1000 Organometallics, Vol. 30, No. 5, 2011
Li et al.
(C6H3), 139.4 (C4H3N), 136.1 (C4H3N), 129.5 (C6H3), 128.7
(C6H3), 123.9 (C4H3N), 120.4 (C6H3), 112.5 (C4H3N), 67.7
(THF), 25.3 (THF), 18.7 (CH3). IR (KBr pellet, cm-1): ν 3202
(s), 2967 (m), 2859 (w), 1632 (s), 1589 (m), 1558 (w), 1509 (w),
1474 (m), 1339 (m), 1312 (m), 1261 (m), 1188 (m), 1134 (s), 1088
(s), 1034 (s), 918 (m), 860 (m), 833 (m), 767 (m), 741 (m), 606 (m).
Anal. Calcd for C34H42O2N4Li2þ2THF: C, 72.39; H, 8.39; N,
8.04. Found: C, 73.04; H, 8.60; N, 8.16.
Reaction of 1a with [(Me3Si)2N]3Eu(μ-Cl)Li(THF)3: Charac-
terization of the Mixture of {[η2:η1-2-(2,6-Me2C6H3NdCD)-
C4H3N]Li(THF)}2 (4a) and 4. Compound 1a was treated with
2 equiv of [(Me3Si)2N]3Eu(μ-Cl)Li(THF)3 following procedures
similar to those used for the preparation of 4 to give a mixture of
4a and 4. 1H NMR (300 MHz, C6D6): δ 7.84 (s, 0.47H, CHdN),
7.38 (s, 1H, C4H3N), 7.22-7.09 (m, 3H, C6H3), 6.96 (s, 1H,
C4H3N), 6.57 (s, 1H, C4H3N), 3.13 (m, 4H, THF), 2.29 (s, 6H,
CH3), 1.21 (m, 4H, THF). 13C NMR (75.0 MHz, C6D6): δ 160.3
(NdCH), 151.9 (C6H3), 139.1 (C4H3N), 135.8 (C4H3N), 129.2
(C6H3), 128.4 (C6H3), 123.6 (C4H3N), 120.1 (C6H3), 112.2
(C4H3N), 67.4 (THF), 25.0 (THF), 18.4 (CH3).
(KBr pellets, cm-1): ν 3086 (s), 2868 (s), 1591 (w), 1576 (m), 1462
(s), 1442 (s), 1364 (m), 1256 (m), 1186 (m), 1101 (w), 1043 (m),
1024 (m), 934 (m), 883 (m), 837 (m), 802 (m), 762 (s), 721 (s), 609
(m). Anal. Calcd for C46H80D2Li4N6Si4: C, 64.15; H, 9.83; N,
9.76. Found: C, 63.87; H, 9.72; N, 9.55.
Preparation of {(μ-η5:η1:η1-2-[(2,6-iPr2C6H2)NCH2]C4H3N)-
YbN(SiMe3)2}2 (7). This complex was isolated as dark red
crystals in 57% yield by treatment of 2 (0.477 g, 1.86 mmol)
with [(Me3Si)2N]3Yb(μ-Cl)Li(THF)3 (1.698 g, 1.86 mmol) using
procedures similar to those described above for the preparation
of 4. Mp: 270-272 °C. IR (KBr pellets, cm-1): ν 2958 (s), 2864
(m), 1624 (w), 1575 (w), 1441 (s), 1385 (m), 1331 (m), 1312 (m),
1256 (m), 1198 (m), 1184 (m), 1099 (m), 1043 (m), 1026 (m), 968
1
(w), 934 (w), 883 (m), 804 (s), 766 (m), 723 (m), 610 (m). H
NMR spectrum of the complex gave several resonances that
cannot be assigned. Anal. Calcd for C46H80N6Si4Yb2: C, 47.00;
H, 6.86; N, 7.15. Found: C,47.05; H, 6.98; N, 7.03.
Hydrolysis of complex 7 gave pure compound 2, which was
identified by 1H NMR and 13C NMR spectra analyses.
Refluxing the toluene solution of 7 did not lead to reduction
and formation of imino-functionalized product by careful anal-
ysis of the 1H NMR spectra of hydrolysis product.
