4278 Organometallics, Vol. 22, No. 21, 2003
Shim et al.
[2-(Cycloh exylid en ea m in o)b en zoa t o-K2N,O](η3-m et h -
a llyl)n ick el(II) (6). 2-(Cyclohexylideneamino)benzoic acid
(54.3 mg, 0.250 mmol) and KH (10.0 mg, 0.250 mmol) were
weighed into a vial inside a glovebox, and THF (1.0 g) was
added. The mixture was stirred for 1 h at room temperature,
upon which a white thick slurry was formed. Acetonitrile (1.0
g) was added, and the mixture was stirred further for 30 min.
Bis(µ-chloro)bis(η3-methallyl)dinickel(II) (37.3 mg, 0.125 mmol)
was added, and the solution was stirred for 30 min. Solvent
was removed under vacuum, and the product was extracted
with THF. Removal of the solvent gave a red crystalline
22.29 ppm. Anal. Calcd for C16H21NNiO2: C, 60.4; H, 6.66; N,
4.40. Found: C, 60.0; H, 6.64, N; 4.36.
[(2-(Cycloh exylid en ea m in o)b en zoa t o)t r is(p en t a flu -
or oph en yl)bor ato-K2N,O](η3-m eth allyl)n ickel(II) (9). When
1 equiv of B(C6F5)3 is added to 6 in C6D6, two sets of signals
are observed in the
1H NMR spectrum, but a set of clean 1H
NMR signals is observed when only 0.9 equiv of B(C6F5)3 (23.0
mg, 0.0450) is added to 6 (16.5 mg, 0.0500 mmol). Analytically
pure single crystals, which were suitable for X-ray crystal-
lography, were obtained by layer diffusion of pentane into the
C6D6 solution in the NMR cell. Light yellow crystals were
1
1
isolated (16 mg, 69%). H NMR (C6D6): δ 8.29 (br d, J ) 7.6
complex (83 mg, 100%) which was pure by the analysis of H
or
or
Hz, 1 H, Ph H3 6), 6.86 (br t, J ) 8.8, 1 H, Ph H4 5), 6.82
and 13C NMR spectra. Single crystals suitable for X-ray
crystallography and elemental analysis were grown from
(br t, J ) 8.8 Hz, 1 H, Ph H4 5), 5.96 (br d, J ) 7.6 Hz, Ph
or
H3 6), 2.54-2.26 (br, 2 H, methallyl CH2 and Cy H), 2.24-
or
1
toluene solution at -30 °C overnight. H NMR (C6D6): δ 8.50
or
(d, J ) 7.2 Hz, 1 H, Ph H3 6), 7.07 (t, J ) 7.2 Hz, 1 H, Ph
1.88 (br, 1 H, methallyl CH2), 1.59 (s, 3 H, methallyl CH3),
1.8-0.65 (m, 11 H, methallyl CH2 and Cy H) ppm. 13C{1H}
NMR (C6D6): δ 189.15 (carbonyl or imine), 173.04 (carbonyl
or
or
H4 5), 7.02 (t, J ) 7.2 Hz, 1 H, Ph H4 5), 6.34 (d, J ) 7.2
Hz, 1 H, Ph H3 6), 2.70 (br, 1 H, methallyl CH2), 2.52 (br,
or
1
or imine), 148.7 (dm, J CF ) 240 Hz), 143.10, 139.7 (dm,
1 H, methallyl CH2), 2.41 (br, 1 H, methallyl CH2), 2.23 (br,
1 H, methallyl CH2), 1.87 (s, 3 H, methallyl CH3), 1.80-0.80
(m, 10 H, Cy H) ppm. 13C{1H} NMR (C6D6): δ 184.04 (carbonyl
or imine), 168.24 (carbonyl or imine), 142.29, 135.40, 131.90,
129.30, 127.06, 123.37, 120.11, 42.19, 32.37, 27.86, 27.69,
25.39, 22.84 ppm. Anal. Calcd for C17H22NNiO2: C, 61.7; H,
6.71; N, 4.23. Found: C, 61.6; H, 7.01; N, 4.55.
1
1J CF ) 245 Hz), 137.4 (dm, J CF ) 245 Hz), 133.18, 132.34,
128.53, 127.23, 126.53, 121.34, 42.54, 33.00, 28.48, 27.98,
3
25.09, 22.22 ppm. 19F{1H} NMR (C6D6): δ -134 (d, J FF ) 18
3
3
Hz), -159 (t, J FF ) 18 Hz), -165 (t, J FF ) 18 Hz) ppm.
