Ytterbium and Europium Complexes Stabilized by Dipyridylamides
the supplementary crystallographic data for this publication. These
data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html (or from the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: + 44-
1223-336-033; E-mail: deposit@ccdc.cam.ac.uk).
1 H, 4-H), 7.40 (d, 3J = 8.5 Hz, 1 H, 17-H) ppm. 13C NMR
(100.5 MHz, [D8]THF): δ = 24.6 (C-21, C-24, C-25), 24.8 (C-22,
C-23/C-26, C-27), 25.0 (C-22, C-23/C-26, C-27), 26.3 (β-CH2,
THF), 30.8 (C-13, C-14), 35.3 (C-15), 68.2 (α-CH2, THF), 108.2
(C-19), 110.5 (C-17), 111.0 (C-5), 113.2 (C-3), 120.7 (C-9, C-11),
135.5 (C-4), 136.6 (C-18), 140.3 (C-7), 146.9 (C-8, C-12), 147.6 (C-
10), 156.4 (C-20), 158.5 (C-6), 166.8 (C-16), 167.0 (C-2) ppm.
Synthesis of (Ap*py)H (1): {(Ap*py)H = (6-methylpyridin-2-yl)-
[6-(2,4,6-triisopropylphenyl)pyridin-2-yl]amine; for the atom
numbering of Ap*pyH (1) and complexes thereof see formula} A
mixture of 2-bromo-6-(2,4,6-triisopropylphenyl)pyridine (10.8 g,
30.0 mmol), 2-amino-6-methylpyridine (4.00 g, 37.0 mmol), and so-
dium tert-butoxide (3.00 g, 31.3 mmol) was dissolved in toluene
(150 mL). Then a solution of 1,3-bis(diphenylphosphanyl)propane
(1.00 g, 2.42 mmol) and tris(dibenzylideneacetone)dipalladium(0)
(1.00 g, 1.09 mmol) in THF (30 mL) was added and the resulting
reaction mixture was stirred at 90 °C for 16 h. After cooling to
room temperature, water (20 mL) was added, the organic phase was
separated and the aqueous phase was washed with diethyl ether
(3ϫ20 mL). The combined organic phases were washed with a sat-
urated sodium chloride solution and dried with sodium sulfate. The
volatiles were removed in a vacuum leaving an orange-brown resi-
due that was purified by column chromatography on a silica gel
using dichloromethane as eluent. Removal of dichloromethane and
washing with cold pentane afforded a beige solid; yield 9.50 g
(82%); m.p. 159 °C. C26H33N3 (387.56): calcd. C 80.58, H 8.58, N
Synthesis of Yb2I(Ap*py)3(THF) (3a): In a glove box, [YbI2(thf)4]
(2.13 g, 2.98 mmol) and 2 (1.90 g, 3.82 mmol) were combined in a
flask and THF (100 mL) was added at 0 °C. The resulting dark red
reaction mixture was stirred at room temperature for 16 h. After
separation of the solution from the precipitated potassium iodide
by filtration, the solvent was removed under reduced pressure. The
resulting solid was dissolved in toluene (100 mL) and again filtered.
The filtrate was reduced to dryness, and a dark red-black product
was obtained. Crystals of 3a were grown from a concentrated tolu-
ene
solution;
yield
2.06 g
(72%);
m.p.
190 °C.