Preparation of {[η2:η1-2-(2,6-iPr2C6H3NdCH)C4H3N]Li-
(THF)]}2 (5). This compound was isolated as colorless crystals
in 53% yield (based on amine) by treatment of [(Me3Si)2N]3-
Eu(μ-Cl)Li(THF)3 (1.925 g, 2.16 mmol) with 2-(2,6-iPr2C6H3-
NHCH2)C4H3NH (2) (0.277 g, 1.08 mmol) following proce-
dures similar to those used for the preparation of 4. Mp:
201-203 °C. 1H NMR (300 MHz, CDCl3): δ 7.96 (s, 2H,
CHdN), 7.26-7.17 (m, 6H, C6H3), 7.08 (s, 2H, C4H3N), 6.76
(d, J = 3.3 Hz, 2H, C4H3N), 6.27 (dd, J = 3.3 Hz, 2H, C4H3N),
3.41 (m, 8H, THF), 3.23 (hepta, J = 6.8 Hz, 4H, CHMe2), 1.75
(m, 8H, THF), 1.19 (d, J = 6.8 Hz, 24H, CH(CH3)2). 13C NMR
(75.0 MHz, CDCl3): δ 160.3 (NdCH), 149.2 (C6H3), 140.3
(C6H3), 139.1 (C4H3N), 136.2 (C4H3N), 124.1 (C4H3N), 123.2
(C6H3), 119.3 (C6H3), 111.2 (C4H3N), 67.6 (THF), 27.5 (CH3),
25.4 (THF), 24.4 (CHMe2). IR (KBr pellets, cm-1): ν 3059 (w),
2926 (m), 2900 (m), 2868 (m), 1747 (w), 1722 (w), 1626 (s), 1585
(m), 1552 (m), 1458 (m), 1418 (m), 1339 (s), 1310 (m), 1254 (w),
1180 (m), 1132 (m), 1090 (m), 1032 (m), 932 (w), 885 (m), 860
(m), 781 (m), 745 (m), 608 (w). Anal. Calcd for C42H58O2N4Li2:
C, 75.88; H, 8.79; N, 8.43. Found: C, 75.85; H, 8.63; N, 9.04.
Reaction 2a with [(Me3Si)2N]3Eu(μ-Cl)Li(THF)3: Character-
ization of the Mixture of {[η2:η1-2-(2,6-iPr2C6H3NdCD)C4-
H3N]Li(THF)]}2 (5a) and 5. Compound 2a was treated with 2 equiv
of [(Me3Si)2N]3Eu(μ-Cl)Li(THF)3 following procedures similar to
those used for the preparation of 5 to give a mixture of 5a and 5. 1H
NMR (300 MHz, CDCl3): δ 7.92 (s, 0.43H, CHdN), 7.21-7.16
(m, 3H, C6H3), 7.04 (s, 1H, C4H3N), 6.73 (d, 1H, C4H3N), 6.24 (s,
1H, C4H3N), 3.28 (m, 4H, THF), 3.17 (hepta, J = 6.9 Hz, 2H,
CHMe2), 1.69 (s, 4H, THF), 1.14 (d, J = 6.9 Hz, 12H, CHMe2).
13C NMR (75.0 MHz, CDCl3): δ 160.1 (NdCH), 149.1 (C6H3),
140.3 (C6H3), 138.6 (C4H3N), 135.5 (C4H3N), 124.2 (C4H3N),
123.2 (C6H3), 119.3 (C6H3), 111.3 (C4H3N), 67.6 (THF), 27.6
(CHMe2), 25.4 (THF), 24.3 (CH3).
Preparation of {[μ-η5:η1:η1-2-(2,6-iPr2C6H3N(Me2SiO)-
CH2)C4H3N]Eu[μ-η5:η1:η2-2-(2,6-iPr2C6H3NdCH)C4H3N]Li2-
[N(SiMe3)2]}2 C6H14 (8). This complex was isolated as red crystals
3
in 39% yield (based on amine) by treatment of [(Me3Si)2N]3-
Eu(μ-Cl)Li(THF)3 (1.823 g, 2.04 mmol) with 2-(2,6-iPr2C6H3-
NHCH2)C4H3NH (2) (0.524 g, 2.04 mmol) and (Me2SiO)3
(0.152 g, 0.68 mmol) by employing procedures similar to those
used for the preparation of 4. Mp: 236-237 °C. IR (KBr pellets,
cm-1): ν 2960 (s), 2866 (m), 1624 (s), 1587 (m), 1560 (m), 1496
(m), 1460 (m), 1436 (m), 1383 (m), 1361 (m), 1340 (m), 1319 (m),
1274 (s), 1232 (m), 1203 (w), 1182 (m), 1140 (w), 1098 (m), 1043
(s), 1001 (w), 932 (w), 868 (m), 777 (m), 745 (m), 704 (m), 657
(m), 633 (w), 550 (w). Attempts to get NMR spectra of the
complex failed due to lack of locking signals for the paramag-
netic property of the complex. Anal. Calcd for C93H155Eu2Li4-
N10O2Si6þ2C6H14: C, 59.55; H, 8.71; N, 6.61. Found: C, 59.59;
H, 8.13; N, 6.80.
