836 Organometallics, Vol. 26, No. 4, 2007
Pilyugina et al.
precipitate to form, which was filtered off. The solution volume
was reduced to 1 mL, and ether was layered on top. The mixture
was left at -30 °C overnight, and the white crystalline material
was filtered off. Two more crops were collected in a similar manner
to give 2.9 g of white crystals (3.7 mmol, 51%): 1H NMR (C6D6)
were filtered off, and the solvent was removed in Vacuo to give a
yellow solid. The solid was triturated with pentane to give a pale
yellow powder; yield 4.6 g (0.07 mmol, 97%): 1H NMR (C6D6) δ
7.40 (br s, 4H), 7.30 (br s, 6H), 3.80 (s, 4H), 2.86 (s, 4H), 1.99 (s,
2H), 1.68-1.57 (m, 18H), 1.32 (s, 4H). Anal. Calcd for C36H46-
Cl2MoN2O: C, 62.70; H, 6.72; N, 4.06; Cl, 10.28. Found: C, 62.86;
H, 6.65; N, 4.14; Cl, 10.34.
δ 13.96 (s, 1H), 7.57 (d, 2H, JHH ) 8.5 Hz), 7.51 (d, 2H, JHH
)
8.5 Hz), 7.28 - 7.00 (m, 6H), 3.32 (s, 4H), 2.68 (m, 2H), 2.46 (s,
6H), 2.12 (m, 2H), 1.84 (s, 6H), 1.59-1.14 (m, 6H). Anal. Calcd
for C28H37F6MoS2NO8: C, 42.59; H, 4.72; N, 1.77. Found: C,
42.68; H, 4.79; N, 1.77.
Mo(NPhAd)2(CH2CMe2Ph)2. Procedure A. Mo(NPhAd)2Cl2
(3.0 g, 4.8 mmol) was dissolved in 100 mL of ether, and the solution
was cooled to -78 °C. A solution of PhMe2CCH2MgCl in ether
(10.2 mmol) was added dropwise to the reaction mixture. The
mixture was stirred at -78 °C for 30 min and then stirred at room
temperature overnight. The solution was diluted with 10 mL of
1,4-dioxane and stirred for 1 h. The solids were filtered off, and
the solvents were removed from the filtrate to give a brown oil.
The oil was dissolved in 10 mL of pentane. This solution was cooled
to -30 °C, and two crops of bright yellow crystals were collected;
Mo(NPhCy)(CHCMe2Ph)[(S)-Biphen] (7a). (S)-BiphenH2 (99.3
mg, 0.28 mmol) was dissolved in 10 mL of THF, and the solution
was cooled to -35 °C. Benzyl potassium (74.2 mg, 0.57 mmol)
was added, and the mixture was stirred for 1 h. The mixture was
added to a solution of Mo(NPhCy)(CHCMe2Ph)(OTf)2(dme)
(240 mg, 0.28 mmol) in 20 mL of ether that had been cooled to
-35 °C, and the mixture was stirred for 5 h. The solvent was
removed in Vacuo, and the resulting solid was extracted with 50
mL of pentane. The white precipitate was filtered off, and the
resulting yellow-orange solution was taken to dryness in Vacuo to
give an orange powder (180 mg, 0.22 mmol, 79%): 1H NMR
(C6D6) δ 10.95 (s, 1H), 7.41 (m, 1H), 7.39 (m, 2H), 7.37 (m, 2H),
7.22-7.19 (m, 2H), 7.13 (br s, 1H), 7.08-7.04 (m, 1H), 7.00-
6.95 (m, 3H), 2.27 (m, 1H), 2.18 (m, 1H), 2.09 (s, 3H), 2.07 (s,
3H), 1.75 (s, 3H), 1.71 (s, 3H), 1.68 (s, 3H), 1.62 (m, 2H), 1.59 (s,
9H), 1.55-1.49 (m, 4H), 1.45 (s, 9H), 1.16 (s, 3H), 1.03 (m, 2H);
13C NMR (C6D6) δ 273.6 (d, JCH ) 119.8 Hz). Anal. Calcd for
C46H59MoNO2: C, 73.28; H, 7.89; N, 1.86. Found: C, 73.20; H,
8.05; N, 1.84.
yield 1.7 g (2.0 mmol, 42%): 1H NMR (C6D6) δ 7.44 (d, JHH
7.5 Hz, 4H), 7.33 (d?, JHH ) 7.5 Hz, 4H), 7.24 (m, 8H), 7.10 (m,
4H), 2.62 (s, 4H), 2.48 (d, 2H, JHH ) 12 Hz), 1.82 (d, 4H, JHH
)
)
12 Hz), 1.78 (s, 2H), 1.66-1.58 (m, 22H), 1.26 (s, 12H). Anal.
Calcd for C52H64N2Mo: C, 76.82; H, 7.93; N, 3.45. Found: C,
76.88; H, 8.02; N, 3.54.
