101–102 ◦C. (Found: C, 79.1; H, 11.1; N, 4.8. C40H68N2O2 requires
3.93 (2H, d, J 13.0 Hz, ArCH2N), 6.19 (2H, s, Ar), 7.08 (2H, s,
Ar), dC{H} (125.8 MHz, C4D8O, 298K) 20.1 (NCH2CH2CH2N),
29.1 (CMe3), 31.2 (CMe3), 32.9 (CMe3), 34.6 (CMe3), 44.6
(NMe2), 46.2 (NCH2CH2CH2N), 58.7 (NCH2CH2CH2N), 59.8
(ArCH2N), 121.9 (arom-CH), 125.6 (arom-CBut), 127.5 (arom-
CH), 129.9 (arom-CBut), 133.9 (arom-CCH2N), 165.5 (arom-
CO).
C, 78.9; H, 11.3; N, 4.6%); nmax/cm-1 3345 s, 2730w, 2356 m, 1600
˜
m, 1261 m, 1095 s, 1049 m, 1022 s, 872w, 802 s, 725 m, 609 w (Nu-
jol); MS: m/z 609.5 [M + H]+. dH (500.1 MHz, C4D8O, 298 K) 0.65
(6H, t, J 7.0 Hz, CCH2CH3), 0.70 (6H, t, J 8.1 Hz, CCH2CH3),
1.51 (6H, t, J 7.0 Hz, N(CH2CH3)2), 1.29 (12H, s, C(CH3)2),
1.41 (12H, s, C(CH3)2), 1.63 (4H, q, J 7.0 Hz CCH2CH3),
1.95 (4H, q, J 8.1 Hz, CCH2CH3), 2.68-2.63 (8H, overlapping
signals of NCH2CH2N and N(CH2CH3)2), 3.75 (4H, s, ArCH2N),
6.88 (2H, s, Ar), 7.12 (2H, s, Ar), 9.7 (2H, s, OH), dC{H}
(125.8 MHz, C4D8O, 298K) 9.6 (CCH2CH3), 10.0 (CCH2CH3),
28.14 (C(CH3)2Et), 29.0 (C(CH3)2Et), 33.2 (C(CH3)2Et),
34.0 (C(CH3)2Et), 37.6 (CCH2CH3), 38.9 (CCH2CH3), 45.7
(NCH2CH3), 48.1 (NCH2CH3), 49.2 (NCH2CH2N), 50.4
(NCH2CH2N), 57.1 (ArCH2N), 121.6 (arom-CH), 125.9 (arom-
CPet), 127.2 (arom-CH), 124.4 (arom-CPet), 138.6 (arom-
CCH2N), 155.5 (arom-CO).
Synthesis of [YbL3a]2 (3). Using
for the synthesis of 1, hexanes solution (10 mL) of
a similar procedure
a
[Yb(N(SiMe3)2)2(THF)2] (0.64 g, 1.00 mmol) and a colorless
hexanes solution (5 mL) of H2L3a (0.58 g, 1.00 mmol) yielded a
greenish-brown solution from which 3 (0.59 g, 78%) precipitated
as dark green needle-like crystals. These were isolated from the
solution and dried in vacuo. Mp 224–226 ◦C. (Found: C, 60.7;
H, 8.3; N, 3.7. C76H124N4O4Yb2 requires C, 61.3; H, 8.5; N,
3.9%); nmax/cm-1 1739 w, 1600 w, 1299 w, 1261 s, 1214 w, 1161
˜
w, 1095 s, 1022 s, 933 w, 872 m, 802 s, 725 m, 602 m (Nujol);
dH (500.1 MHz, C4D8O, 298 K) 0.61–0.64 (12H, m, overlapping
signals of o-C(CH3)2CH2CH3 and p-C(CH3)2CH2CH3), 1.20
(12H, s, C(CH3)2CH2CH3), 1.41 (12H, s, C(CH3)2CH2CH3),
1.55 (6H, s, NMe2), 1.72 (4H, q, J 2 Hz, C(CH3)2CH2CH3),
1.81 (4H, q, J 2 Hz, C(CH3)2CH2CH3), 2.34 (2H, t, J
5.5 Hz, NCH2CH2N), 2.87 (2H, t, J 5.5 Hz, NCH2CH2N),
2.89 (2H, d, J 12.1 Hz, ArCH2N), 4.14 (2H, d, J 12.1 Hz,
ArCH2N), 6.74 (2H, s, Ar), 6.99 (2H, s, Ar), dC{H} (125.8 MHz,
C4D8O, 298K) 6.9 (C(CH3)2CH2CH3), 7.5 (C(CH3)2CH2CH3),
25.4 (C(CH3)2CH2CH3), 25.9 (C(CH3)2CH2CH3), 26.9
(C(CH3)2CH2CH3), 30.5 (C(CH3)2CH2CH3), 34.8 (C(CH3)2-
CH2CH3), 36.5 (C(CH3)2CH2CH3), 42.9 (NMe2), 44.9
(NCH2CH2N), 57.6 (NCH2CH2N), 62.7 (ArCH2N), 123.3
(arom-CH), 125.3 (arom-CPet), 126.2 (arom-CH), 126.6
(arom-CPet), 130.8 (arom-CCH2N), 164.2 (arom-CO).
