2
84
L. Maria et al. / Polyhedron 119 (2016) 277–285
NCH
2
), 1.89 (br, 4H, CH
2
CH
).
C NMR (75 MHz, chloroform-d
30.44 (ArC-H), 128.70 (ArC-H), 126.37 (ArC), 124.76 (ArC),
23.15 (ArC), 54.98 (NCH Ar), 54.40 (NCH ), 51.50 (NCH ), 51.02
), 48.15 (NCH ), 43.59 (NCH ), 24.33 (CH CH CH ), 20.61
), 16.38 (CH ).
C NMR (75 MHz, chloroform-d
30.20 (ArC-H), 128.86 (ArC-H), 126.14 (ArC), 124.63 (ArC),
23.24 (ipso-ArC), 54.64 (NCH Ar + NCH ), 53.54 (NCH ), 50.83
), 23.85 (CH CH CH ),
2
CH
2
and NCH
2
), 1.46 (br, 2H, CH
2
CH
2
-
vigorous reaction took place and after 16 h the reaction mixture
was centrifuged. The resulting clear solution of 2-K was added to
a yellow solution of [YbI (thf)2.5] (689 mg, 1.135 mmol) in thf
2
CH ), 1.03 (br, 2H, NCH
2
1
2
3
1
, 23 °C) d: 153.40 (ArC-O),
1
1
(15 mL), and the color changed immediately to a strong orange-
red. After continued stirring overnight, at room temperature, the
reaction mixture was centrifuged to separate the KI, and the
orange-red solution was concentrated to a small volume and lay-
ered with n-hexane. An orange microcrystalline solid precipitated
and was collected by centrifugation and dried under vacuum
(450 mg, 0.363 mmol, 64% yield). Orange-red crystals of 5 suitable
for X-ray diffraction analysis were grown from a concentrated thf
2
2
2
(
(
NCH
CH
2
2
3
2
2
2
3
3
1
3
1
, ꢀ40 °C) d: 153.04 (ArC-O),
1
1
2
2
2
(
NCH
2
), 50.57, 47.34 (NCH
2
), 43.63 (NCH
3
2
2
2
2
0.64 (CH ), 16.71 (CH ).
3
3
solution. Analysis for C38
62 8 6 2 2
H N O I Yb : Calcd. C, 36.84; H, 5.04;
N, 4.52; Found C, 36.74; H, 5.15; N, 4.53%.
tBu2
1
4
.3. Reaction of [YbI
2
(thf)2.5] with K
2
(
2
ArO) Me
2
-cyclam (1-K):
H NMR (300 MHz, thf-d
Ar-H), 5.76 (2H, d, 12 Hz NCH
8
, 23 °C): d 6.82 (2H, Ar-H), 6.68 (2H,
CH ), 3.62 ( -thf), 3.30 (t, 2H,
), 2.75 (2H, d, 12 Hz, NCH CH ), 2.47 (6H,
), 2.60–2.31 (6H, CH ), 2.13 (6H, CH ), 2.08 (6H, NCH ),
), 1.77 (b-thf), 0.97 (4H, br, CH CH CH ).
, 23 °C): d 161.05 (ArC-O), 132.64
compound 3
2
3
a
CH
CH
2
), 2.83 (t, 2H, CH
2
2
3
Excess of potassium hydride (64 mg, 1.59 mmol) was added to a
3
2
3
3
tBu2
solution of H
15 mL). After stirring for 16 h at room temperature, the resulting
colorless solution was separated by centrifugation and added to a
solution of 1 equiv. of [YbI (thf)2.5] (274 mg, 0.451 mmol) in thf
15 mL). The solution turned orange and KI precipitated. After stir-
2
(
ArO)
2
Me
2
-cyclam (300 mg, 0.451 mmol) in thf
2.18–1.98 (6H, CH
2
2
2
2
1
3
(
C NMR (75 MHz, thf-d
8
(ArC-H), 130.85 (ArC-H), 129.10 (ArC), 126.16 (ArC), 123.96 (ArC),
68.38 (thf), 66.68 (NCH Ar), 62.71 (CH ), 60.12 (CH ), 59.85 (CH ),
56.62 (CH ), 40.50 (NCH ), 26.51 (thf), 25.89 (CH CH CH ), 22.38
(CH ), 20.77 (CH ).}
2
2
2
2
2
(
2
3
2
2
2
ring over 14 h at room temperature, the reaction mixture was cen-
trifuged, the supernatant was decanted off and the solvent was
removed under reduced pressure. The resulting solid was washed
with n-hexane and after drying in vacuo 3 was isolated as an
3
3
4.6. Single crystal X-ray diffraction
orange solid (268 mg).
Crystallographic and experimental details of data collection and
1
H NMR (300 MHz, thf-d
8
, 23 °C) d: 7.12 (2H, d, Ar-H), 6.76 (2H,
Ar), 3.06 (2H, t, CH ), 2.95–2.41 (10H,
), 2.39–2.13 (14H, CH ), 2.19 (6H, NCH ), 1.66 (2H, CH
), 1.53 (18H, C(CH ), 1.24 (18H, C(CH ).
