A. A. Trifonov, R. Kempe et al.
FULL PAPER
Synthesis of 9: A solution of 2 (0.49 g, 1.24 mmol) in thf (30 mL)
of was added to a suspension of LaCl3 (0.152 g, 0.61 mmol) in thf
(5 mL) and the reaction mixture was stirred for 20 h at 65 °C. After
cooling to the room temperature thf was evaporated in vacuo and
the remaining residue was extracted with toluene (30 mL). The sol-
vent was removed under vacuum and the resulting solid residue
was redissolved in thf. Slow condensation of hexane into concen-
trated thf solution afforded complex 9 as brown crystals. The crys-
tals were washed with cold hexane and dried in vacuo at room
temperature; yield (0.12 g, 32%). C75H87LaN6 (1211.44): calcd. C
for 30 min at room temperature and for 1 h at 50 °C. After cooling
to room temperature the mixture was filtered and toluene was re-
moved in vacuo. The solid residue was dissolved in thf/hexane mix-
ture (≈ 1:2). Slow cooling of the concentrated solution of complex
12 to –20 °C afforded brown crystals of 12. The crystals were sepa-
rated from the mother liquor by decantation, washed with cold
hexane and dried in vacuo at room temperature (30 min); yield
(0.28 g, 61%). C58H73LaN4O2 (997.1): calcd. C 69.86, H 7.38, N
5.62; found C 69.73, H 7.81, N 5.66. 1H NMR (400 MHz, C6D6,
25 °C): δ = 1.03, 1.21, 1.27 [d, J = 6.8 Hz, 24 H, H,23,24,25,26], 1.35
74.36, H 7.24, N 6.94; found C 73.81, H 7.42, N 7.10. 1H NMR [br. s together, 10 H, β-CH2, thf, CH2La], 2.27, 2.42 [s, 9 H, H13,14],
(250 MHz, C6D6, 298 K): δ = 0.57–1.16 [br. m, 36 H, H23,24,25,26],
1.59 [br. s, 6 H, H13,14], 2.24 [br. s, 6 H, H13,14], 2.34 [br. s, 6 H,
H13,14], 2.83 [sept, J = 6.7 Hz, 2 H, H21,22], 3.33 [sept, J = 6.7 Hz,
4 H, H21,22], 5.57 [d, J = 8.7 Hz, 3 H, H3], 5.78 [d, J = 7.0 Hz, 3
3.33 [br. s, 2 H, H21,22], 3.48 [m, 2 H, H21,22], 3.51 [br. s, 8 H, α-
CH2, thf], 5.79, 5.81 [d, J = 8.4 Hz, 2 H, H3], 5.94, 6.46 [d, J =
7.2 Hz, 2 H, H5,], 6.56–7.35 [m, 14 H, H4,9,10,11,17,18,19] ppm. 13C
NMR (100 MHz, C6D6, 25 °C): δ = 20.4, 22.4 [C13,14], 24.1, 25.1
H, H5], 6.61 [dd, J = 8.7, J = 7.1 Hz, 3 H, H4], 6.82–7.23 [m,18 H, [C23,24,25,26], 25.2 [β-CH2, thf], 28.4, 28.5 [C21,22], 68.8[α-CH2, thf],
H9,10,11,17,18,19] ppm. 13C NMR (C6D6, 298 K): δ = 20.5 [C13,14]; 68.9 [s, CH2], 106.4, 108.4 [C3], 108.0, 109.0 [C5], 118.2, 122.8,
24.7, 26.5, 26.7 [C23,24,25,26]; 28.8, 29.1 [C21,22], 109.0 123.6, 123.8, 124.0, 127.4, 127.5, 127.6, 128.1 [C9,10,11,17,18,19],
[C3/5], 112.0 [C3/5], 124.5 [C17,19], 125.0 [C9,11], 125.3 [C10,18], 138.1
[C8,12], 140.9 [C7], 144.0 [C4], 145.7 [C16,20], 145.9 [C15], 156.0 [C6],
171.0 [C2] ppm.
