Organometallics
Article
(ppm) 7.50 (d, 3JH,H = 7.5 Hz, 8 H, o-Ph), 7.25 (t, 3JH,H = 7.5 Hz, 8 H,
m-Ph), 7.08 (t, 3JH,H = 7.5 Hz, 4 H, p-Ph), 4.83 (q, 3JH,H = 6.6 Hz, 4 H,
CH), 1.73 (d, JH,H = 6.6 Hz, 12 H, CH3), 1.06 (s, 18 H, C(CH3)3).
85), 481 ([(PETA)Lu]+, 2), 308 ([PETA]+, 2), 293 ([PETA − CH3]+,
100), 203 ([(PETA) − PhEt]+, 10), 120 ([PhEtN]+, 53), 105
([PhEt]+, 100), 91 ([Bz]+, 7), 77 ([Ph]+, 21), 57 ([tBu]+, 30). IR
(ATR): ν (cm−1) 3059 (w), 3025 (w), 2963 (w), 2922 (w), 2869 (w),
1629 (m), 1551 (w), 1489 (m), 1447 (m), 1401 (w), 1365 (w), 1326
(w), 1298 (w), 1253 (w), 1187 (w), 1152 (w), 1068 (w), 1022 (w),
909 (w), 754 (m), 696 (s), 616 (w), 544 (w). Anal. Calcd for
C42H54N4ClLu (825.32 g/mol): C, 61.12; H, 6.59; N, 6.79. Found: C,
61.51; H, 6.52; N, 6.54.
[{(S)-PETA}2Sm(μ-Cl)2Li(thf)2] (6). THF (ca. 10 mL) was condensed
at −78 °C onto a mixture of 163 mg (0.64 mmol) of SmCl3 and 400
mg (1.27 mmol) of (S)-LiPETA, and the reaction mixture was stirred
overnight at room temperature. The solvent was removed in vacuo,
and the residue was extracted with 10 mL of toluene. The solvent was
removed in vacuo, and the residue was washed with 10 mL of n-
pentane. The product was crystallized from THF/n-pentane to yield
148 mg (0.15 mmol, 24%) of 6. MS (EI, 70 eV): m/z (%) 843 ([M]+,
1), 766 ([M − LiCl2]+, 15), 709 ([M − LiCl2 − tBu]+, 23), 496
([(PETA)SmCl]+, 20), 308 ([PETA]+, 100), 293 ([PETA − CH3]+,
100), 251 ([PETA − tBu]+, 65), 203 ([(PETA) − PhEt]+, 100), 189
([(PETA) − PhEtCH3]+, 100), 147 ([(PETA) − PhEt − tBu]+, 100),
120 ([PhEtN]+, 100), 105 ([PhEt]+, 100), 91 ([Bz]+, 100), 77 ([Ph]+,
100), 57 ([tBu]+, 100). IR (ATR): ν (cm−1) 3058 (w), 3024 (w), 2963
(w), 2922 (w), 2871 (w), 1625 (m), 1551 (w), 1489 (m), 1447 (m),
1398 (w), 1364 (w), 1301 (w), 1275 (w), 1252 (w), 1185 (w), 1147
(w), 1068 (w), 1044 (w), 1024 (w), 908 (w), 845 (w), 755 (m), 697
(s), 665 (w), 611 (w), 586 (w), 545 (w). Anal. Calcd for
C50H70LiN4O2Cl2Sm (987.32 g/mol): C, 60.82; H, 7.15; N, 5.67.
Found: C, 60.37; H, 7.09; N, 5.57.
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13C{1H} NMR (75 MHz, C6D6, 298 K): δ (ppm) 187.3 (NCN), 148.2
(i-Ph), 128.6 (Ph), 127.0 (Ph), 126.5 (Ph), 55.9 (CH), 41.2
(C(CH3)3), 30.0 (C(CH3)3), 27.5 (CH3). EI-MS (70 eV): m/z (%)
694 ([M]+, 6), 659 ([M − Cl]+, 13), 607 ([M − tBu − 2 CH3]+, 10),
601 ([M − Cl − tBu]+, 21), 589 ([M − PhEt]+, 100), 501 (17), 449
([M − 2 tBu − PhEtNC]+, 7), 425 (15), 410 (14). IR (ATR): ν
(cm−1) 3482 (w), 3082 (w), 3059 (w), 3024 (w), 2964 (m), 2925 (w),
2870 (w), 1947 (w), 1872 (w), 1803 (w), 1772 (w), 1631 (m), 1602
(w), 1583 (w), 1543 (w), 1490 (m), 1476 (w), 1446 (w), 1430 (w),
1401 (w), 1361 (m), 1336 (w), 1297 (m), 1253 (w), 1189 (w), 1156
(m), 1074 (w), 1026 (m), 966 (w), 909 (w), 841 (w), 791 (w), 758
(m), 697 (vs), 670 (w), 624 (w), 612 (w), 587 (w), 537 (w), 509 (w),
476 (m), 417 (w), 365 (s). Anal. Calcd for C42H54N4ClSc·1/3 LiCl
(709.36 g/mol): C, 71.10; H, 7.67; N, 7.90. Found: C, 71.12; H, 7.38;
N, 7.93.
