3714 Organometallics, Vol. 19, No. 18, 2000
Alexander et al.
10.94 (s, 1, J CH ) 120 Hz, CHR), 7.47 (d, 2, J HH ) 7.5 Hz, o-Ph),
7.34 (s, 1, Biad), 7.25 (t, 2, J HH ) 8 Hz, m-Ph), 7.11 (s, 1, Biad),
7.06 (t, 1, J HH ) 7.5 Hz, p-Ph), 6.91 (s, 3, m,p-Ar), 3.65 (sept,
2, J HH ) 7.0 Hz, CHMe2), 2.37 (AB q, 6, Ad-CH2), 2.28 (AB q,
6, Ad-CH2), 2.21 (s, 3, Biad), 2.14 (br d, 6, Ad-CH), 2.13 (s, 3,
Biad), 1.90 (s, 3, CH(CH3)(MePh)), 2.1-1.82 (m, 12, Ad), 1.78
(s, 3, Biad), 1.74 (s, 3, Biad), 1.16 (d, 6, J HH ) 7.0 Hz, CH-
(CH3)(Me)), 1.15 (s, 3, C(CH3)(Me)Ph)), 0.94 (d, 6, J HH ) 7.0
mg (33%); 1H NMR δ 11.04 (s, 1, J CH ) 122 Hz, CHR), 7.37 (s,
1, Biad), 7.31 (d, 2, o-Ph), 7.13 (t, 2, m-Ph), 7.10 (s, 1, Biad),
6.98 (t, 1, p-Ph), 6.69 (s, 3, Ar), 2.34 (br AB pattern, 12 H,
Ad-CH2), 2.31 (s, 6, Ar(CH3)2), 2.22 (s, 3, Biad), 2.14 (br s, 6,
Ad-CH), 2.08 (s, 3, Biad), 1.86 (br AB pattern, 12, Ad-CH2),
1.80 (s, 3, Biad), 1.71 (s, 3, Biad), 1.65 (s, 3, C(CH3)(MePh)),
1.24 (s, 3, C(CH3)(MePh)); 13C{1H} NMR δ 278.09, 125.89,
154.98, 154.13, 151.11, 140.26, 138.55, 137.27, 136.43, 135.34,
132.16, 131.14, 131.04, 130.90, 130.42, 129.64, 128.50, 128.27,
127.42, 127.20, 126.28, 54.21, 41.67, 41.56, 38.33, 38.15,
38.10, 37.99, 32.94, 32.26, 30.10, 21.10, 20.96, 19.92, 17.43,
17.01.
Hz, CH(CH3)(Me)), anti δ 12.88 (s, 1, CHR), 7.75 (d, 2, J HH
)
7.5 Hz, o-Ph), 7.29 (t, 2, J HH ) 8.0 Hz, m-Ph), 7.12 (s, 1, Biad),
3.48 (sept, 2, CHMe2), 1.42 (d, 6, CH(CH3)(Me)), 1.03 (d, 6, CH-
(CH3)(Me)); 13C{1H} NMR δ 274.88, 155.61, 154.41, 154.23,
151.48, 146.48, 139.78, 138.68, 135.97, 135.70, 131.80, 131.12,
130.97, 130.45, 130.43, 128.70, 127.77, 127.30, 126.60, 126.36,
123.64, 53.61, 41.64, 41.51, 38.30, 38.12, 37.97, 37.90, 37.82,
33.42, 33.26, 29.97, 29.93, 29.27, 24.55, 25.52, 23.09, 20.97,
20.76, 17.00, 16.66, 14.65. Anal. Calcd for C58H73MoNO2: C,
76.37; H, 8.07; N, 1.54. Found: C, 76.45; H, 8.14; N, 1.47.
Mo(N-2,6-i-P r 2C6H3)(CHCMe2P h )[(S)-Bia d ]. Solid ben-
zylpotassium (2.04 equiv, 53 mg, 0.41 mmol) was added in
portions to a solution of (S)-H2[Biad] (102 mg, 0.2 mmol) in
THF (6 mL). After 10 min, Mo(N-2,6-i-Pr2C6H3)(CHCMe2Ph)-
(OTf)2(DME) (158 mg, 0.2 mmol) in THF (2 mL) was added.
After 1 h, the volatile components were removed in vacuo. The
residue was dissolved in toluene (2 mL), and the solution was
concentrated again in vacuo in order to remove residual THF.