11B{1H} NMR (C6D6): δ -3.4 ppm. Anal. Calcd for C35H21BF15
-
NNiO2: C, 49.9; H, 2.52; N, 1.66. Found: C, 50.2; H, 2.95;
N, 2.03.
[2-(1-(Ethylpropylidene)amino)benzoato-K2N,O](η3-meth-
a llyl)n ick el(II) (7). Compound 4 (1.00 g, 4.87 mmol) and KH
(195 mg, 4.87 mmol) were weighed into a flask inside a
glovebox, and THF (20 mL) was added. The mixture was
stirred overnight at room temperature, upon which a white
thick slurry was formed. Solvent was removed under vacuum.
The potassium salt was triturated in pentane. Pentane was
removed by decantation, and the solid was dried under vacuum
(1.00 g, 85%). The potassium salt (245 mg, 1.01 mmol) and
bis(µ-chloro)bis(η3-methallyl)dinickel(II) (150 mg, 0.500 mmol)
were weighed into a vial, and acetonitrile (5.0 mL) was added.
The solution was stirred overnight. Solvent was removed under
vacuum, and the product was extracted with toluene. Removal
of the solvent gave a red solid, which was purified by
triturating in pentane to give a light yellow solid. The solid
was pure by the analysis of 1H and 13C NMR spectra. The yield
was 84% (270 mg). Single crystals suitable for elemental
analysis were grown by layer diffusion of pentane into a
benzene solution at room temperature overnight. 1H NMR
[(2-((1-Eth ylp r op ylid en e)a m in o)ben zoa to)tr is(p en ta -
flu or op h en yl)bor a to-K2N,O](η3-m eth a llyl)n ick el(II) (10).
The complex was prepared according to the same procedure
and conditions for 9 from 7. The isolated yield was 78%. 1H
or
NMR (C6D6): δ 8.31 (d, J ) 7.6 Hz, 1 H, Ph H3 6), 6.91 (td,
or
J ) 7.6, 1.6 Hz, 1 H, Ph H4 5), 6.85 (td, J ) 7.6, 0.8 Hz, 1 H,
or
or
Ph H4 5), 6.10 (br d, J ) 7.6 Hz, Ph H3 6), 2.35 (br s, 1 H,
methallyl CH2), 2.07 (br s, 1 H, methallyl CH2), 2.03 (q, J )
7.6 Hz, 2 H, CH2CH3), 1.62 (br s, 1 H, methallyl CH3), 1.54 (q,
J ) 7.6 Hz, 2 H, CH2CH3), 1.31 (br s, 1 H, methallyl CH2),
1.13 (br s, 1 H, methallyl CH2), 0.97 (t, J ) 7.6 Hz, 3 H,
CH2CH3), 0.35 (t, J ) 7.6 Hz, 3 H, CH2CH3) ppm. 13C{1H} NMR
(C6D6): δ 192.37 (carbonyl or imine), 172.74 (carbonyl or
1
1
imine), 148.7 (dm, J CF ) 250 Hz), 143.59, 139.7 (dm, J CF
)
1
230 Hz), 137.5 (dm, J CF ) 240 Hz), 133.33, 132.32, 127.01,
126.51, 121.02, 34.72, 26.87, 22.29, 12.72, 11.00 ppm. 19F{1H}
3
NMR (C6D6): δ -134 (d, J ) 18 Hz), -159 (t, J FF ) 18 Hz),
-165 (t, 3J FF ) 18 Hz) ppm. 11B{1H} NMR (C6D6): δ -2.7 ppm.
Anal. Calcd for C34H21BF15NNiO2: C, 49.2; H, 2.55; N, 1.69.
