1
Analytical, IR and H NMR data of the new ligands are
product was filtered off, and washed several times with water
deposited as Electronic Supplementary Information (ESI).
and ether (yield = 64%) (Found: C, 49.8; H, 4.3; N, 7.2. Calc. for
C24H25BBrF4N3Ni: C, 49.62; H, 4.34; N, 7.23%). 1H NMR [500
MHz, acetone-d6, mixture of three isomers, (Z,Z)-A, and two
rotational isomers of (Z,E)-B]: δ 2.31 (s, Mep, A), 2.44 (s, Mep,
B), 2.47 (s, Mep, B), 3.32 (s, Meo, A), 3.50 (s, Meo, b), 3.55
Synthesis of the neutral complexes
1a. Over a suspension of 3.42 mmol of [Ni(cod)2] in 10 ml of
THF at Ϫ78 ЊC, 3.59 mmol (5% excess) of ligand a were added.
Then the mixture was stirred for 16 h at room temperature. The
formation of an orange solid was observed. The solid was
filtered off, washed several times with diethyl ether and water,
and finally dried in vacuum (yield = 77%) (Found: C, 42.6; H,
3.3; N, 6.3. Calc. for C16H14Br2N2Ni: C, 42.44; H, 3.12; N,
3
(s, Meo, b), 3.83 (t, CH2, B), 3.97 (t, J = 5.6, CHЈ2, A), 3.97
(t, 3J = 6.5, CH2, B), 4.33 (t, 3J = 6.1, CH2, A), 5.23 (d, 3J = 7.5,
H3, A), 5.51 (d, H3, B), 5.57 (d, H3, B), 6.8–7.8 (m), 8.47 (s, Him,
A), 8.48 (s, Him, B) and 9.06 (s, HЈim, A).
2b. The complex was prepared following the procedure
described for 2a, by using 1b (yield = 65%) (Found: C, 53.4;
H, 4.8; N, 7.9. Calc. for C24H25BClF4N3Ni: C, 53.74; H, 4.70;
6.19%). IR: ν(C᎐N) 1638 and 1608 cmϪ1. 1H NMR [500 MHz],
᎐
acetone-d6; mixture of two isomers A (Z,Z), B (Z,E)]: δ 3.75 (t,
3J = 6, CHЈ2 B), 3.86 (t, 3J = 6, CHЈ2 A), 3.97 (t, 3J = 6.5, CH2 B),
4.33 (t, 3J = 6.1, CH2 A), 6.9–7.8 (m), 8.32 (s, Him B), 8.36 (s, Him
A), 8.87 (s, HЈim A), 9.06 (s, HЈim B) and 9.19 (d, 3J = 7.2, H6Ј A).
1
N, 7.83%). H NMR (500 MHz, acetone-d6, mixture of four
isomers, in order of decreasing abundance: A, B, C, D): δ 2.31
(s, Mep, C), 2.37 (s, Mep, D), 2.44 (s, Mep, A), 2.47 (s, Mep,
B), 3.28 (t, CHЈ2, A), 3.31 (s, Meo, C), 3.33 (s, Meo, D), 3.51
1b. The complex was prepared following the above pro-
cedure, but using ligand b (yield = 93%) (Found: C, 51.6; H, 3.4;
N, 7.4. Calc. for C16H14Cl2N2Ni: C, 52.81; H, 3.88; N, 7.70%).
3
(s, Meo, A), 3.55 (s, Meo, B), 3.84 (t, J = 6.3, CH2, A), 3.98
3
3
(t, J = 6.0, CH2, B and C), 4.08 (t, CH2, D), 4.31 (t, J = 6.8,
CHЈ2, B), 4.54 (t, 3J = 5.8, CHЈ2, C), 4.70 (t, CHЈ2, D), 5.14 (d,
IR: ν(C᎐N) 1637 and 1612 cmϪ1. 1H NMR [500 MHz, acetone-
3J = 7.0, H3, D), 5.22 (d, J = 7.5, H3, C), 5.51 (d, J = 7.5, H3,
A), 5.57 (d, 3J = 7.5, H3, B), 6.65–7.70 (m), 8.34 (s, Him, A), 8.46
(s, Him, C), 8.48 (s, Him, B), 8.73 (s, Him, D), 9.07 (s, HЈim, D) and
9.15 (s, HЈim, C).