C82H104IN9OYb2·3C4H8O (1921.06): calcd. C 58.77, H 6.72, N
6.56; found C 58.77, H 6.67, N 6.93. 1H NMR (250 MHz, C6D6,
323 K): δ = 0.67–1.24 (m, 3J = 6.7 Hz, 54 H, 22-H, 23-H, 24-H,
25-H, 26-H, 27-H), 1.43 (br., 4 H, β-CH2,thf), 2.38 (sept, 3J =
3
6.9 Hz, 3 H, 15-H), 2.60 (sept, J = 7.0 Hz, 3 H, 14-H), 2.66 (s, 9
H, 21-H), 2.78 (sept, 3J = 6.7 Hz, 3 H, 13-H), 3.53 (br., 4 H, α-
3
3
CH2,thf), 6.00 (d, J = 6.7 Hz, 3 H, 19-H), 6.16 (d, J = 6.6 Hz, 3
H, H5), 6.83–7.16 (m, 18 H, 3-H, 4-H, 9-H, 11-H, 17-H, 18-
H) ppm. 13C NMR (62.9 MHz, C6D6): δ = 24.0 (s, C-22, C-23, C-
26, C-27), 24.1 (s, C-22, C-23, C-26, C-27), 24.2 (s, C-22, C-23, C-
26, C-27), 24.3 (s, C-22, C-23, C-26, C-27), 26.1 (s, β-CH2,thf), 26.8
(s, C-24, C-25), 27.1 (s, C-24, C-25), 29.8 (s, C-13, C-14), 30.0 (s,
C-13, C-14), 34.6 (s, C-15), 67.7 (s, α-CH2,thf), 109.5 (s, C-19),
113.4 (s, C-17), 114.5 (s, C-5), 116.2 (s, C-3), 121.0 (s, C-9, C-11),
135.8 (s, C-4), 137.5 (s, C-7, C-18), 137.6 (s, C-7, C-18), 146.9 (s,
C-8, C-12), 147.1 (s, C-8, C-12), 148.5 (s, C-10), 156.8 (s, C-2, C-
16), 157.4 (s, C-2, C-16), 164.2 (s, C-20), 169.1 (s, C-6) ppm. 171Yb
1
10.84; found C 80.56, H 8.56, N 10.21. H NMR (400 MHz, [D8]-
THF): δ = 1.09 (d, 3J = 6.8 Hz, 6 H, 22-H, 23-H/26-H, 27-H), 1.10
(d, 3J = 6.8 Hz, 6 H, 22-H, 23-H/26-H, 27-H), 1.28 (d, 3J = 7.2 Hz,
3
6 H, 24-H, 25-H), 2.38 (s, 3 H, 21-H), 2.70 (sept, J = 6.8 Hz, 2 H,
13-H, 14-H), 2.91 (sept, 3J = 7.2 Hz, 1 H, 15-H), 6.59 (d, 3J =
7.2 Hz, 1 H, 19-H), 6.69 (dd, 3J = 7.2, 4J = 0.4 Hz, 1 H, 5-H), 7.06
(s, 2 H, 9-H, 11-H), 7.35 (dd, 3J = 7.2, 3J = 8.0 Hz, 1 H, 18-H),
3
3
3
7.52 (d, J = 8.0 Hz, 1 H, 17-H), 7.57 (dd, J = 7.2, J = 8.4 Hz, 1
3
H, 4-H), 7.66 (d, J = 8.4 Hz, 1 H, 3-H), 8.8 (br., 1 H, N-H) ppm.
13C NMR (100.5 MHz, [D8]THF): δ = 24.4 (C-21), 24.4 (C-22, C-
23/C-26, C-27), 24.5 (C-22, C-23/C-26, C-27), 24.6 (C-24, C-25),
31.1 (C-13, C-14), 35.3 (C-15), 109.3 (C-17), 110.2 (C-3), 115.2 (C-
19), 117.4 (C-5), 120.9 (C-9, C-11), 137.6 (C-4), 138.1 (C-7, C-18),
147.0 (C-8, C-12), 148.8 (C-10), 155.1 (C-16), 155.3 (C-2), 156.8
(C-20), 158.7 (C-6) ppm.
1
NMR (70 MHz, C4H8O): δ = 646.6 [s, J(171Yb, 171Yb) = 76.1 Hz,
Yb-thf], 585.6 (br., Yb-I) ppm.
