A R T I C L E S
Sadow and Togni
added slowly, and the mixture was allowed to warm to room
temperature (r.t.) and then was heated to reflux for 2 h. The reaction
Calcd for C17
H, 10.99; N, 4.93. [R]
H
30NP: C, 73.08; H, 10.82; N, 5.01; Found: C, 73.23;
20
D
) 2.29 ( 0.08 (CH
2
Cl
2
, c ) 1 M) at 70% ee.
-
2
mixture was filtered and purified by distillation (40 °C at 2 × 10
mbar). In a separate flask, OEt (70 mL) was added to LiAlH (3.59
g), and the flask was cooled to 0 °C. The distilled (EtMe C) PCl was
3
[Ni((R)-(S)-κ -Pigiphos)(NCMeCCH
2
)][ClO
4
]
2
‚(NCMeCCH ) ([3]-
2
-3
2
4
[
ClO
]
)‚(NCMeCCH
O) ](ClO
). Pigiphos (1.153 g, 1.27 × 10 mol) and
4
2
2
-3
2
2
[Ni(H2
6
4
)
2
(0.464 g, 1.27 × 10 mol) were mixed in meth-
added in a dropwise fashion to this mixture, and the reaction mixture
was then heated to reflux overnight. Degassed water was added slowly
acrylonitrile (3 mL) to give a purple solution. The solution was filtered,
and [3][ClO ] was crystallized by slow diffusion of OEt into the
4
2
2
(
0 °C), and the mixture was filtered, dried over MgSO
4
, and distilled
methacrylonitrile solution at -20 °C. The compound was barely soluble
in THF-d and was slightly more soluble (but reacted slowly) in CD Cl
under reduced pressure. Yield: 5 g, 28%, density ) 0.76 g/mL.
8
2
2
1
1
3
1
31
1
H NMR (C
6
D
6
, 400 MHz): δ 3.12 (d, 1 H, HP, JPH ) 202 Hz),
.55-1.39 (m, 4 H, ((H CCH )(CH C) PH), 1.13 (d, 6 H, ((CH (H
PH, JPH ) 10 Hz), 1.11 (d, 6 H, ((CH (H CCH )C) PH,
PH, JHH ) 8 Hz).
CCH )(CH C)
PH, 1JPC ) 20 Hz),
PH, JPC ) 11 Hz), 29.0 (d, ((H CCH )-
PH, JPC ) 13 Hz), 9.529 (d, ((H CCH )(CH C) PH, JPC
, 162 MHz): δ 2.9. Anal. Calcd for
23P: C, 68.92; H, 13.30. Found: C, 68.97; H, 13.18.
Representative Procedure for Hydrophosphination Catalysis. The
to form [Ni(κ -Pigiphos)Cl][ClO ]. Thus, H and P{ H} NMR spectra
4
1
3
2
)
3 2
2
)
3 2
3
-
were obtained in CD Cl . Excess methacrylonitrile was required to
2
2
2
13
1
CCH
2
)C)
2
3
)
2
3
2
2
obtain a C{ H} NMR spectrum, and the resulting spectrum was
unfortunately obscured by the large methacrylonitrile peaks. Yield )
2
3
J
PH ) 11 Hz), 0.898 (t, 6 H, ((H
3
CCH
2
)(CH
3
)
2
C)
2
13
1
-3
1
C{ H} NMR (C
D
6 6
, 100.6 MHz): δ 36.8 (d, ((H
3
2
)
3 2
2
-
1.37 g (1.03 × 10 mol, 80.7%). H NMR (THF-d
P(C ), 7.75 (br m, 1 H, P(C ), 7.61 (br t, 5 H, P(C