3
3
᎐
d6, isolated isomer Z,E]: δ 3.76 (td, 3J = 6.8, 4J = 1.3, CHЈ2), 4.01
3
4
4
(td, J = 6.8, J = 2.0, CH2), 6.9–7.6 (m), 8.29 (t, J = 1.8, Him)
and 8.91 (t, 4J = 2.0 Hz, HЈim). 1H NMR (500 MHz, acetone-d6,
isomer Z,Z from the mixture of both isomers): δ 3.8 (td,
3J = 6.3, 4J = 1.7, CHЈ2), 4.3 (td, 3J = 6.3, 4J = 1.2, CH2), 6.9–7.7
2c. The complex was prepared following the procedure
described for 2a, by using 1c and acetone as the solvent
(yield = 91%) (Found: C, 47.0; H, 4.1; N, 6.9. Calc. for
C24H23BCl3F4N3Ni: C, 47.62; H, 3.83; N, 6.94%). 1H NMR (500
MHz, acetone-d6): δ 2.32 (s, Mep), 3.27 (s, Meo), 4.03 (t, 3J = 6.2,
CHЈ2), 4.66 (t, 3J = 6.2, CH2), 5.14 (d, 3J = 7.4, H3), 6.86
(t, 3J = 7.8), 7.02 (d, 3J = 8.0 Hz), 7.3–7.5 (m), 8.70 (s, Him) and
9.04 (s, HЈim).
4
(m), 8.31 (t, J = 1.8, Him), 8.9 (broad singlet, HЈim) and 9.15
(dd, 3J = 8.5, 4J = 1.5, H6Ј).
1c. The complex was prepared following the general pro-
cedure described for 1a, by using ligand c (yield = 86%) (Found:
C, 43.9; H, 2.8; N, 6.3. Calc. for C16H12Cl4N2Ni: C, 44.40; H,
1
2.79; N, 6.47%). IR: ν(C᎐N) 1651 and 1604 cmϪ1. H NMR
᎐
3
4
(acetone-d6): δ 3.93 (td, J = 6.4, J = 2.1, 2H, CHЈ2), 4.39 (td,
3J = 7.0, J = 1.3, 2H, CH2), 6.9–7.5 (m, 6H), 8.57 (t, J = 1.7,
4
4
2d. The complex was prepared following the procedure
described for 2a, by using 1d (yield = 78%) (Found: C, 48.0; H,
4.1; N, 6.8. Calc. for C25H25BCl3F4N3Ni: C, 48.48; H, 4.07; N,
6.78%). 1H NMR: δ 2.31 (s, 3H, Mep), 2.43 (m, 2H, CHЈ2), 3.17
1H, Him) and 8.80 (broad singlet, 1H, HЈim).
1d. The complex was prepared following the general pro-
cedure described for 1a, by using ligand d and toluene as the
solvent (yield = 87%) (Found: C, 44.8; H, 3.3; N, 6.1. Calc. for
3
3
(s, 6H, Meo), 3.75 (t, J = 6.8, 2H, CHЉ2), 4.88 (t, J = 6.5, 2H,
CH2), 4.90 (d, 3J = 7.5 Hz, H3), 6.6–7.5 (m, 7H), 8.33 (s, br, Him)
and 8.67 (s, br, HЈim).
C H Cl N Ni: C, 45.70; H, 3.16; N, 6.27%). IR: ν(C᎐N) 1647
᎐
17 14
4
2
1
3
and 1601 cmϪ1. H NMR (acetone-d6): δ 2.41 (q, J = 6.1, 2H,
3
4
3
CHЈ2), 3.69 (td, J = 6.1, J = 1.3, 2H, CHЉ2), 4.43 (td, J = 6.9,
2e. The complex was prepared following the procedure
described for 2a, by using 1e (yield = 77%) (Found: C, 49.7; H,
4.5; N, 6.6. Calc. for C26H27BCl3F4N3Ni: C, 49.30; H, 4.30; N,
4J = 1.2, 2H, CH2), 6.8–7.6 (m, 6H), 8.42 (t, J = 1.3, Him) and
4
8.65 (t, 4J = 1.8, HЈim).
