7.59 (dd, J 5.5 and 1.5, 1 H, H2ꢀ ), 7.46 (dd, J 5.5 and 1.5, 1 H, H1),
7.40 (tt, J 7 and 1.5, 2 H, H8, 8 ), 7.33 (tt, J 7.5 and 1.5, 1 H, H9),
5.23 (s, 2 H, CH2), 6.55 (s, 2 H, m-H), 2.57 (s, 6 H, o-CH3), 2.02*
(s, 3 H, p-CH3); *overlapped signals of both isomers.
2.33 (s, 6 H, m-CH3), 2.20 (s, 3 H, p-CH3). trans Isomer, d 9.08 (s,
3
4
=
1 H, HC N), 8.40 (td, J 8 and 1.5, 1 H, H ), 8.31 (d, 1 H, H ),
8.10 (s, 2 H, o-H), 7.73 (ddd, 1 H, H2), 7.64 (d, J 5, 1 H, H1), 7.52
ꢀ
ꢀ
(s, 1 H, p-H), 7.31–7.23 (m, 3 H, H9, 8, 8 ), 7.02 (d, J 7.5, 2 H, H7,7 ),
6.58 (s, 2 H, m-H), 5.01 (s, 2 H, CH2), 2.68 (s, 6 H, o-CH3), 2.20 (s,
6 H, m-CH3), 2.15 (s, 3 H, p-CH3).
Synthesis of the ionic complexes
=
{Ni(Mes)[NH C(Mes)(Me)](DAD)}BF4 (7a). To a solution
[Ni(Mes)(3,5-lut)(DAD)]BF4 (5a). 0.30 g (1.03 mmol) of TlBF4
was added over a stirred solution of 0.11 g (1.0 mmol) of 3,5-
lutidine and 0.52 g (1.00 mmol) of the neutral complex 3a
in 30 cm3 of tetrahydrofuran. A reddish suspension containing
white insoluble thallium halide was slowly formed. After 14 h
the thallium bromide was separated by filtering over Celite. The
solvent was then evaporated to dryness and the remaining resin
stirred with diethyl ether until a suspension with an orange solid
was obtained. The solid was filtered off, and washed several times
with water and diethyl ether (yield = 60%) (Found: C, 63.4; H, 6.2;
N, 6.6. Calc. for C34H40BF4N3Ni: C, 64.19; H, 6.34; N, 6.60%). 1H
NMR (500 MHz, CDCl3), d 2.03 (s, 6 H, m-CH3), 2.06 (s, 3 H, p-
of 0.40 g (0.91 mmol) of 3a and 0.11 g of CH3CN (2.7 mmol,
300% excess) in 50 cm3 of acetone, 0.27 g (0.94 mmol) of TlBF4 was
added. The reaction mixture was stirred for 12 h, during which time
a fine precipitate of thallium bromide was formed. The mixture was
filtered off through Celite and then concentrated under reduced
pressure. The complex was precipitated as an orange–reddish solid
by replacing the tetrahydrofuran by toluene. The solid was filtered
off and washed with water and ether (yield = 23%, based on nickel)
(Found: C, 64.3 H, 6.9; N, 6.7. Calc. for C38H46BF4N3Ni: C, 66.12;
H, 6.72; N 6.09%). H NMR (acetone-d6, 250 MHz), E Isomer,
d 1.54 (s, 6 H, p-CH3), 2.13 (s, 3 H, CH3 ), 2.15 (s, 3 H, CH3 ),
2.41 (s, 3 H, o-CH3-imine), 2.46 (s, 3 H, o-CH3-imine), 2.89 (br s,
9 H, o-CH3-Mes and N CCH3), 4.48 (s, 2 H, CH2 ), 4.97 (s, 2 H,
CH2 ), 6.40 (s, 2 H, m-H Mes), 6.66 (s, 2 H, m-H imine), 6.78 (m,
2 H, o-Ph), 7.25–7.70 (m, 8 H), 9.16 (s, 1 H, NH).
1
5
6
5
6
CH3), 2.25 (s, 3 H, CH3 ), 2.34 (s, 3 H, CH3 ), 2.65 (s, 6 H, o-CH3),
1
1
7
=
4.17 (s, 2 H, CH2 ), 4.29 (s, 2 H, CH2 ), 6.22 (s, 2 H, m-H), 6.73
ꢀ
ꢀ
7
(d, J 7, 2 H, H2, 2 ), 6.93 (d, J 7.5, 2 H, H8, 8 ), 7.06 (s, 1 H, p-H),
7.22–7.40 (m, 6 H), 8.02 (s, 2 H, o-H).
