3414 Organometallics, Vol. 23, No. 14, 2004
Culkin and Hartwig
toluene gave 138 mg (68.7%) of the product as a slightly yellow
solid after crystallization from toluene layered with pentane
cooled at -35 °C. The compound was recrystallized as colorless
needles from a THF solution of the product layered with
pentane at -35 °C. 1H NMR (C6D6) δ 0.90 (d, 6.5 Hz, 3H), 1.06
(d, 6.5 Hz, 3H), 1.99 (m, 1H), 2.17 (s, 3H), 2.52 (ddd, 8.8 Hz,
3.8 Hz, 1.5 Hz, 1H), 6.81 (m, 2H), 6.89-6.94 (m, 8H), 7.00-
7.03 (m, 4H), 7.12 (m, 2H), 7.23 (m, 2H), 7.29 (virtual t, 7.0
Hz, 1H), 7.33-7.41 (m, 3H), 7.47 (m, 2H), 7.70 (br s, 2H), 7.87
(dd, 8.3 Hz, 1 Hz, 2H); 31P{1H} NMR (C6D6) δ 45.8 (d, 14.6
Hz), 47.3 (d, 14.6 Hz); 13C{1H} NMR (CD2Cl2) δ 19.32 (dd, 90.4
Hz, 6.1 Hz), 21.13 (s), 24.93 (d, 10.3 Hz), 25.71 (s), 31.75 (dd,
4.7 Hz, 1.9 Hz), 125.81 (s), 127.77 (d, 8.2 Hz), 128.96 (d, 10.4
Hz), 128.98 (d, 9.9 Hz), 129.35 (d, 9.1 Hz), 129.61 (d, 9.7 Hz),
130.80 (d, 3.1 Hz), 130.89 (d, 2.9 Hz), 130.95 (d, 2.3 Hz),
131.08-132.66 (4 overlapping doublets), 131.64 (d, 2.0 Hz),
132.22 (dd, 5.5 Hz, 2.0 Hz), 132.36 (dd, 4.7 Hz, 1.8 Hz), 133.63
(d, 13.1 Hz), 133.81 (d, 12.6 Hz), 134.07 (d, 12.6 Hz), 134.20
(d, 14.3 Hz), 134.60 (d, 15.3 Hz), 134.74 (d, 15.1 Hz), 136.34
(virtual t, 3.3 Hz), 138.54 (s), 144.14 (dd, 69.2 Hz, 40.2 Hz),
144.61 (virtual t, 36.7 Hz), 161.48 (dd, 120.8 Hz, 9.2 Hz); IR
(KBr, cm-1) ν(CN) 2171. Anal. Calcd for C42H39NP2Pd‚C4H8O:
C, 69.21; H, 5.93; N, 1.75. Found: C, 69.52; H, 5.93; N, 1.49.
[P d (DiP r P F )(CHP h CN)(C6H4-4-t-Bu )] (30). Following the
procedure for the preparation of 26, reaction of 215 mg (0.291
mmol) of [Pd(DiPrPF)(C6H4-4-t-Bu)(Br)] and 59 mg (0.38 mmol)
of KN(C)CHPh in 6 mL of toluene gave 124 mg (55.0%) of the
product as a bright yellow solid after crystallization from
toluene layered with pentane cooled at -35 °C. 1H NMR (C6D6)
δ 0.73 (dd, 12.8 Hz, 6.8 Hz, 3H), 0.83 (dd, 14.8 Hz, 7.3 Hz,
6H), 0.94 (dd, 11.8 Hz, 6.3 Hz, 3H), 1.17 (dd, 13.8 Hz, 6.8 Hz,