138.4, 139.3 [C4], 134.3, 136.0, 141.7, 143.2, 143.6, 146.4, 147.1,
153.1 [C7,8,12,15,16,20], 153.7, 155.8 [C6], 166.7, 170.4 [C2] ppm.
Synthesis of 13: A solution of LiCH2SiMe3 (0.045 g, 0.48 mmol) in
(30 mL) hexane was added to
a suspension of 5 (0.464 g,
Synthesis of 10: LiCH2SiMe3 (0.105 g, 1.11 mmol) in hexane
0.48 mmol) in hexane (20 mL) and the reaction mixture was stirred
for 1 h. The mixture was filtered and hexane was removed in vacuo.
The solid residue was dissolved in a thf/pentane mixture (≈ 1:10).
Slow cooling of the concentrated solution of complex 13 to –20 °C
afforded brown crystals of 13. The crystals were separated from the
mother liquor by decantation, washed with cold hexane and dried
in vacuo at room temperature; yield (0.29 g, 63%). C54H65N4NdO
(930.36): calcd. C 69.71, H 7.04, N 6.02; found C 69.05, H 7.44, N
6.04.
(30 mL) was added to
a stirred suspension of 3 (0.886 g,
1.11 mmol) in hexane and the reaction mixture was stirred for 24 h.
The mixture was filtered and volume of the filtrate was reduced
under vacuum. A light yellow crystalline material deposited at
–25 °C after standing overnight; yield (0.572 g, 62%).
C54H69N4ScSi (847.19): calcd. C 76.56, H 8.21, N 6.61; found C
77.25, H 7.82, N 6.72. 1H NMR (250 MHz, C6D6, 298 K): δ = 0.13
[s, 9 H, CH2Si(CH3)3], 0.22 [s, 2 H, CH2Si(CH3)3], 0.81–1.27 [m,
24 H, H23,24,25,26], 1.45 [s, 6 H, H13,14], 2.18 [s, 6 H, H13,14], 3.18–
3.44 [sept, 4 H, H21,22], 5.62 [br., dd, 4 H, H3/5], 6.65 [br., dd, 2 H,
H4], 7.01–7.37 [m, 12 H, H9,10,11,17,18,19] ppm. 13C NMR (C6D6,
298 K): δ = 3.62 [Si(CH3)3], 21.26 [C13,14], 23.66 [C13,14], 24.7 and
24.8 [C23,24,25,26], 25.1 and 25.4 [C21,22], 29.2 [C21,22], 105.5 [C3/5],
110.4 [C3/5], 124.4 [C17,19], 125.9 [C9,11], 128.4 [C10,18], 136.3
[C8,12],139.4 [C7], 142.8 [C16,20], 144.1 [C4], 144.1 [C15], 144.5 [C6],
169.2 [C2] ppm. (CH2 signal could not be observed).
Synthesis of 14: A solution of PhSiH3 (0.061 g, 0.57 mmol) in tolu-
ene solution (3 mL) was added to a solution of 11 (0.600 g,
0.57 mmol) in toluene (30 mL) at room temperature and the reac-
tion mixture was stirred for 72 h. The solution was concentrated
to small volume and cooled to –25 °C affording yellow crystalline
material; yield (0.319 g, 60%). C54H65LuN4O (961.09): calcd. C
67.48, H 6.82, N 5.83; found C 67.28, H 7.20, N 5.99. 1H NMR
(400 MHz, C7D8, 298 K): δ = 0.80–1.58 [m, together 32 H,
H23,24,25,26, β-CH2, thf, CH2Lu],1.78–2.33 [m,together 9 H, H13,14],
3.19–3.45 [br., sept, 8 H, (4 H, α-CH2, thf) (4 H, H21,22)], 5.64 [m,
4 H, H3/5], 6.63–7.27 [m,14 H, H4,9,10,11,17,18,19] ppm. 13C NMR
(C7D8, 298 K): δ = 20.3, 20.5 [C13,14], 23.0, 25.0 [C23,24,25,26], 25.2
[β-CH2, thf], 28.1,28.6 [C21,22], 68.6 [α-CH2, thf], 72.1 [s,CH2],
103.7, 108.8 [C3/5], 110.1, 114.5 [C3/5], 124.2, 124.3, 124.8, 125.0,
127.5, 127.7, 128.5, 129.7 [C9,10,11,17,18,19], 134.7, 135.2 [C4], 135.9,
136.0, 138.9, 139.5, 140.8, 141.8, 144.4 [C7,8,12,15,16,20], 148.0, 156.3
[C6], 159.3, 159.9 [C2] ppm.