C NMR (75 MHz, thf-d , 23 °C) d 166.96 (ArC-O), 136.92 (ArC),
31.86 (ArC), 126.89 (ArC-H), 124.01 (ArC), 123.79 (ArC-H), 62.83
crystal structure determinations for the compounds 2, 4 and 5 are
given in Table 3. Suitable crystals of compounds 4 and 5 were
selected and coated in FOMBLIN oil under an inert atmosphere.
Crystals were then mounted on a loop and the data for compounds
d, Ar-H), 4.30 (2H, br, NCH
2
2
CH
CH
2
+ NCH
CH
2
2
3
2
-
2
1
2
3
)
3
3 3
)
3
8
2
(
1
, 4 and 5 were collected using graphite-monochromated Mo K
k = 0.71073 Å) on a Bruker AXS-KAPPA APEX II area detector at
50 K. Cell parameters were retrieved using Bruker SMART and
a
1
(
3
2
NCH
2
Ar), 57.43 (CH
6.47 (C(CH ), 34.50 (C(CH
4.16 (CH CH CH ).
2
), 56.27 (CH
2
), 54.22 (CH
2
), 43.17 (NCH
3
),
),
3
)
3
3
)
3
), 32.85 (C(CH
3
)
3
), 31.09 (C(CH )
3
3
refined using Bruker SAINT on all observed reflections. Absorption
corrections were applied using SADABS [24]. The structures were
2
2
2
solved by direct methods using either SHELXS-97 [25] or SIR 97 [26]
Me2
4.4. Synthesis of [Yb
3
(l
-{( ArO)
2
Me
2 2
-cyclam}) I]I (4)
and refined using full-matrix least squares refinement against F2
using SHELXL-97 [25]. In the former case, all programs are included
in the WINGX software package [27]. All non-hydrogen atoms were
refined anisotropically, unless it was mentioned in the cif files of
the structures, and all hydrogen atoms were placed in idealized
positions and allowed to refine riding on the parent carbon atom.
In complex 5 some carbons of the ligand are disordered and a con-
straint model was used (see cif files in ESI).
Solid KH (40 mg, 1 mmol) was added to a solution of
Me2
H
2
(
2 2
ArO) Me -cyclam (134 mg, 0.271 mmol) in thf (15 mL).
After 16 h of stirring at room temperature, the reaction mixture
was centrifuged. The resulting clear solution of 2-K was added to
2
a yellow solution of [YbI (thf)2.5] (247 mg, 0.406 mmol) in thf
(
10 mL), and the color changed immediately to a strong orange.
After continued stirring overnight, at room temperature, the reac-
tion mixture was centrifuged to separate the KI, and the orange
solution was concentrated to a small volume and layered with
n-hexane. An orange microcrystalline solid precipitated and was
collected by centrifugation and dried under vacuum (103 mg,
Acknowledgements
The experimental support of Adelaide Cruz is gratefully
acknowledged. The work was supported by Fundação para a Ciên-
cia e a Tecnologia (FCT) through a post-doctoral grant (SFRH/
BPD/101840/2014) to L.M., RNEM-Portuguese Mass Spectrometry
Network and projects PTDC/QUI-QUI/109846/2009, RECI/QEQ-
QIN/0189/2012 and UID/Multi/04349/2013.
0
.058 mmol, 43% yield).
Analysis for C60
Found C, 40.97; H, 5.87; N, 6.35%.
92 8 4 2 3
H N O I Yb : Calcd. C, 40.89; H, 5.26; N, 6.36;
1
H NMR (300 MHz, thf-d
8
, 23 °C) d: 6.71 (Ar-H), 6.47 (Ar-H),
Me2
2
.55, 2.12 (s), 2.07 (s), 1.50. Not all of the ligand ( ArO) Me -
2 2
2ꢀ
cyclam resonances were observed at 23 °C.
1
H NMR (300 MHz, thf-d
8
, ꢀ60 °C): d 6.73 (1H, Ar-H), 6.67 (1H,
), 2.23 (3H,
), 1.75 (3H,
, overlapping with solvent), 3.40–1.28 (broad resonances,
Appendix A. Supplementary data
Ar-H), 6.49 (1H, Ar-H), 6.42 (1H, Ar-H), 2.63 (3H, NCH
NCH
NCH
3
3
), 2.09 (3H, CH
3
), 2.07 (3H, CH
3
), 2.02 (3H, CH
3
CCDC 1487952–1487954 contains the supplementary crystallo-
from the Cambridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
3
macrocycle CH
2
). See Figs. S11 and S12 in ESI.
Me2
4
2 2 2 2 4 8 2
.5. Synthesis of [Yb (l-{(Ar O) Me -cyclam})I (C H O) ] (5)
Solid KH (79 mg, 1.98 mmol) was added to a solution of
Me2
H
2
(
2 2
ArO) Me -cyclam (281 mg, 0.567 mmol) in thf (20 mL). A