3H), 1.28 (dd, 16.0 Hz, 7.0 Hz, 3H), 1.35 (s, 9H), 1.43 (dd, 14.5
Hz, 7.5 Hz, 3H), 1.56 (dd, 14.3 Hz, 7.3 Hz, 3H), 1.99 (m, 1H),
2.10 (m, 1H), 2.23 (m, 2H), 3.92 (m, 1H), 3.95 (m, 2H), 3.97
(m, 1H), 3.99 (m, 1H), 4.05 (m, 2H), 4.10 (m, 1H), 4.35 (dd,
14.5 Hz, 9.5 Hz, 1H), 6.69 (m, 1H), 6.75 (dt, 7.5 Hz, 2.3 Hz,
1H), 6.90 (td, 7.0 Hz, 1.0 Hz, 1H), 7.03 (m, 4H), 7.30 (dt, 7.5
Hz, 2.0 Hz, 1H), 8.09 (m, 1H); 31P{1H} NMR (C6D6) δ 25.5 (d,
22.0 Hz), 32.7 (d, 22.0 Hz); 13C NMR (C4D8O) δ 15.25 (dd, 82.9
Hz, 7.5 Hz), 18.57 (s), 19.23 (s), 19.33 (s), 19.45 (br s), 19.96
(s), 20.45 (d, 6.0 Hz), 21.01 (d, 5.3 Hz), 21.54 (d, 6.8 Hz), 25.44
(d, 23.1 Hz), 25.70 (d, 22.3 Hz), 25.80 (d, 15.5 Hz), 26.07 (d,
15.8 Hz), 32.13 (s), 34.39 (s), 71.38 (d, 3.5 Hz), 71.87 (d, 4.0
Hz), 71.97 (d, 3.6 Hz), 72.41 (d, 5.0 Hz), 73.73 (d, 4.8 Hz), 74.04
(d, 5.3 Hz), 74.12 (d, 7.3 Hz), 74.20 (d, 8.4 Hz), 76.07 (dd, 27.4
Hz, 4.8 Hz), 79.98 (dd, 23.7 Hz, 8.4 Hz), 121.84 (s), 123.82 (d,
7.8 Hz), 124.57 (d, 7.7 Hz), 125.15 (d, 8.4 Hz), 126.09 (s), 127.62
(s), 135.36 (virtual t, 3.2 Hz), 137.68 (virtual t, 3.6 Hz), 145.19
(s), 145.74 (dd, 4.0 Hz, 4.0 Hz), 158.25 (dd, 110.9 Hz, 16.5 Hz);
IR (KBr, cm-1) ν(CN) 2176. Anal. Calcd for C37H57FeNP2Pd:
C, 62.06; H, 7.16; N, 1.81. Found: C, 62.01; H, 7.21; N, 1.78.
[P d (DiP r P F )(N(C)CMe2)(C6H4-4-t-Bu )] (31). Following
the procedure for the preparation of 26, reaction of 152 mg
(0.206 mmol) of [Pd(DiPrPF)(C6H4-4-t-Bu)(Br)] and 42 mg (0.39
mmol) of KN(C)CMe2 in 7 mL of toluene gave 62 mg (41%) of
the product as red crystals after crystallization from toluene
layered with pentane cooled at -35 °C. These crystals were
[P d (P h 2P (C6H4)P P h 2)(CHP h CN)(C6H4-4-Me)] (28). Fol-
lowing the procedure for the preparation of 26, reaction of 200
mg (0.276 mmol) of [Pd(DPPBz)(C6H4-4-Me)(Br)] and 49 mg
(0.32 mmol) of KN(C)CHPh in 10 mL of toluene gave 171 mg
(81.3%) of the product as a yellow solid after crystallization
from toluene layered with pentane cooled at -35 °C. 1H NMR
