Organometallics 2010, 29, 2430–2445 - Chemistry - University of ...

Article Organometallics, Vol. 29, No. 11, 2010 2443
room temperature; then 1,3-dicyanobenzene (3.0 mg, 0.023
mmol) was added. 1 H and 31 P NMR spectra were recorded at
25 °C in the NMR probe showing B6. NMR spectra for B6 in
THF-d 8 (25 °C), 1 H: δ 1.05 (dd, J = 6.8, 15.6 Hz, 12 H, CH 3 ),
1.09-1.17 (overlapped, 24 H, CH 3 ), 1.27 (dd, J = 7.2, 14.8 Hz,
12 H, CH 3 ), 1.66 (m, CH 2 , 8H), 2.16 (m, 8 H, CH), 7.32 (t, J =
7.6 Hz, 1 H, meta-H), 7.61 (d, J H-H = 8.0 Hz, 2 H, ortho-H),
8.12 (s, 1 H, ortho-H); 31 P{H}: δ 61.0 (d, J P-P = 69 Hz), 73.1 (d,
J P-P = 69 Hz); 13 C: δ 19.04 (s, CH 3 ), 19.34 (d, J = 2.6 Hz, CH 3 ),
19.84 (d, J = 7.6 Hz, CH 3 ), 20.50 (d, J = 9.0 Hz, CH 3 ), 20.88
(dd, J = 14.9, 19.1 Hz, CH 2 ), 23.13 (t, J = 27.3 Hz, CH 2 ), 25.46
(dd, J = 3.4, 13.4 Hz, CH), 26.38 (dd, J = 5.1, 17.4 Hz, CH),
128.4 (s, CH), 130.0 (s, C), 130.1 (d, J = 2.5 Hz, CH), 131.7 (s,
CH), 168.7 (dd, J = 8.5, 28.6 Hz, CN). Upon heating at 100 °C
for 1 h, the C-CN cleavage product B7 appeared, but the major
products were from decomposition. NMR spectra for B7 in
C 6 D 6 (25 °C), 1 H: δ 7.05 (t, J = 7 Hz, 1 H), 7.15 (m, overlapped,
2 H), 8.04 (d, J = 7 Hz, 1 H); 31 P{H}: δ 63.2 (d, J P-P = 68 Hz),
75.3 (d, J P-P = 68 Hz), 67.3 (d, J P-P = 16 Hz), 76.0 (d, J P-P =
17 Hz). The crystallization of B7 was unsuccessful because of
decomposition and B5 easily deposited from the solution.
Reaction of [Ni(dippe)H] 2 with 1,4-Dicyanobenzene. [Ni-
(dippe)H] 2 (9.6 mg, 0.015 mmol) was dissolved in THF-d 8 ,
transferred into an NMR tube capped with a septum, and
cooled to -78 °C in a dry ice/acetone bath. Then 1,4-dicyanobenzene
(4.0 mg, 0.030 mmol, dissolved in 0.02 mL of THF) was
added while the tube was still in the bath. 1 H and 31 P NMR
spectra were recorded once every 10 °C as the reaction mixture
was warmed from -60 to 60 °C in the NMR probe. NMR
spectra for C1 in THF-d 8 (-60 °C), 1 H: δ 7.81 (s, 4 H, ortho-H);
31 P{H}: δ 62.8 (d, J P-P = 62 Hz), 74.5 (d, J P-P = 62 Hz); NMR
spectra for C2 in THF-d 8 (-60 °C), 1 H: δ 5.91 (s, br, 4 H, ortho-
H); 31 P{H}: δ 55.9 (d, J P-P = 71 Hz), 60.1 (d, J P-P = 72 Hz).
NMR spectra for C1 in THF-d 8 (25 °C), 1 H: δ 1.05-1.18 (m, 18
H), 1.23-1.29 (m, 6 H), 1.65-1.73 (m, 4 H), 2.06-2.22 (m, 4 H),
7.69 (d, J = 8 Hz, 2 H), 7.75 (d, J = 8.0 Hz, 2 H); 31 P{H}: δ 67.5
(d, J=63 Hz), 79.3 (d, J=63 Hz). NMR spectra for C3 in
THF-d 8 (25 °C), 1 H: δ 0.92 (m, 6 H), 1.13 (m, 6 H), 1.27 (m, 6 H),
1.44 (m, 6 H), 1.72-1.82 (m, 4 H), 2.06-2.10 (m, 2 H),
2.38-2.41 (m, 2 H), 7.14 (d, J=8 Hz, 2 H), 7.6 (d, br, J=8
Hz, 2 H); 31 P{H}: δ (ppm) 73.1 (d, J=24 Hz), 83.6 (d, J =24
Hz). NMR spectra for C4 in THF-d 8 (25 °C), 31 P{H}: δ (ppm)
66.4 (d, J=68 Hz), 78.7 (d, J=68 Hz). 5b C1-C4 were reported
previously. 6b IR data for C4 were recorded in the solid state
(ν CN = 1739 cm -1 ) and in THF solution (ν CN = 1738 cm -1 ),
indicating the same structure as seen in the X-ray study. 6b
Reaction of [Ni(dippe)H] 2 with 1-Cyanonaphthalene. [Ni(dippe)H] 2
(9.8 mg, 0.015 mmol) was dissolved in THF-d 8 , transferred into an
NMR tube capped with a septum, and cooled to -78 °Cinadryice/
acetone bath. Then 1-cyanonaphthalene (4.9 mg, 0.031 mmol,
dissolved in 0.02 mL of THF) was added while the tube was still in
the bath. 1 Hand 31 P NMR spectra were recorded once every 10 °Cas
the reaction mixture was warmed from -60 to 80 °C intheNMR
probe. NMR spectra for D1 in THF-d 8 (-60 °C), 1 H: δ 7.50 (m,
3 H), 7.54 (t, J = 8 Hz, 1 H), 7.86 (t, J = 8 Hz, 2 H), 9.51 (d, J P-H =
8Hz,1H); 31 P{H}: δ61.5 (d, J P-P =68Hz),72.6(d,J P-P =68Hz).