[{(S)-PETA}2YCl]2 (3). THF (ca. 10 mL) was condensed at −78 °C
onto a mixture of 79 mg (0.406 mmol) of YCl3 and 255 mg (0.812
mmol) of (S)-LiPETA, and the reaction mixture was stirred overnight
at room temperature. The solvent was removed in vacuo, and the
residue was extracted with 10 mL of hot toluene. The solvent was
removed in vacuo, and the product was crystallized from hot toluene
to yield 123 mg (0.166 mmol, 41%) of 3. 1H NMR (300 MHz, C6D6,
298 K): δ (ppm) 7.73−7.70 (m, 4 H, Ph), 7.38−7.33 (m, 4 H, Ph),
3
7.16−7.08 (m, 12 H, Ph), 5.33 (q, JH,H = 5.7 Hz, 2 H, CH), 4.21 (q,
3JH,H = 6.0 Hz, 2 H, CH), 2.04 (d, 3JH,H = 6.3 Hz, 6 H, CH3), 1.18 (s,
3
18 H, C(CH3)3), 0.68 (d, JH,H = 6.3 Hz, 6 H, CH3). 13C{1H} NMR
2
Tris(amidinate)yttrium Complex. [{(S)-PETA}3Y] (7). Toluene
(ca. 10 mL) was condensed at −78 °C onto a mixture of 300 mg
(0.406 mmol) of 3 and 128 mg (0.406 mmol) of (S)-LiPETA, and the
reaction mixture was refluxed overnight. The solvent was removed in
vacuo, and the residue was extracted with 10 mL of n-pentane. The
product was crystallized from toluene/n-pentane to yield 43 mg (0.043
(75 MHz, C6D6, 298 K): δ (ppm) 184.2 (d, JC,Y = 1.5 Hz, NCN),
150.8 (i-Ph), 146.7 (i-Ph), 127.9 (Ph), 127.1 (Ph), 125.9 (Ph), 56.0
(CH), 54.6 (CH), 41.1 (d, 3JC,Y = 3.9 Hz, C(CH3)3), 30.5 (C(CH3)3),
29.5 (CH3), 25.5 (CH3). IR (ATR): ν (cm−1) 3482 (w), 3083 (w),
3059 (w), 3023 (w), 2966 (m), 2923 (w), 2870 (w), 1945 (w), 1877
(w), 1807 (w), 1631 (m), 1601 (w), 1583 (w), 1549 (w), 1491 (m),
1446 (w), 1420 (w), 1406 (m), 1363 (m), 1322 (w), 1299 (m), 1271
(w), 1253 (w), 1220 (w), 1187 (m), 1151 (m), 1069 (m), 1027 (m),
968 (w), 909 (w), 843 (w), 794 (w), 753 (m), 698 (vs), 673 (w), 613
(w), 589 (w), 529 (w), 500 (w), 456 (w), 396 (m), 363 (w). Anal.
Calcd for C42H54N4ClY (739.26 g/mol): C, 68.24; H, 7.36; N, 7.58.
Found: C, 67.88; H, 7.23; N, 7.23.
[{(S)-PETA}2NdCl]2 (4). THF (ca. 10 mL) was condensed at −78 °C
onto a mixture of 95 mg (0.378 mmol) of NdCl3 and 237 mg (0.755
mmol) of (S)-LiPETA, and the reaction mixture was stirred overnight
at room temperature. The solvent was removed in vacuo, and the
residue was extracted with 10 mL of hot toluene. The solvent was
removed in vacuo, and the residue was washed with 10 mL n-pentane.
The product was crystallized from hot toluene to yield 80 mg (0.101
mmol, 27%) of 4. IR (ATR): ν (cm−1) 3482 (w), 3060 (w), 3026 (w),
2963 (m), 2922 (w), 2869 (w), 1967 (w), 1869 (w), 1717 (w), 1699
(w), 1684 (w), 1653 (w), 1630 (s), 1583 (w), 1558 (w), 1541 (w),
1490 (s), 1476 (m), 1448 (m), 1397 (w), 1363 (m), 1277 (w), 1252
(w), 1191 (m), 1147 (w), 1066 (m), 1026 (m), 937 (w), 909 (w), 843
(w), 755 (m), 697 (vs), 668 (w), 613 (w), 543 (m), 368 (w). Anal.
Calcd for C42H54N4ClNd (794.60 g/mol): C, 63.48; H, 6.85; N, 7.05.
Found: C 63.71; H, 6.89; N, 6.96.