Synthesis of Yb2(Ap*py)4(THF)2 (4): In a NMR tube a solution of
3a (0.250 g, 0.147 mmol) in [D8]THF (0.5 mL) was combined with
2 (0.062 g, 0.127 mmol) and the black solution was filtered. The
solution was kept at –30 °C for 48 h to afford deep red nearly black
crystals of 4; yield (0.075 g, 29%). C112H144N12O2Yb2 (2036.50):
1
calcd. C 66.05, H 7.13, N 8.25; found C 66.23, H 7.16, N 8.03. H
NMR (500.13 MHz, [D8]THF): δ = 1.08 (d, 3J = 6.9 Hz, 24 H, 22-
H, 26-H), 1.11 (d, 3J = 6.9 Hz, 24 H, 23-H, 27-H), 1.26 (d, 3J =
6.9 Hz, 24 H, 24-H, 25-H), 2.05 (s, 12 H, 21-H), 2.86 (m, 12 H, 13-
H, 14-H, 15-H), 6.04 (d, 3J = 4.7 Hz, 4 H, 3-H), 6.28 (d, 3J =
Synthesis of K(Ap*py)·THF (2): To a mixture of 1 (3.00 g,
7.74 mmol) and potassium hydride (0.70 g, 17.5 mmol) was slowly
added diethyl ether (150 mL) at 0 °C. The reaction mixture was
stirred at ambient temperature for 16 h. The volatiles were removed
in a vacuum and the product was extracted twice with THF and
the solution was filtered. The solvent was removed under reduced
pressure and the resulting beige solid was washed with hexane;
yield 3.00 g (77.9%); m.p. 110 °C. C26H32KN3·C4H8O (497.76):
3
5.7 Hz, 4 H, 17-H), 6.68 (d, J = 6.2 Hz, 4 H, 19-H), 7.00 (s, 8 H,
3
9-H, 11-H), 7.08 (dd, 3J = 4.7, J = 8.0 Hz, 4 H, 4-H), 7.23 (dd, 3J
= 5.7, 3J = 6.2 Hz, 4 H, 18-H), 7.74 (d, 3J = 8.0 Hz, 4 H, 5-H) ppm.
13C NMR (125.8 MHz, [D8]THF): δ = 24.0 (C-21), 25.1, 25.3, 25.4
(C-22, C-23, C-24, C-25, C-26, C-27), 31.5 (C-13, C-14), 35.9 (C-
15), 109.9 (C-3), 110.6 (C-5), 113.6 (C-17), 114.8 (C-19), 121.2 (C-
9, C-11), 136.2 (C-18), 138.3 (C-4), 140.3 (C-20), 147.4 (C-8, C-12),
148.5 (C-7), 155.4 (C-6), 158.9 (C-10), 165.0 (C-2/C-16), 166.9 (C-
2/C-16) ppm. 171Yb NMR (69.96 MHz, [D8]THF): δ = 679.8 ppm.
1
calcd. C 72.39, H 8.10, N 8.44; found C 72.17, H 8.87, N 8.43. H
3
NMR (400 MHz, [D8]THF): δ = 1.06 (d, J = 6.8 Hz, 6 H, 22-H,
23-H/26-H, 27-H), 1.07 (d, 3J = 6.8 Hz, 6 H, 22-H, 23-H/26-H, 27- Synthesis of Eu2I(Ap*py)3(THF)·3THF (3b): To a mixture of EuI2
3
H), 1.24 (d, J = 7.2 Hz, 6 H, 24-H, 25-H), 1.71 (br., 4 H, β-CH2,
THF), 2.15 (s, 3 H, 21-H), 2.86 (sept, 3J = 7.2 Hz, 1 H, 15-H), 2.90
(sept, 3J = 6.8 Hz, 2 H, 13-H, 14-H), 3.57 (br., 4 H, α-CH2, THF),
(0.812 g, 2.0 mmol) and 2 (1.40 g, 2.82 mmol) was added THF
(100 mL) at 0 °C. The resulting orange reaction mixture was stirred
at room temperature for 16 h. Potassium iodide was removed by
filtration and the solvent was removed under reduced pressure. The
3
3
6.01 (d, J = 6.9 Hz, 1 H, 19-H), 6.05 (d, J = 7.0 Hz, 1 H, 5-H),
3
3
3
6.74 (d, J = 8.5 Hz, 1 H, 3-H), 6.96 (dd, J = 6.9, J = 8.5 Hz, 1 resulting solid was dissolved in toluene (100 mL) and again filtered.
H, 18-H), 6.97 (s, 2 H, 9-H, 11-H), 7.07 (dd, 3J = 7.0, J = 8.5 Hz, The filtrate was concentrated to a small volume and cooled to
3
Eur. J. Inorg. Chem. 2009, 1051–1059
© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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