Chiral Terminal Pt(II) Phosphido Complexes
Organometallics, Vol. 18, No. 24, 1999 5149
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(Ph)Is, diastereomer b), 6.45 (dd, J PH ) 375, J PH ) 10, 1H,
PH(Ph)Is, diastereomer a), 3.10-2.99 (m, 2H, o-CHMe2), 2.92-
(Ar), 127.0 (Ar), 126.7 (Ar), 126.4 (Ar), 126.3 (Ar), 126.2 (Ar),
126.0 (Ar), 125.0 (Ar), 123.7 (Ar), 123.2 (Ar), 122.1 (Ar), 121.3
(Ar), 21.5 (p-tol Me), 21.4 (p-tol Me), 21.2 (p-tol Me), 21.1 (p-
2.83 (m, 1H, p-CHMe2), 2.51-2.23 (m, 2H, CHMe), 1.25-1.21
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(m, 6H, p-CHMe2), 1.18-1.01 (m, 6H, CHMe), 0.97 (d, J HH
)
tol Me), 11.2 (dd, J PC ) 97, 6, Pt-Me, Pt satellites were not
6, 3H, o-CHMe2), 0.96 (d, 3J HH ) 6, 3H, o-CHMe2), 0.82 (d, 3J HH
resolved). Anal. Calcd for C49H43ClP2Pt‚2/3Et2O: C, 63.73; H,
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) 6, 3H, o-CHMe2), 0.80 (d, J HH ) 6, 3H, o-CHMe2), 0.39-
5.14. Found: C, 63.40; H, 5.17. The presence of ether in the
0.32 (m, J Pt-H ) 60, 3H, Pt-Me). 13C{1H} NMR (CDCl3): δ
analytical sample was confirmed by H NMR.
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153.0-152.7 (m, quat. Ar), 136.0-135.5 (m, Ar), 134.2-134.1
(m, Ar), 132.9 (broad, Ar), 132.4-132.0 (m, Ar), 131.2-130.8
(m, Ar), 129.6-128.9 (m, Ar), 128.6-128.4 (m, Ar), 127.0-
[P t (R -Tol-Bin a p )(Me)(P H (Me)Mes*)][BF 4] (4). To a
stirred solution of Pt(R-Tol-Binap)(Me)(Cl) (302 mg, 0.33
mmol) in CH2Cl2 (5 mL) was added AgBF4 (64 mg, 0.33 mmol)
dissolved in CH3CN (5 mL). Immediate formation of AgCl
occurred, as indicated by a white precipitate. PH(Me)Mes* (105
mg, 0.36 mol) dissolved in CH2Cl2 (2 mL) was added to the
reaction mixture, which was stirred vigorously for 2 h. The
pale yellow solution was filtered, and the solvent was removed
in vacuo. The resulting solid was washed with three 2 mL
portions of petroleum ether. Recrystallization from CH2Cl2/
ether at -25 °C yielded 329 mg (80%) of a pale yellow
crystalline solid shown to be a single diastereomer by NMR.
1H NMR (CD2Cl2): 7.71-7.29 (m, 18H, Ar), 7.09-7.01 (m, 6H,
123.3 (m, quat. Ar), 122.8-122.5 (m, Ar), 38.5-36.0 (m,
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CHMe), 34.1 (p-CHMe2, b), 34.0 (p-CHMe2, a), 33.2 (d, J PC
)
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10, o-CHMe2, a), 33.0 (d, J PC ) 10, o-CHMe2, b), 24.4
(o-CHMe2, a), 24.2 (o-CHMe2, a), 24.1 (o-CHMe2, b), 24.0 (o-
CHMe2, b), 23.6 (p-CHMe2, a), 23.5 (p-CHMe2, b), 14.0-13.2
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(m, CHMe), 2.2 (dm, J PC ) 70, Pt-Me, b, Pt satellites were
not resolved), 0.2 (dm, 2J PC ) 65, Pt-Me, a, Pt satellites were
not resolved). IR: 3055, 2955, 2877, 2400 (w, PH), 1533, 1477,
1438, 1400, 1366, 1311, 1277, 1233, 1211, 1183, 1055 (BF4),
916, 883, 750, 688, 550, 527. Anal. Calcd for C50H60BF4P3Pt:
C, 57.97; H, 5.85. Found: C, 57.52; H, 5.83.