(br t, 5 H, P(C ), 7.35 (br t, 3 H, P(C ), 7.10 (br t, 1 H,
P(C ), 5.79 (s, 2 H, H CCMeCN), 5.75 (s, 2 H, H CCMeCN), 5.07
(s, 2 H, C ), 4.86 (s, 1 H, C ), 4.78 (s, 1 H, C ), 4.70 (s, 1 H,
), 4.20 (s, 5 H, C ) 4.18 (s, 1 H, C ), 3.69 (s, 7 H, C and
CHCH ), 2.55 (br, 1 H, C 11 and CH ), 1.95
(s, 6 H, H /methacrylonitrile, 100
8
): δ 8.98 (m, 5 H,
PH, 2JPC ) 14.2 Hz), 33.8 (d, ((H
CCH )(CH C)
)
3
2
2
3
2
2
6
H
5
)
2
6
H
5
)
2
6 5 2
H )
), 7.52
2
(
)
9.4 (d, ((H
CH C)
10 Hz). P{ H} NMR (C
3
CCH
2
)(CH
3
)
2
C)
2
3
2
6
H
5
)
2
6 5 2
H )
2
3
3
)
2
2
3
2
3
)
2
2
6
H
5
)
2
2
2
3
1
1
D
6 6
5
H
3
5
H
3
5 3
H
C
10
H
C
5
H
3
5
H
5
5
H
3
5 5
H
3
6
H
1
11), 2.21 (m, 13 H, C
6
H
3
3
2
CCMeCN). 13C{ H} NMR (CD
2
Cl
2
compound [Ni(κ -Pigiphos)(NCMeCCH
2
4 2 4 2
)][ClO ] ([3][ClO ] , 0.0044
-
6
MHz): δ 135.1 (br, Pigiphos-Ph), 134.0 (Pigiphos-Ph), 133.8 (Pigiphos-
Ph), 133.4 (br, Pigiphos-Ph), 133.3 (Pigiphos-Ph), 132.2 (br, Pigiphos-
g, 2.28 × 10 mol) was dissolved in a mixture of acetone (1 mL) and
-
3
methacrylonitrile (0.284 mL, 3.39 × 10 mol) to give a deep purple
2
solution. The reaction mixture was cooled to -20 °C, and (EtMe C) -
Ph), 131.5 (NC(CH
Pigiphos-Ph), 119.6 (NC(CH
Pigiphos-C ), 74.1 (br, Pigiphos-C
Pigiphos-C ), 72.2 (Pigiphos-C
Pigiphos-C ), 71.5 (br, Pigiphos-C
(Pigiphos-C ), 39.9 (Pigiphos), 33.3 (Pigiphos), 29.2 (Pigiphos), 27.2
Pigiphos), 26.0 (Pigiphos), 26.0 (Pigiphos), 25.9 (Pigiphos), 20.8
3
)CCH
2
), 130.5 (br, Pigiphos-Ph), 130.3 (br,
)CCH ), 118.5 (NC(CH )CCH ), 75.0 (br,
), 73.2 (br, Pigiphos-C ), 73.0
), 71.8 (Pigiphos-C ), 71.8 (br,
), 69.7 (Pigiphos-C ), 69.6
2
-
4
3
2
3
2
PH (3.93 × 10 mol) was added. After 24 h, pentane was added to
precipitate the dicationic Ni complex. The suspension was filtered, and
the mother liquor was concentrated to an oil. The oil was redissolved
in pentane and filtered through Al
gave analytically pure (EtMe C) PCH
mol, 86%).
Me EtC)
δ 2.20 (m, 1 H, CH
H
5 3
5
H
3
5 3
H
(
H
5 3
5
H
5
5 5
H
H
5 3
5
H
3
5 3
H
O
2 3
. Removal of volatile materials
-4
5 3
H
2
2
2
CHMeCN (0.0815 g, 3.38 × 10
(
(
(
)
(
3
1
1
NC(CH
CD Cl , -20 °C): δ 85.8 (CyP, JPP(cis) ) 62, 81 Hz), 19 (Ph
208 Hz), 8.9 (Ph
w), 1480 (w), 1436 (m), 1150 (w), 999 (w), 751 (m), 700 (m), 623
m). Anal. Calcd for C62 Fe NiO : C, 56.48; H, 5.12; N,
.12. Found: C, 56.17; H, 5.34; N, 2.31.