Procedure B. Mo(NPhAd)2Cl2(thf) (4.4 g, 6.4 mmol) was
dissolved in 50 mL of ether, and the solution was cooled to
-78 °C. A solution of PhMe2CCH2MgCl in ether (11.8 mmol) was
added dropwise to the reaction mixture. The mixture was stirred at
-78 °C for 30 min, then stirred at room temperature overnight.
The solvents were removed in Vacuo, and the resulting solid was
extracted with toluene. The white precipitate was filtered off, and
the toluene was removed in Vacuo to give a yellow solid. The solid
was triturated with pentane and isolated via filtration. The filtrate
was reduced to 5 mL in Vacuo and the solution cooled to -30 °C
overnight. A crop of yellow solid was collected and combined with
the triturated powder to give 2.7 g of the product (3.3 mmol, 52%).
The spectral data and elemental analysis results of this material
match the data obtained for the product synthesized via method A.
Mo(NPhCy)(CHCMe2Ph)[(R)-Trip](thf) (7b). (R)-TripK2 (214
mg, 0.25 mmol) was dissolved in 10 mL of THF. The solution
was cooled to -35 °C and added to a cold solution of Mo(NPhCy)-
(CHCMe2Ph)(OTf)2(dme) (200 mg, 0.25 mmol) in 15 mL of THF.
The mixture was stirred for 5 h, and the solvent was removed in
Vacuo. The solid was extracted with 50 mL of pentane, and the
white precipitate was filtered off. The resulting yellow solution was
taken to dryness to give a yellow powder (294 mg, 0.24 mmol,
99%): 1H NMR (C6D6) δ 14.02 (s, 1H), 7.73 (s, 1H), 7.71-7.61
(m, 3H), 7.58 (s, 1H), 7.49 (m, 1H), 7.46 (s, 1H), 7.37 (m, 1H),
7.24-7.17 (m, 3H), 7.13 (br s, 1H), 7.12-6.58 (m, 13H), 3.53 (m,
2H), 3.25 (septet, JHH ) 7 Hz, 1H), 3.07 (septet, JHH ) 7 Hz, 1H),
2.95 (septet, JHH ) 7 Hz, 1H), 2.78 (septet, JHH ) 7 Hz, 1H), 2.56
(br d, JHH ) 8 Hz, 1H), 2.32 (br d, JHH ) 8 Hz), 2.14 (br s, 4H),
1.85 (d, JHH ) 6.6 Hz, 6H), 1.77 (s, 3H), 1.64 (br s, 1H), 1.51 (d,
JHH ) 6.6 Hz, 6H), 1.42 (d, JHH ) 6.9 Hz, 6H), 1.37 (d, JHH ) 6.9
Hz, 12H), 1.34-1.20 (m, 3H), 1.24 (s, 3H), 1.17 (d, JHH ) 6.9 Hz,
6H), 1.08-1.04 (m, 4H), 0.69 (br s, 4H); 13C NMR (C6D6, ppm) δ
308.6 (d, JCH ) 145 Hz). Anal. Calcd for C77H93MoNO3: C, 78.61;
H, 7.97; N, 1.19. Found: C, 78.47; H, 8.09; N, 1.14.