(C6D6) δ 2.16 (s, 3H), 4.40 (dd, 11.3 Hz, 9.8 Hz, 1H), 6.75-
6.85 (m, 9H), 6.88-6.91 (m, 6H), 6.98 (m, 4H), 7.08-7.13 (m,
4H), 7.17-7.27 (m, 6H), 7.34 (br s, 2H), 7.66 (ddd, 11.0 Hz,
8.5 Hz, 1.5 Hz, 2H); 31P{1H} NMR (C6D6) δ 42.3 (d, 17.1 Hz),
47.3 (d, 17.1 Hz); 13C{1H} NMR (CD2Cl2) δ 17.25 (dd, 81.4 Hz,
5.2 Hz), 21.08 (s), 122.35 (d, 2.1 Hz), 125.87 (d, 3.5 Hz), 127.38
(dd, 7.2 Hz, 2 Hz), 127.96 (s), 128.07 (d, 6.8 Hz), 128.86 (d,
10.6 Hz), 128.97 (d, 10.4 Hz), 129.42 (d, 4.2 Hz), 129.49 (d, 4.3
Hz), 130.82 (d, 2.3 Hz), 131.02 (d, 1.8 Hz), 131.18 (d, 1 Hz),
131.28 (d, 2.4 Hz), 130.86-131.75 (4 overlapping doublets),
132.24 (dd, 4.2 Hz, 2.0 Hz), 132.38 (dd, 4.5 Hz, 2.1 Hz), 133.84
(d, 12.6 Hz,), 134.10 (d, 12.8 Hz), 134.30 (d, 12.3 Hz), 134.38
(d, 14.1 Hz), 134.05-134.44 (2 obscured doublets), 136.40
(virtual t, 3.6 Hz), 138.53 (s), 143.86 (virtual t, 42.3 Hz), 144.26
(dd, 39.7 Hz, 39.2 Hz), 144.70 (dd, 5.7 Hz, 3.1 Hz), 161.29 (dd,
118.4 Hz, 9.4 Hz); IR (KBr, cm-1) ν(CN) 2180. Anal. Calcd for
1
suitable for X-ray structural analysis. H NMR (C6D6) δ 0.88
(dd, 14.0 Hz, 7.0 Hz, 6H), 1.12 (m, 12H), 1.41 (s, 9H), 1.62
(dd, 15.8 Hz, 7.3 Hz, 6H), 1.71 (d, 6.5 Hz, 6H), 2.05 (m, 2H),
2.46 (m, 2H), 3.94 (m, 2H), 3.98 (m, 2H), 4.07 (m, 2H), 4.10
(m, 2H), 7.32 (dd, 8.3 Hz, 1.8 Hz, 2H), 7.76 (dd, 8.0 Hz, 7.0
Hz, 2H); 31P{1H} NMR (C6D6) δ 28.2 (d, 31.7 Hz), 36.7 (d, 31.7
Hz); 13C{1H} NMR (C4D8O, -10 °C) δ 18.39 (d, 4.8 Hz), 19.37
(br s), 19.89 (d, 4.15 Hz), 20.02 (br s), 20.81 (d, 7.0 Hz), 25.13
(d, 17.0 Hz), 26.14 (d, 26.7 Hz), 32.31 (s), 33.52 (d, 12.6 Hz),
34.71 (s), 71.53 (d, 5.4 Hz), 72.23 (d, 4.8 Hz), 74.01 (d, 7.8 Hz),
74.16 (d, 6.4 Hz), 75.46 (dd, 24.5 Hz, 3.2 Hz), 81.99 (dd, 29.5
Hz, 9.9 Hz), 123.68 (d, 8.6 Hz), 137.48 (s), 145.32 (s), 159.99
C
45H37NP2Pd: C, 71.10; H, 4.91; N, 1.84. Found: C, 71.07; H,
(dd, 116.5 Hz, 16.7 Hz) 175.45 (d, 8.2 Hz); IR (KBr, cm-1
)
4.94; N, 1.77.
ν(ΝdCdC) 2186, 1997. Anal. Calcd for C36H55FeNP2Pd: C,
59.55; H, 7.64; N, 1.93. Found: C, 59.09; H, 7.61; N, 1.73.