The solid was then extracted with pentane (10 mL). The
suspension was filtered through Celite, and the filtrate’s
volume was reduced to ∼1 mL. A golden precipitate formed
when the solution stood for 1 h at room temperature, which
was collected by filtration and dried in vacuo; yield 62 mg
(34%).
Mo(N-2,6-Et2C6H3)(CHCMe2P h )[(S)-Bia d ]. Benzylpotas-
sium (2.08 equiv, 146 mg, 1.12 mmol) was added in portions
to a stirred solution of (S)-H2[Biad] (275 mg, 0.54 mmol) in
THF (30 mL). After 30 min solid Mo(N-2,6-Et2C6H3)(CHCMe2-
Ph)(OTf)2(DME) (412 mg, 0.54 mmol) was added. After 1 h,
the volatile components were removed in vacuo and the residue
was dissolved in pentane (5 mL). The red slurry was filtered
through Celite. Orange microcrystals formed in the filtrate.
Two crops were collected by filtration and dried in vacuo: yield
145 mg (30%); 1H NMR syn δ 11.03 (s, 1, J CH ) 121 Hz, CHR),
7.37 (d, 2, J HH ) 7.0 Hz, o-Ph), 7.37 (s, 1, Biad), 7.19 (t, 2, J HH
) 8.0 Hz, m-Ph), 7.08 (s, 1, Biad), 7.02 (t, 1, J HH ) 7.5 Hz,
p-Ph), 6.86-6.79 (m, 3, m, p-Ar), 2.93 (ABX3 sextet, 2, CHaHb-
Me), 2.74 (ABX3 sextet, 2, CHaHbMe), 2.37 (AB q, 6, Ad-CH2),
2.28 (AB q, 6, Ad-CH2), 2.21 (s, 3, Biad), 2.16 (br s, 3, Ad-CH),
2.11 (br s, 3, Ad-CH), 2.10 (s, 3, Biad), 1.93-1.80 (2 overlapping
AB q, 12, 2 Ad-CH2), 1.97 (s, 3, Me), 1.769 (s, 3, Biad), 1.73 (s,
3, C(CH3)(MePh)), 1.20 (s, 3, C(CH3)(MePh)), 1.01 (t, 6, J )
7.5 Hz, CHaHbCH3); anti δ 12.91 (s, 1, CHR), 3.35 (ABX3 m, 4,
CHaHbMe), 0.95 (t, 6, CH2CH3); 13C{1H} NMR 276.84, 155.76,
155.13, 153.82, 151.27, 142.37, 140.21, 138.70, 136.32, 135.49,
132.11, 131.19, 131.00, 130.80, 130.52, 129.37, 128.68, 127.76,
127.40, 126.27, 125.69, 53.77, 41.56, 41.49, 38.25, 38.02, 37.96,
37.85, 32.94, 32.92, 30.01, 29.98, 25.60, 20.95, 20.79, 17.95,
16.79, 14.30. Anal. Calcd for C56H69MoNO2: C, 76.08; H, 7.87;
N, 1.58. Found: C, 75.92; H, 7.96; N, 1.51.
Mo(N-2,6-Me2C6H3)(CHCMe2P h )[(S)-Bia d ]. Benzylpotas-
sium (146 mg, 1.12 mmol) was added in portions to a stirred
solution of (S)-H2[Biad] (255 mg, 0.5 mmol) in THF (30 mL).
After 30 min, solid Mo(N-2,6-Me2C6H3)(CHCMe2Ph)(OTf)2-
(DME) (368 mg, 0.5 mmol) was added. After 1 h, the volatile
components were removed in vacuo and benzene (10 mL) was
added to the residue. The slurry was filtered through Celite,
and the solvents were removed from the filtrate in vacuo. The
residue was dissolved in isopropyl ether (4 mL). An orange-
red precipitate formed on standing at room temperature. The
orange-red powder was collected by filtration, washed with cold
isopropyl ether, and dried in vacuo; yield 190 mg (44%).