NMR spectra for D3/D5 in THF-d 8 (-60 °C), 1 H: δ 4.66 (dd, J =5,
10 Hz, 1 H), 5.93 (d, J =8Hz,1H),6.15(dd,J =6,8Hz,1H),6.84
(t, J = 8 Hz, 1 H), 6.92 (d, J =8Hz,1H),7.02(t,J =8Hz,1H),
7.91 (d, J =7Hz,1H); 31 P{H}: δ 57.4 (d, J P-P =60Hz),60.7
(d, J P-P =61Hz).
Isolation of Ni(dippe)(1-naphthyl)(CN). The mixture from the
above reaction, upon standing at room temperature, eventually
converted to a new species, which is the oxidative addition
product Ni(dippe)(1-naphthyl)(CN), D13. Yellow crystals were
obtained by vapor diffusion of a benzene solution with hexanes
under an N 2 atmosphere at room temperature. NMR spectra for
D13 in THF-d 8 (25 °C), 1 H: δ 0.051 (dd, J = 7, 14 Hz, 3 H, CH 3 ),
0.927 (dd, J = 7, 16 Hz, 3 H, CH 3 ), 1.050 (dd, J = 7, 12 Hz, 3 H,
CH 3 ), 1.29 (dd, J = 7, 12 Hz, 3 H, CH 3 ), 1.34 (dd, J = 7, 16 Hz,
3H,CH 3 ), 1.37 (dd, J = 7, 14 Hz, 3 H, CH 3 ), 1.48 (dd, J =7,16
Hz, 3 H, CH 3 ), 1.57 (dd, J = 7, 15 Hz, 3 H, CH 3 ), 2.29-2.58 (m,
8 H, CH and CH 2 ), 7.04 (t, J = 7 Hz, 1 H), 7.24-7.29 (m, 3 H),
7.39 (t, J = 6 Hz, 1 H), 7.54 (d, J = 8 Hz, 1 H), 8.54 (d, J = 8 Hz,
1 H); 31 P{H}: δ 64.9 (d, J P-P = 20 Hz), 75.0 (d, J P-P = 20 Hz).;
13 C: δ 16.75 (s, CH 3 ), 17.02 (s, CH 3 ), 18.78 (s, CH 3 ), 18.92
(s, CH 3 ), 19.91 (s, CH 3 ), 20.44 (s, CH 3 ), 20.48 (s, br, CH 3 ), 21.24
(s, CH 3 ), 21.68 (s, CH 2 ), 22.43 (s, CH 2 ), 22.55 (s, CH), 22.78
(s, CH), 122.6 (s, CH), 123.2 (s, CH), 124.9 (s, CH), 125.3 (s, C),
126.2 (s, CH), 128.7 (s, CH), 129.9 (s, CH), 133.8 (s, C), 135.0 (s,
CN), 135.5 (s, CH), 143.9 (s, C). Anal. Calcd for C 25 H 39 NNiP 2 :
C, 63.32; H, 8.29; N, 2.95. Found: C, 62.85; H, 8.32; N, 2.97.
Reaction of [Ni(dippe)H] 2 with 2-Cyanonaphthalene. [Ni(dippe)H] 2
(9.8 mg, 0.015 mmol) was dissolved in THF-d 8 , transferred into an
NMR tube capped with a septum, and cooled to -78 °Cinadryice/
acetone bath. Then 2-cyanonaphthalene (4.9 mg, 0.031 mmol,
dissolved in 0.02 mL of THF) was added while the tube was still in
the bath. 1 Hand 31 P NMR spectra were recorded once every 10 °Cas
the reaction mixture was warmed from -60 to 80 °C intheNMR
probe. NMR spectra for E1 in THF-d 8 (-60 °C), 1 H: δ 7.46 (m, 2 H),
7.84 (d, J =8Hz,2H),7.91(d,J =8Hz,2H),8.14(s,1H); 31 P{H}:
δ 62.0 (d, J P-P =65Hz),73.8(d,J P-P =65Hz).NMRspectrafor
E3/5 in THF-d 8 (-60 °C), 1 H: δ 6.12 (dd, J = 9, 3 Hz, 1 H), 6.46 (d,
J =9Hz,1H),6.82(t,J = 8 Hz, 1 H), 6.84 (s, 1 H), 6.96 (t, J =
6 Hz, 1 H), 7.27 (t, J =8Hz,1H),7.84(t,1H); 31 P{H}: δ 55.0 (d,
J P-P =61Hz),64.1(d,J P-P =61Hz).