1
6.63%). H NMR (250 MHz, acetone-d6): between δ 1.5 and 3
1e. The complex was prepared following the procedure
described for 1d, by using ligand e (yield = 85%) (Found: C,
47.8; H, 3.7; N, 6.0. Calc. for C18H16Cl4N2Ni: C, 46.91; H, 3.50;
(broad signals, CHЈ2 and CHЉ2), 2.32 (s, 3H, Mep), 2.88 (s, 3H,
2
Meo), 3.35 (s, 3H, Meo), 3.56 (dm, J = 210, 2H, CHЉ2), 4.58
(dm, 2J = 340, 2H, CH2), 4.78 (d, 3J = 7.5, 1H, H3), 6.57 (s, Hm),
6.6–7.6 (m), 8.29 (s, Him) and 8.67 (s, HЈim).
N, 6.08%). IR: ν(C᎐N) 1629 and 1604 cmϪ1. 1H NMR (acetone-
᎐
d6): very broad signals in the aliphatic zone, corresponding to
the (CH2)4 bridge, δ 6.6–7.6 (m, 6H), 8.35 (broad singlet, Him)
and 8.67 (broad singlet, HЈim).
2f. The complex was prepared following the procedure
described for 2a, by using 1f (yield = 71%) (Found: C, 62.5; H,
5.2; N, 5.6. Calc. for C38H37BClF4N3Ni: C, 63.68; H, 5.20; N,
1
1f. The complex was prepared following the procedure
described for 1d, by using ligand f (yield = 85%) (Found: C,
64.4; H, 5.1; N, 4.4. Calc. for C30H26Cl2N2Ni: C, 66.22; H, 5.15;
N, 4.82%). 1H NMR (acetone-d6): δ 3.68 (t, 3J = 6.6, 2H, CHЈ2),
5.86%). H NMR (250 MHz, acetone-d6): δ 2.17 (s, 3H, Mep),
3.24 (s, 6H, Meo), 3.86 (t, 3J = 6.5, 2H, CHЈ2), 4.37 (s, 2H,
3
CH2bz), 4.60 (s, 2H, CH2bz), 4.86 (t, J = 6.5, 2H, CH2), 6.02
(d, 3J = 7.6, 1H, H3), 6.54 (t, 3J = 6.8, 1H), 6.76 (s, 2H, Hm), 6.79
(t, 3J = 6.9, 1H) and 6.9–7.7 (m, 15H).
3
4.29 (t, J = 6.5, 2H, CH2), 4.24 (s, 2H, CH2bz), 4.43 (s, 2H,
CH2bz) 6.6–7.6 (m, 16H) and 8.63 (m, 2H).
Synthesis of ionic complexes with acetonitrile
Synthesis of ionic complexes with 2,4,6-Me3C5H2N
3c. The complex was prepared following the procedure
described for 2a, by using a 300% excess of acetonitrile instead
of 2,4,6-Me3C5H2N (yield = 68%) (Found: C, 40.4; H, 3.0; N,
7.9. Calc. for C18H15BCl3F4N3Ni: C, 41.17; H, 2.88; N, 8.00%).
1H NMR (240 K, 250 MHz, acetone-d6): δ 2.18 (s, 3H, Menit),
3.92 (broad triplet, 2H, CHЈ2), 4.52 (broad triplet, 2H, CH2),
6.66 (broad singlet, 1H, H3), 7.0–7.7 (m, 5H), 8.58 (s, 1H, Him)
and 9.02 (s, 1H, HЈim).
2a. In 20 ml of THF, 9.1 mmol of 2,4,6-Me3C5H2N were
added over 8.8 mmol of the neutral complex 1a, and,
while stirring, 9.1 mmol of TlBF4. A suspension of the insol-
uble thallium halide was formed instantaneously, and after
30 minutes was separated by filtering over zeolite. The solvent
was then evaporated to dryness and the remaining resin stirred
with ether until a suspension of yellow solid was obtained. The
J. Chem. Soc., Dalton Trans., 2001, 977–985
983