3
)CCH
2
), 15.3 (Pigiphos), 15.2 (Pigiphos). P{ H} NMR
1
(
2
2
PCH
2
CHMeCN (2f). H NMR (benzene-d
CHMeCN), 1.62 (ddd, 1 H, CH
CHMeCN, 2JHH
HH ) 6.60 Hz, 2
PH ) 3 Hz), 1.37-1.19 (m, 4 H,
CH ), 1.14 (ddd, 1 H, CH
9 Hz, 2JPH ) 3 Hz), 1.0 (d, 3 H, CH
6
, 500 MHz):
2
2
2
2
2
P, JPP(trans)
2
2
-
1
2
P). IR (Nujol, cm ): 2856 (s), 2254 (m), 2224
3
)
15 Hz,
J
J
2
3
P(CMe CH
)
0
MHz): δ 123.5 (d, CH
CH
2
2
)
3 2
2
CHMeCN, JHH ) 15 Hz, JHH
CHMeCN, JHH ) 7 Hz), 0.90-
(
2
H67Cl
2
2
N
2
9 3
P
3
2
3
1
1
.73 (m, 18 H, P(CMe
2
CH
2 3 2 6
CH ) ). C{ H} NMR (benzene-d , 125
3
[
f f 2
Ni((R)-(S)-κ -Pigiphos)Br][BAr ] ([6][BAr ]). NiBr (0.024 g, 1.11
3
2
CHMeCN, JPC ) 9 Hz), 35.4 (d, P(CMe -
2
-
4
-4
×
10 mol) and Pigiphos (0.101 g, 1.11 × 10 mol) were stirred in
-4
f
1
1
2
CH
3
)
2
, JPC ) 24 Hz), 35.2 (d, P(CMe
2
CH
2
CH
3
)
2
, JPC ) 23 Hz),
THF giving a red mixture. Addition of K[BAr
] (0.099 g, 1.01 × 10
2
3
4.6 (d, P(CMe
PC ) 16 Hz), 26.9 (d, CH
2
CH
2
CH
3
)
2
, JPC ) 16 Hz), 34 6 (d, P(CMe
CHMeCN, JPC ) 33 Hz), 26.48 (d, CH
2
CH
2
CH
3
)
2
,
mol, BAr ) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) as a solution
f
2
2
J
2
2
-
in THF gave a homogeneous purple solution, which was stirred for 3
h. Volatiles were removed in vacuo, and the purple solid was extracted
1
2
CHMeCN, JPC ) 27 Hz), 26.3 (d, P(CMe
2
CH
2
CH
3
)
2
, JPC ) 14 Hz),
2
2
6.3 (d, P(CMe
PC ) 10 Hz), 25.87 (d, P(CMe
2
CH
2
CH
3
)
2
, JPC ) 14 Hz), 25.9 (d, P(CMe
2
CH
2
3
CH )
2
,
with benzene (3 × 15 mL). The benzene solution was frozen, and
2
2
J
2
CH
2
CH
3
)
2
, JPC ) 10 Hz), 19.9 (d,
3
lyophilization afforded [Ni((R)-(S)κ -Pigiphos)Br][BAr
f
] as a purple
3
3
CH
2
CHMeCN, JPC ) 10 Hz), 8.9 (d, P(CMe
2
CH
CH )
2 3 2
, JPC ) 8 Hz),
-
5
1
powder (0.190 g, 9.92 × 10 mol, 90.5%). H NMR (toluene-d
C, 400 MHz): δ 8.29 (br s, 8 H, ortho-B(C (CF ), 7.87 (br s, 2
H, P(C ), 7.71 (br s, 6 H, overlapping B(C (CF and
P(C ), 7.13 (br s, P(C ), 7.08 (m, 10 H, P(C ), 6.82 (m, 2
H, P(C ), 4.30 (s, 1 H, C ), 4.20 (s, 1 H, C ), 4.09 (s, 2 H,
), 3.97 (s, 1 H, C ), 3.92 (s, 1 H, C ), 3.46 (s, 5 H, C ),
.39 (s, 5 H, C ), 3.27 (m, 1 H, PCHMeC FeCp), 3.12 (m, 1 H,
PCHMeC FeCp), 2.36 (br s, 2 H, C 11), 1.78 (s, 1 H, C 11), 1.56
q, 3 H, PCHMeC FeCp), 1.46 (q, 3 H, PCHMeC FeCp), 1.42
br m, 4 H, C 11), 1.09 (br m, 1 H, C 11), 0.87 (q, 1 H, C 11), 0.67
8
, 47
3
31
1
8
2
1
.8 (d, P(CMe
2
CH
2
3
CH )
2
6
, JPC ) 8 Hz). P{ H} NMR (benzene-d ,
°
H
6 3
3 2 4
) )
-
1
02.5 MHz): δ 18.5. IR (neat, cm ): 2966 (s), 2239 (m), 1462 (s),
6
H
5
)
2
6
H
3
3 2 4
) )
413 (m), 1379 (s), 1364 (s), 1144 (m), 1109 (m), 1054 (m), 1008
6 5
H )
2
6 5
H
)
2
6 5 2
H )
(m), 904 (w). Anal. Calcd for C14
H28NP: C, 69.67; H, 11.69; N, 5.80;
6 5
H
)
2
5
H
3
5 3
H
2
0
Found: C, 69.43; H, 11.94; N, 5.94. [R]
)