Found: C, 49.6; H, 2.68; N, 1.65.
or
(C6D6): δ 8.46 (br d, J ) 6.4 Hz, 1 H, Ph H3 6), 7.06 (t, J )
7.2 Hz, 1 H, Ph H4 or 5), 7.02 (td, J ) 7.6, 1.6 Hz, 1 H, Ph H4 or 5),
6.34 (br d, J ) 7.2 Hz, 1 H, Ph H3 or 6), 2.51 (br s, 2 H, methallyl
CH2), 2.36 (br, 2 H, methallyl CH2), 1.85 (s, 3 H, methallyl
CH3), 1.78 (br q, J ) 7 Hz, 2 H, CH2CH3), 1.68 (br q, J ) 7 Hz,
2 H, CH2CH3), 1.12 (t, J ) 7.6 Hz, 3 H, CH2CH3), 0.47 (t, J )
7.6 Hz, 3 H, CH2CH3) ppm. 13C{1H} NMR (C6D6): δ 187.51
(carbonyl or imine), 168.14 (carbonyl or imine), 142.55, 134.89,
131.65, 129.53, 127.01, 123.43, 119.65, 34.73, 26.20, 22.76,
12.51, 11.42 ppm. Anal. Calcd for C16H21NNiO2: C, 60.4; H,
6.66; N, 4.40. Found: C, 60.0; H, 6.49; N, 4.19.
[(2-((2,2-Dim et h ylp r op ylid en e)a m in o)b en zoa t o)t r is-
(p en t a flu or op h en yl)bor a t o-K2N,O](η3-m et h a llyl)n ick el-
(II) (11). The complex was prepared according to the same
procedure and conditions for 9 from 8. The isolated yield was
1
75%. H NMR (C6D6): δ 8.32 (br, 1 H), 6.93 (br, 2 H), 6.54 (s,
1 H, CHdN), 6.40 (br, 1 H), 2.43 (br, 1 H, methallyl CH2), 1.85
(br, 1 H, methallyl CH2), 1.54 (s, 3 H, methallyl CH3), 1.1-0.5
(br, 11 H, tBu H and methallyl CH2) ppm. 13C{1H} NMR
(C6D6): δ 187.25 (carbonyl or imine), 172.83 (carbonyl or
1
1
imine), 148.6 (dm, J CF ) 240 Hz), 138.8 (dm, J CF ) 250 Hz),
[2-((2,2-Dim eth ylp r op ylid en e)a m in o)ben zoa to-K2N,O]-
(η3-m eth a llyl)n ick el(II) (8). The compound was prepared
under conditions and by procedures similar to those for 7. The
reaction time was 2 h, and the product was extracted with
THF. The yield was 90%. Single crystals suitable for elemental
analysis were grown by layer diffusion of pentane into a
benzene solution at room temperature overnight. 1H NMR
(CD3CN/C6D6 (v/v, 1:1)): δ 7.89 (br t, J ) 7.6 Hz, 1 H, Ph
1
137.3 (dm, J CF ) 240 Hz), 134.74, 131.73, 128.96, 127.04,
26.75, 22.07 ppm. 19F{1H} NMR (C6D6): δ -134 (d, J ) 18
Hz), -159 (t, J FF ) 18 Hz), -165 (t, J FF ) 18 Hz) ppm. 11B-
3
3
{1H} NMR (C6D6): δ 0.0 ppm. Anal. Calcd for C34H21BF15
-
NNiO2: C, 49.2; H, 2.55; N, 1.69. Found: C, 49.0; H, 2.56;
N, 1.63.
(η3-Ben zyl)ch lor o(tr im eth ylp h osp h in e)n ick el(II). The
compound was reported and can be synthesized according to
the reported procedure and conditions.20 We have developed
a more convenient procedure. Thus, Ni(COD)2 (2.74 g, 10.0
mmol) was dissolved in THF (20 g). Benzyl chloride (1.27 g,
10.0 mmol) and PMe3 (0.76 g) were added rapidly and
successively. The solution was stirred for 1 h at room temper-
ature. The solvent was removed, and the residue was dissolved
in toluene (10 mL). The solution was filtered over Celite and
or
H4 5), 7.75 (s, 1 H, CHdN), 7.51 (br t, J ) 7.6 Hz, 1 H, Ph
or
3 or
H4 5), 7.42 (br d, J ) 7.2 Hz, 1 H, Ph H
6), 6.98 (br d, J )
7.2 Hz, 1 H, Ph H4 6), 2.65 (br s, 2 H, methallyl CH2), 2.13
(s, 3 H, methallyl CH3), 1.94 (br s, 2 H, methallyl CH2), 1.56
(s, 9 H, tBu) ppm. 13C{1H} NMR (CD3CN/C6D6 (v/v, 1:1)): δ
184.53 (carbonyl or imine), 168.42 (carbonyl or imine), 146.48,
133.38, 131.69, 129.99, 127.55, 124.88, 119.09, 36.72, 27.14,
or