Synthesis of 11: LiCH2SiMe3 (0.094 g, 1.00 mmol) in hexane
(30 mL) was added to a stirred suspension of 8 (1.0 g, 1.00 mmol)
in hexane and the reaction mixture was stirred for 24 h. The mix-
ture was filtered and yellow crystals of 11 suitable for X-ray analy-
sis were obtained by slow cooling of the concentrated mixture thf/
hexane (1:5). The crystals were dried under vacuum for two hours
for elemental analysis; yield (0.900 g, 86%). C58H77LuN4OSi
(1049.31): calcd. C 66.39, H 7.40, N 5.34; found C 66.73, H 7.29,
N 5.71. 1H NMR (250 MHz, C6D6, 298 K): δ = –0.65 [s, 2 H,
CH2Si(CH3)3], 0.15 [s, 9 H, CH2Si(CH3)3], 0.92–1.22 [m, 24 H,
H23,24,25,26], 1.40 [br. s, 4 H, -CH2, thf], 1.46 [s, 6 H, H13,14], 2.16
[s, 6 H, H13,14], 3.29 [sept, J = 6.8 Hz, 4 H, H21,22], 3.59 [thf, 4 H,
β-CH2], 5.62 [d, J = 8.4 Hz, 2 H, H3/5], 5.67 [d, J = 6.9 Hz, 2
H, H3/5], 6.70 [br., H4, J = 7.9 Hz, 2 H, dd], 6.96–7.22 [m, 12 H,
H9,10,11,17,18,19] ppm. 13C NMR (C6D6, 298 K): δ = 4.34 [Si(CH3)3],
CCDC-740977 (for 7), -740978 (for 4), -740979 (for 13),
-740980 (for 11), -740981 (for 3), -740982 (for 9), -740983 (for 6),
-740984 (for 12) and -741180 (for 8) contain the supplementary
Crystallographic details for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data centre
via: www.ccdc.cam.ac.uk/conts/retrieving.html.
19.5 [C13,14], 21.1 [C13,14], 24.1[C23,24,25,26], 24.7[C23,24,25,26
]
25.0[C23,24,25,26] 25.7 [β-CH2, thf], 28.0 [C21,22], 29.3 [C21,22],
47.8[CH2], 68.4 [β-CH2, thf], 106.3 [C3/5], 109.8 [C3/5], 124.1 [C17,19],
124.4 [C17,19], 125.4 [C9,11], 127.8 [C9,11],128.5 [C10,18], 135.7 [C8,12],
136.2 [C8,12], 139.4 [C7], 140.8 [C4], 144.1 [C15], 144.2 [C16,20], 156.0
[C6], 168.0 [C2] ppm.
Acknowledgments
Financial support from the Deutsche Forschungsgemeinschaft
(DFG) (Schwerpunktprogramm 1166 “Lanthanoid-spezifische
Funktionalitäten in Molekül und Material), the Russian Founda-
tion for Basic Research (Grant No 08-03-00391, 06-03-32728), the
RFBR-DFG grant (08-03-91953) is gratefully acknowledged.
Synthesis of 12: A toluene solution of LiCH2SiMe3 (0.043 g,
0.46 mmol) in (30 mL) was added to a suspension of 4 (0.46 g,
0.46 mmol) in toluene (5 mL) and then reaction mixture was stirred
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Eur. J. Inorg. Chem. 2010, 248–257