=
{Ni(Mes)[NH C(Mes)(Me)](PIM)}BF4 (7b). Complex 7b
[Ni(Mes)(3,5-lut)(PIM)]BF4 (5b). Compound 5b was obtained
by the same procedure described for complex 5a by using complex
3b (yield = 80%) (Found: C, 61.0; H, 5.6; N, 7.5. Calc. for
C29H32BF4N3Ni: C, 61.31; H, 5.68; N, 7.40%). 1H NMR (250 MHz,
acetone-d6), obtained from the mixture of the isomers cis (20%)
was obtained by the same procedure as 7a from 3b as a yellow–
orange solid (yield = 30%, based on nickel) (Found: C, 63.3 H,
5.8; N, 6.6. Calc. for C33H38BF4N3Ni: C, 63.70; H, 6.16; N 6.75%).
1H NMR (500 MHz, CDCl3), obtained from the mixture of the
four isomers. trans-E isomer (60%), d 1.64 (s, 6 H, o-CH3-imine),
2.19 (s, 3 H, p-CH3-imine), 2.20 (s, 3 H, p-CH3Mes), 2.89 (s, 3 H,
=
and trans (80%). trans Isomer, d: 8.97 (s, 1 H, HC N), 8.32 (s, 2
H, o-H), 8.30 (d, J 7, 1H, H3), 8.16 (d, J 7, 1 H, H4), 7.61 (dd, J
5.5 and 1.5, 1 H, H2), 7.46 (s, 1 H, p-H), 7.34–7.33* ꢀ(m, 3 H, H
=
N CCH3), 3.00 (s, 6 H, o-CH3Mes), 4.84 (s, 2 H, CH2), 6.55 (s, 2
H, m-H Mes), 6.70* (s, 2 H, m-H imine), 7.21–7.80 (m, 7 H), 8.68
ꢀ
8,8 , 9), 7.26 (d, J 5.5, 1 H, H1), 7.06–7.07 (m, 2 H, H 7,7 ), 6.49 (s, 2
=
(s, 1 H, CH N), 10.33 (s, 1 H, NH). cis-E Isomer (25%), d 1.76
(s, 6 H), 2.35 (s, 3 H), 2.18 (s, 3 H), 2.83 (s, 3 H), 2.90 (s, 6 H),
H, m-H), 4.67 (s, 2 H, CH2), 3.06 (s, 6 H, o-CH3), 2.16* (s, 6 H,
m-CH3), 2.12 (s, 3 H, p-CH3). cis Isomer, d 8.76 (s, 2 H, o-H), 8.68
3
4
=
4.18 (s, 2 H), 6.47 (s, 2 H), 6.70* (s, 2 H), 7.2–8 (m, 9 H), 8.11 (s,
1 H, CH N), 9.20 (s, 1 H, NH); *overlapped signals between the
cis and trans isomers. Most representative signals for the minor
isomers, cis-Z isomer (9%), d 3.79 (2 H, s, CH2), 2.1–2.4 (s, 3 H,
N CCH3), trans-Z isomer (6%), d 5.00 (2 H, s, CH2), 2.1–2.4 (s,
(s, 1 H, HC N), 8.30 (d, J 7, 1 H, H ), 8.19 (d, J 7, 1 H, H ),
7.74 (dd, J 5ꢀ.5 and 1.5, 1 H, H2), 7.65 (s, 1 H, p-H), 7.34–7.33*
=
ꢀ
(m, 3 H, H8, 8 , 9), 7.18 (d, J 5.5, 1 H, H1), 6.86 (d, 2 H, H7,7 ), 6.45
(s, 2 H, m-H), 4.23 (s, 2 H, CH2), 3.01 (s, 6 H, o-CH3), 2.31 (s, 6
H, m-CH3), 2.16* (s, 3 H, p-CH3). * Overlapped signals of both
isomers.