Preparation of {[(5-tBu-C4H2N-2-CHdNCH2)2]4(5-tBu-2-
CH3NdCHC4H2N)Eu3Li3}2 (9). To a toluene (30.0 mL) solu-
tion of [(Me3Si)2N]3Eu(μ-Cl)Li(THF)3 (2.327 g, 2.61 mmol) was
added a toluene (10.0 mL) solution of [5-tBu-C4H2NH-2-
CH2NHCH2]2 (3) (0.216 g, 0.65 mmol) at room temperature.
After the reaction mixture was stirred for 24 h at 100 °C. The
solvent was evaporated under reduced pressure. The residue was
extracted with hexane (2 ꢀ 15.0 mL). The extraction was com-
bined and dried under vacuum to afford complex 9 in 53% yield
(0.149 g, based on amine). Red crystals for X-ray analysis were
obtained from hexane at 0 °C within a week. Mp: 247-248 °C.
IR (KBr pellets, cm-1): ν 3263 (m), 2965 (s), 2338 (m), 1635 (s),
1568 (s), 1492 (m), 1461 (s), 1415 (m), 1367 (m), 1280 (m), 1251
(m), 1203 (m), 1145 (m), 1041 (s), 962 (m), 929 (w), 880 (m), 843
(m), 785 (m). Attempts to get NMR spectra of the complex failed
due to lack of locking signals for the paramagnetic property of
the complex. Anal. Calcd for C180H254Eu6Li6N36þC6H14: C,
56.39; H, 6.82; N, 12.73. Found: C, 56.15; H, 7.14; N, 12.27.
Preparation of {η2:η2-[η1:η1-(μ-η5:η5-[5-tBu-C4H2N-2-CH2-
NCH2CH2N-2-CH2-5-tBu-C4H2N]Li)2]Dy2(μ3-Cl)Li}2 (10).
This complex was isolated as colorless crystals in 46% yield by
treatment of 3 (0.396 g, 1.20 mmol) with [(Me3Si)2N]3Dy-
(μ-Cl)Li(THF)3 (2.165 g, 2.40 mmol) using procedures similar
to those described above for the preparation of 9. Mp: 265-266
°C. IR (KBr pellets, cm-1): ν 3085 (m), 2988 (s), 2850 (w), 1564
(m), 1480 (m), 1450 (m), 1389 (m), 1368 (w), 1342 (m), 1300 (m),
1240 (m), 1198 (w), 1185 (m), 1148 (m), 1102 (m), 1068 (s), 1019
(m), 967 (w), 915 (m), 883 (m), 876 (m), 858 (m), 782 (m), 728
(m), 656 (m), 605 (m). Attempts to get NMR spectra of the
complex failed due to lack of locking signals for the strong
paramagnetic property of the complex. Anal. Calcd for
Preparation of {[η5:η2:η1-2-(2,6-iPr2C6H3NHCHD)C4H3N]-
Li2N(SiMe3)2}2 (6). To a toluene solution (10 mL) of 2--
(2,6-iPr2C6H3NHCHD)C4H3NH (2a) (0.969 g, 3.8 mmol) was
added a toluene (20 mL) solution of (Me3Si)2NLi (1.908 g, 11.4
mmol) at room temperature. After the reaction mixture was
stirred at 100 °C for 48 h, the solvent was evaporated under
reduced pressure. The residue was extracted with n-hexane
(10 mL). The colorless crystals were obtained upon standing
the solution at room temperature for 12 h (1.01 g, 62%). Mp:
93-94 °C. 1H NMR (300 MHz, C6D6): δ 7.06 (s, 2H, C4H3N),
6.96-6.86 (m, 6H, C6H3), 6.32 (s, 2H, C4H3N), 5.96 (s, 2H,
C4H3N), 4.03 (br, 2H, CHD), 3.93 (br, 2H, CHMe2), 3.10 (br,
2H, CH(CH3)2), 2.13 (br, 2H, NH), 0.95 (s, 24H, CH(CH3)2),
0.15 (s, 36H, Si(CH3)3). 13C NMR (75.0 MHz, C6D6): δ 140.3
(C6H3), 139.3 (C4H3N), 137.3 (C6H3), 128.1 (C6H3), 123.9
(C6H3), 121.8 (C4H3N), 106.4 (C4H3N), 102.6 (C4H3N), 50.6,
50.3, 50.0 (CHD), 25.6 (CHMe2), 21.7 (CH3), 3.5 (SiMe3). IR