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Ar), 6.50-6.39 (m, 6H, Ar), 6.17 (dm, J PH ) 381, 1H, PH),
2.51 (3H, p-tol Me), 2.42 (3H, p-tol Me), 2.01 (6H, p-tol Me),
1.76 (9H, o-CMe3), 1.49 (9H, o-CMe3), 1.26 (9H, p-CMe3), 1.04-
[P t (S,S-Ch ir a p h os)(Me)(P H(Me)Mes*)][BF 4] (3). To a
stirred slurry of Pt(S,S-Chiraphos)(Me)(Cl) (320 mg, 0.476
mmol) in CH2Cl2 (10 mL) was added a solution of AgBF4 (93
mg, 0.48 mmol) dissolved in CH3CN (2 mL). Immediate
reaction occurred as indicated by the formation of AgCl. PH-
(Me)(Mes*) (153 mg, 0.524 mmol) dissolved in CH2Cl2 (2 mL)
was added to the reaction mixture, which was stirred vigor-
ously for 30 min. The pale yellow solution was filtered, and
the solvent was removed under vacuum. The white solid was
washed with ether (three 5 mL portions) and dried. Recrys-
tallization from CH2Cl2/ether at -25 °C yielded 387 mg (80%)
of a mixture of diastereomers in a ratio of approximately 3:1.
The NMR spectra are reported as a mixture of diastereomers
(a and b) unless otherwise indicated. 1H NMR (CD2Cl2): δ
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0.98 (m, J Pt-H ) 24, 3H, PMe), 0.13-0.06 (m, J Pt-H ) 59,
3H, Pt-Me). 13C{1H} NMR (CD2Cl2): δ 154.6 (Ar), 154.5 (Ar),
153.6 (Ar), 152.6-152.5 (m, Ar), 143.0 (Ar), 142.2 (Ar), 141.9
(Ar), 141.7 (Ar), 135.5-135.2 (m Ar), 134.9-134.6 (m, Ar),
134.3 (Ar), 134.1 (Ar), 133.6 (Ar), 130.3 (Ar), 130.2 (Ar), 129.1-
128.9 (m, Ar), 128.4-127.8 (m, Ar), 126.9 (Ar), 126.8 (Ar), 123.5
(Ar), 121.5 (Ar), 120.8 (Ar), 40.5 (o-CMe3), 39.9 (o-CMe3), 35.2
(p-CMe3), 35.1 (o-CMe3), 33.7 (o-CMe3), 30.9 (p-CMe3), 21.5 (p-
tol Me), 21.4 (p-tol Me), 21.3 (p-tol Me), 21.2 (p-tol Me), 14.3
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(d, J PC ) 36, PMe), 9.5 (d, J PC ) 68, Pt-Me, Pt satellites
were not resolved). IR: 2955, 2866, 2400 (w, PH), 1555, 1494,
1450, 1400, 1361, 1305, 1222, 1188, 1055 (BF4), 916, 872, 805,
744, 694, 672, 650, 600, 511, 433. Anal. Calcd for C68H76BF4P3-
Pt: C, 64.40; H, 6.05. Found: C, 64.04; H, 6.17.
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8.02-7.45 (broad m, 22H, Ar), 6.80 (dm, J PH ) 383, 1H, PH,
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diastereomer b), 6.03 (dm, J PH ) 374, 1H, PH, diastereomer
a), 2.29-2.16 (m, 2H, CHMe), 1.39 (broad, 21H, o-CMe3 and
PMe), 1.25 (broad, 9H, p-CMe3), 1.13-1.07 (broad m, 6H,
P t(S,S-Ch ir a p h os)(Me)[P (P h )Is] (5). To a stirred slurry
of [Pt(S,S-Chiraphos)(Me)(PH(Ph)Is)][BF4] (396 mg, 0.382
mmol) in THF (5 mL) was added LiN(SiMe3)2 (121 mg, 0.722
mmol) dissolved in THF (5 mL). The reaction mixture im-
mediately became homogeneous and bright orange and was
stirred at room temperature for 1 h. The solvent was removed
under vacuum, and the orange solid was washed twice with
petroleum ether (5 mL) and dried. The solid was extracted with
toluene (20 mL) and filtered. The filtrate was concentrated
under vacuum (to approximately 5 mL). Petroleum ether was
added to the toluene solution, and cooling of this solution to
-25 °C gave 284 mg (78%) of orange solid in two crops. 1H
NMR (toluene-d8): δ 7.92-7.79 (m, 4H, Ar), 7.54-7.48 (m, 2H,
Ar), 7.15-6.98 (m, 18H, Ar), 6.69-6.58 (m, 3H, Ar), 4.70-4.55
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CHMe), 0.44 (m, J Pt-H ) 60, Pt-Me, a), 0.04 (m, J Pt-H ) 60,
Pt-Me, b). 13C{1H} NMR (CD2Cl2): δ 155.8-155.6 (m, quat.