=
=
3 H, N CCH3).
=
{Ni(Mes)[NH C(Mes)(Me)](bipy)}BF4 (7c). Complex 7b was
[Pd(Mes)(3,5-lut)(DAD)]BF4 (6a). Obtained by the same pro-
cedure described for complex 5a by using complex 4a (yield =
70%) (Found: C, 59.1 H, 6.0; N, 6.4. Calc. For C34H40BF4N3Pd:
C, 59.71; H, 5.90; N, 6.14%). 1H NMR (250 MHz, CDCl3), d 2.04
(s, 6 H, m-CH3), 2.11 (s, 3 H, p-CH3), 2.32 (s, 6 H, CH35, 6), 2.47 (s,
obtained by the same procedure as 7a from 3c as a yellow solid
(yield = 41% based on nickel) (Found: C, 59.4 H, 5.7; N, 6.9.
Calc. for C30H34BF4N3Ni: C, 61.90; H, 5.89; N 7.22%). 1H NMR
(250 MHz, acetone-d6); E Isomer (85%), d 1.89 (s, 6 H, o-CH3),
1
7
=
2.21 (s, 3 H, p-CH3), 2.22 (s, 3 H, N CCH3), 3.06 (s, 3 H, p-CH3),
6 H, o-CH3), 4.51 (s, 2 H, CH2 ), 4.74 (s, 2 H, CH2 ), 6.34 (s, 2 H,
ꢀ
ꢀ
m-H), 6.71 (m, 2 H, H2, 2 ), 6.88 (m, 2 H, H8,8 ), 7.14 (s, 1 H, p-H),
7.16–7.32 (m, 6 H), 7.78 (s, 2 H, o-H).
3.18 (s, 6 H, o-CH3), 6.63 (s, 2 H, m-H), 6.81 (s, 2 H, m-H), 8.50
(d, 1H), 8.41 (d, 1H), 8.32 (m, 2H), 8.20 (dd, 1H), 7.82 (dd, 1H),
7.42 (d, 2H), 9.45 (s, 1 H, NH); Z Isomer (15%), d 1.70 (s, 6 H),
2.29 (s, 6 H), 2.48 (s, 6 H), 2.54 (s, 3 H), 6.39 (s, 2 H), 6.79 (s, 2
H), 7.20–8.65 (m, 8 H), 11.09 (s, 1 H). Mass spectra FAB+ (NBA):
m/z = 495.8 (45), 494.0 (95), 374.9 (8), 332.9 (65), 215.6 (40), 213.7
(100), 161.5 (8).
[Pd(Mes)(3,5-lut)(PIM)]BF4 (6b). The compound was ob-
tained by the same procedure as 5a using complex 4b (yield =
83%) (Found: C, 57.2 H, 5.5; N, 7.1. Calc. for C29H32BF4N3Pd:
1
C, 56.26; H, 5.24; N 6.82%). H NMR (500 MHz, acetone-d6),
obtained from the mixture of the two isomers cis (25%) and trans
ꢀ
=
=
(75%). cis Isomer, d 9.05 (s, 1 H, HC N), 8.49 (s, 2 H, o-H), 8.39
{Ni(Mes)[NH C(Ph)(Mes)](bipy)}BF4 (7c ). To a solution of
(td, J 8 and 2, 1 H, H3), 8.33 (d, J 7.5, 1 H, H4), 7.98 (d, J 5, 1 H,
H1), 7.85 (ddd, J 7.5, 5 and 1.5, 1 H, H2), 7.74 (s, 1 H, p-H), 7.31
0.164 g (0.40 mmol) of [NiBr(Mes)(bipy)] in 30 cm3 of THF were
added an 300% excess of benzonitrile and 0.137 g (0.47 mmol)
of TlBF4. The color of the solution changed slowly from red to
yellow, after 30 min of vigorously stirring, TlBr was filtered off
ꢀ
(t, J 7.5, 1 H, H9), 7.24 (t, J 5.0, 2 H, H8, 8 ), 6.78 (d, J 7.5, 2 H,
ꢀ
H7, 7 ), 6.53 (s, 2 H, m-H), 4.60 (s, 2 H, CH2), 2.51 (s, 6 H, o-CH3),
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The Royal Society of Chemistry 2007
Dalton Trans., 2007, 83–90 | 89
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