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mmol, 11%) of 7. H NMR (400 MHz, C6D6, 298 K): δ (ppm) 7.49
(br, 12 H, Ph), 7.02−6.91 (m, 18 H, Ph), 5.26 (br q, 3JH,H = 5.6 Hz, 6
H, CH), 1.88 (br, 18 H, CH3), 1.21 (s, 27 H, C(CH3)3). 13C{1H}
NMR (101 MHz, C6D6, 298 K): δ (ppm) 184.2 (NCN), 149.4 (i-Ph),
128.4 (Ph), 127.4 (Ph), 125.9 (Ph), 56.9 (CH), 41.3 (C(CH3)3), 31.7
(C(CH3)3), 28.3 (CH3). − EI-MS (70 eV): m/z (%) 931 ([M − Ph]+,
8), 700 ([M − PETA]+, 81), 644 ([M − PETA − tBu]+, 65), 598 ([M
− PETA − PhEt]+, 100), 541 ([M − PETA − PhEt − tBu]+, 11).
Anal. Calcd for C63H81N6Y·1/2C7H8 (1057.33 g/mol): C, 75.54; H,
8.10; N, 7.95. Found: C, 75.79; H, 8.17; N, 7.99.
Amido Complex. [{(S)-PETA}2Y{N(SiMe3)2}] (8). Toluene (ca. 10
mL) was condensed at −78 °C onto a mixture of 428 mg (0.579
mmol) of 3 and 115 mg (0.579 mmol) of KN(SiMe3)2, and the
reaction mixture was stirred overnight at room temperature. The
solvent was removed in vacuo, and the residue was extracted with 10
mL of n-pentane. The solvent was removed in vacuo, and the product
was crystallized from a saturated n-heptane solution to yield 410 mg
(0.474 mmol, 82%) of 8. 1H NMR (400 MHz, C6D6, 298 K): δ (ppm)
7.45−7.44 (m, 4 H, Ph), 7.28−7.27 (m, 4 H, Ph), 7.13−6.92 (m, 12 H,
3
3
Ph), 5.07 (q, JH,H = 6.0 Hz, 4 H, CH), 1.66 (d, JH,H = 6.0 Hz, 6 H,
3
CH3), 1.43 (d, JH,H = 6.0 Hz, 6 H, CH3), 1.16 (s, 18 H, C(CH3)3),
0.53 (s, 18H, Si(CH3)3). 13C{1H} NMR (101 MHz, C6D6, 298 K): δ
[{(S)-PETA}2LuCl]2 (5). THF (ca. 10 mL) was condensed at −78 °C
onto a mixture of 179 mg (0.64 mmol) of LuCl3 and 400 mg (1.27
mmol) of (S)-LiPETA, and the reaction mixture was stirred overnight
at room temperature. The solvent was removed in vacuo, and the
residue was extracted with 10 mL of hot toluene. The solvent was
removed in vacuo, and the residue was washed with 10 mL of n-
pentane. The product was crystallized from hot toluene to yield 202
2
(ppm) 183.4 (d, JC,Y = 1.5 Hz, NCN), 149.1 (i-Ph), 147.2 (i-Ph),
127.3 (Ph), 126.9 (Ph), 126.8 (Ph), 126.5 (Ph), 126.1 (Ph), 56.2
(CH), 54.9 (CH), 41.2 (d, 3JC,Y = 3.9 Hz, C(CH3)3), 30.9 (C(CH3)3),
28.0 (CH3), 26.8 (CH3), 5.9 (Si(CH3)3). EI-MS (70 eV): m/z (%) 863
([M]+, 1), 848 ([M − Me]+, 3), 703 ([M − N(SiMe3)2]+, 12), 556
([M − PETA]+, 91), 368 (22), 308 ([HPETA]+, 88), 293 ([HPETA −
Me]+, 47), 236 ([HPETA − Me − tBu]+, 56), 203 ([HPETA −
PhEt]+, 96), 189 ([HPETA − PhEt − Me]+, 66), 146 ([HPETA −
PhEt − tBu]+, 96), 130 ([PETA − PhEt − tBu − Me]+, 73), 120
([PhEtNH]+, 100), 105 ([PhEt]+, 99). IR (ATR): ν (cm−1) 3483 (w),
3061 (w), 3024 (w), 2964 (s), 1945 (w), 1886 (w), 1805 (w), 1771
(w), 1633 (m), 1602 (w), 1491 (m), 1446 (w), 1422 (m), 1403 (vs),
1362 (m), 1319 (w), 1296 (s), 1273 (w), 1242 (m), 1187 (m), 1142
1
mg (0.25 mmol, 39%) of 5. H NMR (300 MHz, D8-THF, 332 K): δ
(ppm) 7.62 (m, 8 H, o-Ph), 6.96 (m, 12 H, m,p-Ph), 5.20 (q, 3J = 6.7
3
Hz, 4 H, CH), 1.62 (d, J = 6.7 Hz, 12 H, CH3), 1.12 (s, 18 H, tBu).
13C{1H} NMR (75 MHz, D8-THF, 332 K): δ (ppm) 181.3 (NCN),
150.0 (i-Ph), 127.3 (m-Ph), 127.2 (o-Ph), 124.6 (p-Ph), 55.9 (CH),
40.8 (tBu-C), 30.9 (tBu-CH3), 25.3 (CH3). MS (EI, 70 eV): m/z (%)
785 ([M − Cl]+, 80), 718 ([M − PhEt]+, 80), 516 ([M − (PETA)]+,
J
Organometallics XXXX, XXX, XXX−XXX