Mo(NPhAd)(CHCMe2Ph)(OTf)2(DME). Mo(NPhAd)2(CH2-
CMe2Ph)2 (1.0 g, 1.2 mmol) was dissolved in 50 mL of ether, and
2 mL of DME was added. The mixture was cooled to -35 °C, and
a cold solution of freshly distilled TfOH (0.56 g, 3.7 mmol) in 10
mL of ether was added to it slowly. The mixture was stirred for 5
h. The solvents were removed in Vacuo, and the resulting brown
oil was extracted with toluene. The solids were filtered off, and
the toluene solution was reduced to 5 mL. The white solid was
filtered after 48 h at -30 °C; yield 461 mg (0.55 mmol, 54%): 1H
NMR (C6D6) δ 15.65 (s, 0.6 H), 14.89 (s, 0.4H), 14.11 (s, 1H),
7.54 (d, 2H, JHH ) 7 Hz), 7.47-7.18 (m, 8H), 7.14-6.88 (m, 12H),
3.32 (s, 4H), 3.12 (s, 3.6H), 3.31-2.34 (m, 10H), 2.28 (s, 6H),
2.20-1.96 (m, 4H), 1.86 (s, 6H), 1.82-1.22 (m, 24H), 1.64 (s, 2.4
H). Anal. Calcd for C32H41F6MoNO8S2: C, 45.66; H, 4.91; N, 1.66.
Found: C, 45.32; H, 5.02; N, 1.78.
Mo(NPhAd)2Cl2 (9). PhAdNH2 (5.0 g, 0.22 mol) was dissolved
in 150 mL of DME, and Na2MoO4 (2.3 g, 0.011 mol), Et3N (6.1
mL, 0.044 mol), and Me3SiCl (13.9 mL, 0.11 mol) were added.
The mixture was stirred at 60 °C for 18 h. The solids were filtered
off, and the solvent was removed in Vacuo to give a yellow oil.
Treatment of the oil with pentane gave a white powder, which was
removed by filtration. The resulting yellow solution was reduced
to 20 mL and cooled to -30 °C. The yellow product was filtered
off 48 h later; yield 3.0 g (0.05 mol, 44%): 1H NMR (C6D6) δ
7.44 (d, 2H, JHH ) 7.5 Hz), 7.25 (t, 2H, JHH ) 8 Hz), 7.13 (t, 1H,
JHH ) 8 Hz), 2.66 (s, 2H), 2.61 (d, 2H, JHH ) 13 Hz), 1.89 (s,
1H), 1.71 (d, 2H, JHH ) 12.5 Hz), 1.63-1.54 (m, 7H). Anal. Calcd
for C32H38Cl2MoN2: C, 62.24; H, 6.20; N, 4.54. Found: C, 62.14;
H, 6.16; N, 4.38.
Mo(NPhAd)(CHCMe2Ph)[(S)-Biphen] (11a). (S)-BiphenK2
(136 mg, 0.31 mmol) was dissolved in 10 mL of ether, and the
solution was cooled to -35 °C. The solution was added to a solution
of Mo(NPhAd)(CHCMe2Ph)(OTf)2(dme) (266 mg, 0.31 mmol) in
20 mL of ether that had been cooled to -35 °C. The solution was
stirred for 10 h. The solvent was removed in Vacuo, and the resulting
solid was extracted with 50 mL of pentane. The white precipitate
was filtered off, and the resulting orange solution was taken to
dryness to give an orange powder (210 mg, 0.26 mmol, 84%): 1H
NMR (C6D6) δ 10.72 (s, 1H), 7.49 (d, JHH ) 7.2 Hz, 1H), 7.32 (d,
JHH ) 7.2 Hz, 1H), 7.26 (s, 1H), 7.23-6.98 (m, 8H), 2.89 (br s,
1H), 2.54 (br s, 1H), 2.46 (br s, 1H), 2.22 (br s, 1H), 2.16 (s, 1H),
2.09 (s, 3H), 2.08 (s, 1H), 1.88 (br s, 1H), 1.85 (br s, 1H), 1.82 (br
s, 1H), 1.79 (br s, 1H), 1.77 (s, 3H), 1.75 (s, 1H), 1.70 (s, 1H),
1.62 (s, 6H), 1.59 (s, 6H), 1.53 (s, 18H), 1.33 (s, 1H), 1.26 (s, 1H);
Mo(NPhAd)2Cl2(thf) (10). PhAdNH2 (3.2 g, 0.14 mol) was
dissolved in 100 mL of THF, and Na2MoO4 (1.4 g, 0.07 mol), Et3N
(3.9 mL, 0.28 mol), and trimethylchlorosilane (8.8 mL, 0.69 mol)
were added. The mixture was stirred at 85 °C for 48 h. The solids