Mo(N-2-CF 3C6H4)(CHCMe3)[Bia d ]. Benzylpotassium (52
mg, 0.4 mmol) was added in portions to a solution of H2[Biad]
(102 mg, 0.2 mmol) in toluene (6 mL). After 2 h solid Mo(N-
2-CF3C6H4)(CHCMe3)(OTf)2(DME) (142 mg, 0.2 mmol) was
added. After an additional 45 min, all solvents were removed
in vacuo. The dark red residue was extracted with pentane (5
mL), and the suspension was filtered through Celite. The
filtrate was concentrated to 2 mL, at which point red micro-
crystals began to form. The solution was stored at -25 °C
overnight. The red-orange microcrystals were collected by
decanting the liquor and drying in vacuo: yield 68 mg (41%);
1H NMR δ 10.64 (s, 1, J CH ) 120, CH-t-Bu), 7.62 (d, 1, J HH
7.8 Hz, Ar), 7.42 (s, 1, Biad), 7.11 (d, 1, J HH ) 7.5 Hz, Ar),
7.06 (s, 1, Biad), 6.92 (t, 1, J HH ) 7.8 Hz, Ar), 6.53 (t, 1, J HH
)
)
7.8 Hz, Ar), 2.45 (br q, 6, Ad-CH2), 2.31 (br s, 6, Ad-CH2), 2.22
(s, 3, Biad), 2.17 (br q, 6, Ad-CH), 2.06 (s, 3, Biad), 2.02-1.82
(multiple signals, 12, Ad), 1.76 (s, 3, Biad), 1.68 (s, 3, Biad),
1.16 (s, 9, t-Bu); 13C{1H} NMR δ 281.75, 154.53, 154.34, 153.68,
139.86, 139.47, 136.02, 135.49, 132.09, 131.98, 131.48, 131.18,
130.96, 130.62, 130.47, 130.26, 126.93 (q, J CF ) 29.5 Hz),
126.74, 126.52 (q, J CF ) 5.1 Hz), 124.23 (q, J CF ) 272.8 Hz),
46.10, 41.59, 38.47, 38.05, 37.92, 32.70, 30.05, 30.02, 23.10,
21.01, 20.86, 17.32, 16.95, 14.66. Anal. Calcd for C48H58F3-
MoNO2: C, 69.13; H, 7.01; N, 1.68. Found: C, 68.95; H, 6.91;
N, 1.70.
Mo(N-2-CF 3C6H4)(CHCMe3)[(S)-Bia d ]. Solid benzylpo-
tassium (130 mg, 1.0 mmol) was added in portions to a stirred
solution of (S)-H2[Biad] (254 mg, 0.5 mmol) in toluene (40 mL).
After 1 h solid Mo(N-2-CF3C6H4)(CHCMe3)(OTf)2(DME) (356
mg, 0.5 mmol) was added. After 1.5 h, the solvents were
removed in vacuo and the residue was dissolved in pentane
(75 mL). The suspension was filtered through Celite, and the
volume of the filtrate was reduced to approximately 5 mL. Red-
orange microcrystals formed and were collected by decanting
the solution. A second crop of red-orange powder was collected
by filtration and dried in vacuo; yield 180 mg (43%).
Mo(N-2,6-Me2C6H3)(CHCMe2P h )[Bia d ]. Benzylpotassium
(286 mg, 2.2 mmol) was added in portions to a solution of H2-
[Biad] (510 mg, 1 mmol) in THF (25 mL). After 1 h, solid Mo-
(N-2,6-Me2C6H3)(CHCMe2Ph)(OTf)2(DME) (735 mg, 1 mmol)
was added and the resulting dark red solution was stirred for
75 min. The reaction mixture was then concentrated in vacuo
to yield a red film. The product was extracted into benzene
(10 mL), and the suspension was filtered through Celite. The
benzene was removed from the filtrate in vacuo, and the
residue was dissolved in ether (4 mL). Orange crystals began
to form at room temperature. After 20 min, the solution was
cooled to -25 °C to promote additional crystallization. Two
crops were collected by filtration and dried in vacuo: yield 297
Ob ser va t ion of Mo(NAr P r 2)(CH Me)[Bip h en ]. cis-2-
Butene (∼20 mg) was added to a toluene-d8 (0.7 mL) solution
of Mo(NArPr2)(CHCMe2Ph)[Biphen] (25 mg, 0.033 mmol). The
orange solution was transferred to an NMR tube with a 14/20
standard taper joint, and a vacuum adapter was attached. The
solution was degassed with two freeze-pump-thaw cycles and
1
then sealed under an active vacuum. After 18 h, the H NMR
spectrum revealed a mixture of Mo(NArPr2)(CHCMe2Ph)-
[Biphen] (rel 16), Mo(NArPr2)(CHMe)[Biphen] (1.0), and cis-/
trans-2-butene (rel 68): δ 13.37 (q, 1, J HH ) 8.5 Hz, anti
CHMe), 10.64 (q, 1, J HH ) 6.5, syn CHMe); Ksyn/anti ) 2.0.