1947 (s) cmÀ1
,
5.12. [MeC(CH2PPh2)3 W(CO)3Br]Br3 (9b)
1926 (m) cmÀ1. Anal. Calc. for C13H11BF4MoN6O3
(482.01): C, 32.39; H, 2.30; N, 17.44. Found: C, 28.65; H,
2.67; N, 16.60%.
Yield 213 mg (0.176 mmol, 90%) orange-yellow powder,
1
m.p. 72 ꢁC (dec.). H NMR (300 MHz, CD2Cl2, 20 ꢁC):
d = 2.10–2.15 (m, 3H, CH3), 3.09–3.14 (m, 6H, PCH2),
5.17. Protonation of [MeC(CH2PPh2)3 M(CO)3] (5,6)
7.11–7.34 (m, 30H, C6H5). 31P NMR (121.5 MHz, CD2Cl2,
1
20 ꢁC) d = À14.2 (s, JW,P = 157 Hz). IR (CH2Cl2): m
The appropriate tricarbonyl complex (5 175 mg, 6
157 mg, 0.196 mmol) was suspended in dichloromethane
(3 mL). At 20 ꢁC, HBF4 (50 lL 54% in diethyl ether,
0.365 mmol) was added dropwise, resulting in clear solu-
tion. After 1 h, pentane (8 mL) was added, the precipitate
was filtered off, washed twice with pentane (6 mL), and
dried under vacuum.
(CO) = 2043 (s) cmÀ1, 1981 (s) cmÀ1, 1928 (m) cmÀ1
,
1904 (sh) cmÀ1
. Anal. Calc. for C44H39Br4O3P3W
(1212.16): C, 43.60; H, 3.24. Found: C, 43.86; H, 3.19%.
5.13. [MeC(CH2PPh2)3 Mo(CO)3I]I3 (10a)
Yield 257 mg (0.196 mmol, quant.) yellow-brown pow-
der, m.p. 66 ꢁC (dec.). 1H NMR (300 MHz, CD2Cl2,
20 ꢁC): d = 2.37–2.62 (m, 6H, PCH2), 2.99–3.25 (s, b, 3H,
CH3), 7.20–7.78 (m, 30H, C6H5). 31P NMR (121.5 MHz,
CD2Cl2, 20 ꢁC) d = À31.6 (s, b). IR (CH2Cl2): m (CO) =
2043 (s) cmÀ1, 1973 (s) cmÀ1, 1920 (s) cmÀ1. Anal. Calc.
for C44H39I4MoO3P3 (1312.26): C, 40.27; H, 3.00. Found:
C, 39.43; H, 3.16%.
5.18. [MeC(CH2PPh2)3 W(CO)3 H]BF4 (13)
Yield 191 mg (0.195 mmol, quant.) off-white solid, m.p.
106 ꢁC (dec.). 1H NMR (400 MHz, CD2Cl2, 20 ꢁC):
1
2
d = À4.62 (q, JW,H = 12.7 Hz, JP,H = 20.8 Hz, 1H,
4
WH), 1.76 (q, JP,H = 3.2 Hz, 3H, CH3), 2.67–2.73 (m,
6 H, PCH2), 7.05–7.43 (m, 30H, C6H5). 31P NMR
1
(162 MHz, CD2Cl2) d = À9.4 (s, JW,P = 180 Hz). 13C
5.14. Protonation of [HC(pz)3M(CO)3] (3,4)
NMR (100 MHz, CD2Cl2, 20 ꢁC) d = 32.5–32.9 (m,
PCH2), 38.5–38.6 (m, CH2CCH3), 39.2–39.3 (m, CH3),
1
The appropriate tricarbonyl complex (3 189 mg, 4
154 mg, 0.391 mmol) was suspended in dichloromethane
(3 mL) at 20 ꢁC. HBF4 (100 lL 54% in diethyl ether,
0.730 mmol) was added dropwise, resulting in a color
128.4–133.5 (m, C6H5), 206.7 (s, JW,C = 120 Hz, CO). IR
(CH2Cl2): m (CO) = 2027 (s) cmÀ1, 1956 (s) cmÀ1, 1933
(sh) cmÀ1. Anal. Calc. for C44H40BF4O3P3W (980.35): C,
53.91; H, 4.11. Found: C, 45.85; H, 4.31%.