Synthesis of [YbL2c]2 (1). A deep orange hexanes solution
(10 mL) of [Yb(N(SiMe3)2)2(THF)2] (0.64 g, 1.00 mmol) was
treated with a colorless hexanes solution (9 mL) of H2L2c (0.55 g,
1.00 mmol) which resulted instantly in a coffee brown solution.
Stirring was continued for 4 h at room temperature and compound
1·C7H8 (0.96 g, 75%) was obtained as cubic dark brown crystals
from a hexanes/toluene mixture, which was isolated and dried
in vacuo. Mp 220–222 ◦C. (Found: C, 60.2; H, 7.9; N, 4.0.
C72H116N4O4Yb2 requires C, 59.7; H, 8.1; N, 3.9%); nmax/cm-1
˜
1738 w, 1655 m, 1260 s, 1623 m, 1260 s, 1091 s, 1022 s, 866 w,
800 s, 697 w, 570 w, 546 m (Nujol); dH (500.1 MHz, C4D8O,
298K) 0.66 (6H, t, J 7 Hz, N(CH2CH3)2), 1.24 (18H, s, But),
1.47 (18H, s, But), 2.05 (2H, t, J 6.9 Hz, NCH2CH2N), 2.24 (4H,
q, J 7 Hz, N(CH2CH3)2), 2.25 (2H, t, J 6.9 Hz, NCH2CH2N),
2.89 (2H, d, J 12.3 Hz, ArCH2N), 4.55 (2H, d, J 12.3 Hz,
ArCH2N), 6.87 (2H, s, Ar), 7.09 (2H, s, Ar), dH (500.1 MHz,
C6D6) 0.67 (6H, t, J 7.0 Hz, N(CH2CH3)2), 1.34 (6H, t, J
6.7 Hz, N(CH2CH3)2), 1.36–1.80 (80H, overlapping signals of
But and NCH2CH2N), 1.95 (4H, q, J 7.0 Hz, N(CH2CH3)2),
2.97 (4H, q, J 6.7 Hz, N(CH2CH3)2), 3.25 (2H, d, J 12.2 Hz,
ArCH2N), 3.47 (2H, d, J 12.2 Hz, ArCH2N), 4.88 (2H, d, J
12.2 Hz, ArCH2N), 5.68 (2H, d, J 12.2 Hz, ArCH2N), 7.03 (2H, s,
Ar), 7.14 (2H, s, Ar), 7.35 (2H, s, Ar), 7.54 (2H, s, Ar), dC{H}
(125.8 MHz, C4D8O, 298 K) 5.3 (N(CH2CH3)2), 27.7 (CMe3),
29.8 (CMe3), 33.2 (CMe3), 37.7 (CMe3), 41.0 ((N(CH2CH3)2),
44.7 (NCH2CH2N), 49.2 (NCH2CH2N), 62.3 (ArCH2), 120.9
(arom-CH), 122.1 (arom-CBut), 124.4 (arom-CH), 129.0 (arom-
CCH2N), 132.6 (arom-CBut), 164.2 (arom-CO).