Isolation of Ni(dippe)(2-naphthyl)(CN). The mixture from the
above reaction, upon standing at room temperature, eventually
converted to a new species, which was the oxidative addition
product Ni(dippe)(2-naphthyl)(CN), E13. Yellow crystals were
obtained by vapor diffusion of a THF solution with hexanes
under an N 2 atmosphere at room temperature. NMR spectra for
E13 in THF-d 8 (25 °C), 1 H: δ 0.933 (dd, J = 7, 15 Hz, 6 H, CH 3 ),
1.13 (dd, J = 7, 14 Hz, 6 H, CH 3 ), 1.21 (dd, J = 7, 14 Hz, 6 H,
CH 3 ), 1.30 (dd, J = 7, 13 Hz, 6 H, CH 3 ), 1.74-1.89 (m, 4 H,
CH 2 ), 2.10 (m, 2 H, CH), 2.43 (m, 2 H, CH), 7.12 (t, J = 7 Hz,
1 H), 7.20 (t, J = 7 Hz, 1 H), 7.39 (d, J = 8 Hz, 1 H), 7.50 (d,
J = 8 Hz, 1 H), 7.57 (d, J = 8 Hz, 1 H), 7.65 (m, 1 H), 7.71
(d, J = 6 Hz, 1 H); 31 P{H}: δ 67.0 (d, J P-P = 22 Hz), 77.1 (d,
J P-P = 21 Hz).; 13 C: δ 17.70 (s, CH 3 ), 18.72 (s, CH 3 ), 19.07 (s,
CH 3 ), 19.92 (d, J = 3.2 Hz, CH 3 ), 22.49 (t, J = 21.7 Hz, CH 2 ),
25.58 (s, CH), 25.79 (s, CH), 122.8 (s, CH), 124.1 (s, C), 124.5 (s,
CH), 126.2 (s, CH), 127.8 (s, CH), 128.5 (s, CH), 131.5 (s, C),
134.0 (s, CN), 135.1 (s, CH), 136.6 (s, CH), 142.2 (m, C). Anal.
Calcd for C 25 H 39 NNiP 2 : C, 63.32; H, 8.29; N, 2.95. Found: C,
63.08; H, 8.11; N, 2.80.
Reaction of [Ni(dippe)H] 2 with 1-Cyano-4-methylnaphthalene.
[Ni(dippe)H] 2 (10.2 mg, 0.016 mmol) was dissolved in THF-d 8 ,
transferred into an NMR tube capped with a septum, and
cooled to -78 °C in a dry ice/acetone bath. Then 1-cyano-4-
methylcyanonaphthalene (5.3 mg, 0.031 mmol, dissolved in 0.02
mL of THF) was added while the tube was still in the bath. 1 H
and 31 P NMR spectra were recorded once every 10 °C as the
reaction mixture was warmed from -60 to 60 °C in the NMR
probe. NMR spectra for F1 in THF-d 8 (-60 °C), 1 H: δ 2.75 (s,
3H,CH 3 -arene), 7.39 (d, J = 7 Hz, 1 H), 7.55 (m, 2 H), 7.82 (d,
J = 7 Hz, 1 H), 8.01 (d, J = 8 Hz, 1 H), 9.61 (d, J = 8 Hz, 1 H);
31 P{H}: δ 61.4 (d, J P-P = 70 Hz), 72.7 (d, J P-P = 70 Hz); NMR
spectra for F3/5 in THF-d 8 (-60 °C), 1 H: δ 2.93 (s, 3 H, CH 3 -
arene), 6.27 (d, J = 5 Hz, 1 H), 6.90 (t, J = 8 Hz, 1 H), 7.07 (m, 2
H), 7.61 (d, J = 8 Hz, 1 H), 8.18 (t, J = 9 Hz, 1 H); 31 P{H}: δ 56.1
(d, J P-P = 62 Hz), 60.2 (d, J P-P = 62 Hz). Upon heating, F13
appeared as well as decomposition. After one week at room
temperature, single crystals of F13 were formed in THF-d 8
solution. Yellow needle-shaped crystals could also be obtained
by vapor diffusion of a THF solution with hexanes under an
N 2 atmosphere at room temperature. NMR spectra for F13
in THF-d 8 (25 °C) 1 H: δ 0.059 (dd, J = 7.2, 14 Hz, 3 H,
CH 3 ), 0.9391 (dd, J = 7.2, 16 Hz, 3 H, CH 3 ), 1.05 (dd, J =
6.8, 11.2 Hz, 3 H, CH 3 ), 1.29 (dd, J = 7.2, 12.4 Hz, 3 H, CH 3 ),