D
2 2
) 2.27 ( 0.09 (CH Cl , c
C
5
H
3
5
H
3
H
5 3
5 5
H
1 M) at 90% ee.
Cy PCEtHCH CN (2g). H NMR (CD
H, CHCH
CN, 2JHH ) 17 Hz), 2.43 (m, 1 H, CHCH
H, CHCH
), 1.26 (br m, 10 H, C
3
5
H
5
5 3
H
1
2
2
2
Cl
2
, 400 MHz): δ 2.59 (m,
CN), 1.84 (m,
H
5 3
6
H
6
H
1
1
2
2
(
(
H
5 3
5 3
H
2
CN), 1.77 (br m, 8 H, C
6
H
11), 1.68-1.54 (m, 6 H, H
11), 1.06 (t, 3 H, H
3
CH
2
-
H
6
H
6
H
6
3
13
1
CP(C
6
H
11
)
2
6
H
3
CCH
2
P, JHH
)
)
)
6 11 6 11 8
(q, 1 H, C H ), 0.49 (br m, 1 H, C H ). C{ H} NMR (toluene-d ,
47 °C, 100 MHz): δ 162.70 (q, J ) 50 Hz, ipso-C H (CF ) ), 135.9
1
3
1
3
1
7
5
1
Hz). C{ H} NMR (CD
2
Cl
2
, 100 MHz): δ 119.8 (d, CN, JPC
BC
6
3
3 2
2
2
.11 Hz), 32.0 (ortho-C
8 Hz), 31.6 (ipso-C
6
H
11, JPC ) 17 Hz), 32.0 (ortho-C
6
H
1
11, JPC
6 5 6 3 3 2 6 5 6 5
(t, C H ), 135.6 (s, ortho-C H (CF ) ), 135.3 (t, C H ), 134.6 (t, C H ),
134.2 (br t, C H ),132.1 (s, C H ), 131.6 (s, C H ), 131.0 (d, C H ),
6 5 6 5 6 5 6 5
130.5 (br m, C H ), 130.1 (q, C H ), 129.8 (q, C H ), 129.5 (m, C H ),
6 5 6 5 6 5 6 5
6 5 6 3 3 2 6 5
129.5 (s, C H ), 128.7 (m, meta-C H (CF ) ), 128.4 (m, C H ), 125.6
11, 1JPC ) 35 Hz), 31.4 (ipso-C
H
11, JPC ) 36
11, JPC ) 11
11, JPC ) 10
6
H
6
11, 2JPC ) 19 Hz), 31.0 (ortho-C
H
2
Hz), 31.1 (ortho-C
Hz), 30.9 (PCHEtCH
Hz), 27.8 (meta-C
6
H
6
1
3
2
CN, JPC ) 31 Hz), 27.8 (meta-C
6
H
4
3
6
H
11, JPC ) 9 Hz), 26.8 (para-C
6
2
H
11, JPC ) 1 Hz),
6 3 3 2 6 5 6 5 6 3
(q, C H (CF ) ), 124.1 (s, C H ), 121.3 (s, C H ), 118.0 (s, para-C H -
4
2
8
7 (para-C
6
H
11, JPC ) 1 Hz), 25.7 (H
3
CH
2
CCHP, JPC ) 12 Hz), 20.
(CF
71.4 (s, C
(s, C
), 38.1 (d, 1
PCHMeC FeCp), 30.6 (br, PCHMeC
(s, C 11), 26.4 (d, JPC ) 10 Hz, C
3
)
2
), 92.5 (br, C
), 71.3 (s, C
PC ) 17 Hz, C
5
H
3
), 89.7 (br, C
5
H
3
), 75.0 (s, C
), 70.4 (s, 2 C, C
11), 32.0 (d, 1
PC ) 15 Hz,
FeCp), 30.5 (bf, C 11), 28.7
11), 25.8 (d, JPC ) 11 Hz, C 11),
5
H
3
), 74.6 (s, C
5 3
H ),
2
CCHP, 3
(CHCH CN,
2
J
PC ) 14 Hz), 12.8 (H
Cl
3
CH
2
J
PC ) 9 Hz).
5
H
5
5
H
5
), 70.7 (s, C
5
H
H
3
5 3
H ), 69.2
31
1
-1
P{ H} NMR (CD
2
2
, 162 MHz): δ 7.8. IR (neat oil, cm ): 2928
5
H
3
J
6
J
(
(
s), 2851 (s), 2666 (w), 2243 (m), 1448 (s), 1423 (m), 1379 (w), 1343
w), 1293 (w), 1269 (w), 1176 (w), 1115 (w), 1001 (m), 887 (m). Anal.
H
5 3
5
H
3
6
H
2
2
6
H
6
H
6
H
17014 J. AM. CHEM. SOC.
9
VOL. 127, NO. 48, 2005