Synthesis of [YbL3b]2 (4). Using a similar procedure to
that described for the synthesis of 1, a reaction between
[Yb(N(SiMe3)2)2(THF)2] (0.64 g, 1.00 mmol) and H2L3b (0.57 g,
1.00 mmol) in hexanes (25 mL) yielded a yellow microcrystalline
powder of 4 (0.61 g, 83%). Mp 222–223 ◦C. (Found: C, 60.1;
H, 8.1; N, 1.9. C74H118N2O6Yb2 requires C, 60.2; H, 8.3; N,
1.9%); nmax/cm-1 3370 s, 2623 m, 2036w, 1600w, 1299 s, 1261 m,
˜
1211w, 1095 s, 1060 m, 1018 s, 872 m, 802 m, 725 m, 601 w
(Nujol); dH (500.1 MHz, C4D8O, 298 K) 0.62–0.65 (12H, m, over-
lapping signals of o-C(CH3)2CH2CH3 and p-C(CH3)2CH2CH3),
1.22 (12H, s, C(CH3)2CH2CH3), 1.36 (12H, s, C(CH3)2CH2CH3),
1.56 (4H, q, J 5.1 Hz, C(CH3)2CH2CH3), 1.78 (4H, q, J 5.5 Hz,
C(CH3)2CH2CH3), 2.59 (2H, t, J 4.1 Hz, NCH2CH2O), 2.81 (3H,
s, OMe), 2.93 (2H, d, J 11.1 Hz, ArCH2N), 2.98 (2H, t, J 4.1 Hz,
NCH2CH2O), 6.7 (2H, s, Ar), 7.13 (2H, s, Ar), dC{H} (125.8 MHz,
C4D8O, 298K) 7.2 (C(CH3)2CH2CH3), 7.7 (C(CH3)2CH2CH3),
25.6 (C(CH3)2CH2CH3), 25.8 (C(CH3)2CH2CH3), 27.1 (C(CH3)2-
CH2CH3), 27.2 (C(CH3)2CH2CH3), 30.6 (C(CH3)2CH2CH3), 34.9
(C(CH3)2CH2CH3), 35.7 (NCH2CH2O), 38.8 (NCH2CH2O), 55.6
(OCH3), 62.3 (ArCH2N), 122.0 (arom-CPet), 123.3 (arom-CH),
125.4 (arom-CH), 126.9 (arom-CPet), 131.2 (arom-CCH2N),
164.1 (arom-CO).
Synthesis of [YbL2b]2 (2). To a hexanes solution (6 mL) of
[Yb(N(SiMe3)2)2(THF)2] (0.32 g, 0.50 mmol) was added a colorless
hexanes solution (5 mL) of H2L2b (0.27 g, 0.50 mmol) which
led to an instant red solution. The reaction mixture was stirred
for 4 h at room temperature to afford 2 (0.23 g, 65%) as an
orange precipitate which was◦separated from the supernatant and
dried in vacuo. Mp 241–243 C. (Found: C, 60.1; H, 9.1; N, 4.1.
C70H112N4O4Yb2 requires C, 59.2; H, 7.9; N, 3.9%); nmax/cm-1
˜
2370w, 2342w, 1603 s, 1314w, 1261 s, 1093 s, 1024 s, 871 m, 801 s,
680w, 580 m (Nujol); dH (500.1 MHz, C4D8O, 298 K) 1.28 (18H, s,
But), 1.41 (18H, s, But), 1.50 (2H, m, NCH2CH2CH2N), 1.79 (2H,
t, J 7.1 Hz, NCH2CH2CH2N), 1.84 (6H, s, NMe2), 2.32 (2H, t,
J 7.1 Hz, NCH2CH2CH2N), 2.75 (2H, d, J 13.0 Hz, ArCH2N),
Synthesis of [SmL2c] (5). Using a similar procedure to that
described for the synthesis of the divalent ytterbium complexes,
a purple hexanes solution (10 mL) of [Sm(N(SiMe3)2)2(THF)2]
1442 | Dalton Trans., 2009, 1436–1445
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The Royal Society of Chemistry 2009
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