[P d (BINAP )(CH(CHMe2)CN)(C6H4-4-t-Bu )] (32). Follow-
ing the procedure for the preparation of 26, reaction of 190
mg (0.202 mmol) of [Pd(BINAP)(C6H4-4-t-Bu)(Br)] and 28 mg
(0.23 mmol) of KN(C)CH(CHMe2) in 5 mL of toluene gave 119
mg (62.4%) of the product as a pink solid or a mixture of white
and red crystals after cooling a toluene solution layered with
pentane at -35 °C. The bulk material obtained from this
crystallization consistently contained about 10% Pd(BINAP)2,
which was the red crystals. 1H NMR (C6D6) (ratio ) 1:1) δ 0.87
(d, 6.5 Hz, 3H), 1.21 (d, 7.0 Hz, 3H), 1.27 (s, 4.5H), 1.31 (s,
4.5H), 1.80 (m, 0.5H), 1.90 (m, 1.5H), 6.23 (br, 1H), 6.31 (m,
2H), 6.40 (m, 1.5H), 6.46 (m, 2H), 6.54 (m, 1.5H), 6.67 (m,
0.5H), 6.76 (m, 1H), 6.81-6.89 (m, 3H), 6.91 (m, 0.5H), 6.99
(m, 2.5H), 7.01 (m, 1.5H), 7.07-7.15 (m, 3H), 7.17-7.26 (m,
6H), 7.38-7.50 (m, 4H), 7.60 (br, 2H), 7.67 (m, 1H), 7.76 (m,
1H), 7.98-8.07 (m, 2H); 31P{1H} NMR (C6D6) (ratio ) 1:1) δ
18.3 (d, 24.2 Hz), 19.3 (d, 24.2 Hz), 20.3 (d, 22.2 Hz), 22.5 (d,
24.2 Hz); IR (KBr, cm-1) ν(CN) 2176.
[P d (P h 2P (C6H4)P P h 2)(CMe2CN)(C6H4-4-Me)] (29). Fol-
lowing the procedure for the preparation of 26, reaction of 190
mg (0.262 mmol) of [Pd(DPPBz)(C6H4-4-Me)(Br)] and 56 mg
(0.53 mmol) of KN(C)CMe2 in 5 mL of toluene gave 104 mg
(55.6%) of the product as pale yellow crystals after layering a
toluene solution with pentane at -35 °C. Recrystallization by
vapor diffusion of pentane into a toluene solution at -35 °C
gave colorless prism crystals of the toluene solvate that were
1
suitable for X-ray structural analysis. H NMR (C6D6) δ 1.51
(d, 7.0 Hz, 6H), 2.14 (s, 3H), 6.76 (m, 4H), 6.88-6.96 (m, 6H),
7.00-7.11 (m, 7H), 7.25 (ddd, 10.6 Hz, 8.3 Hz, 1.0 Hz, 4H),
7.33 (m, 1H), 7.38 (dd, 7.3 Hz, 6.5 Hz, 2H), 7.91 (ddd, 11.0 Hz,
8.0 Hz, 1.5 Hz, 4H); 31P{1H} NMR (C6D6) δ 43.7 (d, 12.2 Hz),
45.5 (d, 12.2 Hz); 13C{1H} NMR (CD2Cl2) δ 12.45 (dd, 100.8
Hz, 4.1 Hz), 21.06 (s), 30.27 (virtual t, 4.0 Hz), 125.81 (s),
127.95 (d, 7.8 Hz), 128.79 (d, 10.1 Hz), 129.27 (d, 9.8 Hz),
131.07 (d, 2.9 Hz), 131.24 (d, 2.1 Hz), 131.43 (d, 46.7 Hz),
131.92 (dd, 3.0 Hz, 1.8 Hz), 132.16 (d, 49.4 Hz), 132.19 (dd,
3.5 Hz, 1 Hz), 134.03 (d, 11.2 Hz), 134.07 (d, 14.3 Hz), 134.31
(d, 15.6 Hz), 134.71 (d, 13.6 Hz), 136.67 (virtual t, 3.3 Hz),
138.52 (s), 143.67 (virtual t, 39.9 Hz), 146.25 (virtual t, 40.9
Hz), 163.55 (dd, 114.5, 12.5 Hz); IR (KBr, cm-1) ν(CN) 2170.
Anal. Calcd for C41H37NP2Pd‚C7H8: C, 71.68; H, 5.64; N, 1.74.
Found: C, 71.45; H, 5.83; N, 1.63.
[P d (BINAP )(CHP h CN)(C6H4-4-t-Bu )] (33). Following the
procedure for the preparation of 26, reaction of 190 mg (0.202
mmol) of [Pd(BINAP)(C6H4-4-t-Bu)(Br)] and 63 mg (0.40 mmol)
of KN(C)CHPh in 7 mL of toluene gave 111 mg (56.1%) of the