Ar), 155.5-154.7 (broad m, quat. Ar), 152.7 (quat. Ar), 152.5
(quat. Ar), 136.9-136.4 (m, Ar), 133.8 (Ar), 133.4-133.2 (m,
Ar), 133.2 (Ar), 132.7-131.5 (m, Ar), 130.1-129.2 (m, Ar),
128.3-123.2 (m, quat. Ar), 118.6 (quat. Ar), 118.0 (quat. Ar),
39.9-39.3 (m, CHMe), 39.2 (o-CMe3), 38.8-38.4 (broad, o-
CMe3), 37.9-36.5 (m, CHMe), 35.1 (p-CMe3), 34.2 (o-CMe3),
34.2-33.8 (broad, o-CMe3), 30.9 (p-CMe3), 14.8 (dm, 1J PC ) 36,
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P-Me), 14.1-13.4 (m, CHMe), 7.2 (dm, J PC ) 72, J Pt-C
)
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528, Pt-Me, a), 3.2 (dm, J PC ) 71, Pt-Me, b, Pt satellites
were not resolved). IR: 2955, 2877, 2400 (w, PH), 1538, 1477,
1433, 1361, 1183, 1061 (BF4), 916, 883, 750, 694, 550, 527.
Anal. Calcd for C48H64BF4P3Pt: C, 56.74; H, 6.36. Found: C,
56.26; H, 6.00.
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(m, 2H, o-CHMe2), 2.98 (septet, J HH ) 7, 1H, p-CHMe2), 1.94
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(broad, 2H, CHMe), 1.25 (d, J HH ) 7, 6H, p-CHMe2), 1.24 (d,
3J HH ) 7, 6H, o-CHMe2), 1.16 (d, 3J HH ) 7, 6H, o-CHMe2), 0.69-
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0.63 (m, 3H, CHMe), 0.67-0.63 (m, 3H, J Pt-H ) 67, Pt-Me),
P t(R-Tol-Bin a p )(Me)(Cl). In the air, to a stirred solution
of Pt(COD)(Me)(Cl) (350 mg, 0.98 mmol) dissolved in CH2Cl2
(5 mL) was added R-Tol-Binap (671 mg, 0.98 mmol) dissolved
in CH2Cl2 (2 mL). The pale yellow solution was stirred at room
temperature for 10 min. The solvent was removed in vacuo,
and the resulting solid was washed with three 2 mL portions
of ether. The solid was recrystallized from CH2Cl2/ether at -25
°C to yield 703 mg (77%) of pale yellow Pt(R-Tol-Binap)(Me)-
(Cl). 1H NMR (CD2Cl2): δ 7.73-7.28 (broad m, 20H, Ar), 7.06-
7.03 (m, 2H, Ar), 6.70-6.62 (m, 2H, Ar), 6.48-6.42 (m, 4H,
Ar), 2.45 (6H, p-tol Me), 1.99 (3H, p-tol Me), 1.98 (3H, p-tol
0.58-0.52 (m, 3H, CHMe). 13C{1H} NMR (toluene-d8):
δ
155.2-155.1 (m, quat. Ar), 147.6 (quat. Ar), 137.1-136.6 (m,
Ar), 133.7-133.5 (m, Ar), 132.4-132.3 (m, Ar), 132.1-132.0
(m, Ar), 131.2 (Ar), 130.8 (Ar), 130.0 (Ar), 129.4 (Ar), 128.7-
127.8 (m, Ar), 126.5-126.4 (m, Ar), 125.4-124.7 (m, quat. Ar),
123.2 (Ar), 121.2-121.1 (m, Ar), 39.3-38.5 (m, CHMe), 36.6-
35.8 (m, CHMe), 34.7 (p-CHMe2), 33.9 (o-CHMe2), 33.7 (o-
CHMe2), 26.0 (o-CHMe2), 25.2 (p-CHMe2), 24.3 (o-CHMe2),
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14.3-14.0 (m, CHMe), 3.1 (d, J PC ) 73, Pt-Me, Pt satellites
were not resolved). IR: 3055, 2955, 2866, 1477, 1433, 1377,
1311, 1277, 1183, 1100, 1055, 933, 877, 744, 694, 527. Anal.
Calcd for C50H59P3Pt: C, 63.34; H, 6.29. Found: C, 62.51; H,
6.28.
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Me), 0.44 (dd, J PH ) 8, 4, J Pt-H ) 55, 3H, Pt-Me). 13C{1H}
NMR (CD2Cl2): δ 141.1 (Ar), 140.6 (Ar), 140.4 (Ar), 139.9 (Ar),
139.4-139.3 (m, Ar), 137.6-137.4 (m, Ar), 136.1-135.9 (m,
Ar), 135.2-134.8 (m, Ar), 134.0 (Ar), 133.7 (Ar), 133.6 (Ar),
133.2 (Ar), 133.1 (m, Ar), 132.5 (Ar), 132.0 (Ar), 131.2 (Ar),
130.4 (Ar), 128.8-127.8 (m, Ar), 127.6 (Ar), 127.4 (Ar), 127.2
P t(S,S-Ch ir a p h os)(Me)[P (Me)(Mes*)] (6). To a solution
of [Pt(S,S-Chiraphos)(Me)(PH(Me)Mes*)][BF4] (165 mg, 0.163
mmol) in THF (5 mL) was added a solution of LiN(SiMe3)2 (33