Inorganic Chemistry
Article
using the residual solvent resonances and are reported relative to TMS.
Lanthanide metal analysis was carried out by complexometric
titration.31 C, H, N elemental combustion analysis was performed in
the microanalytical laboratory of IOMC.
concentration of the toluene solution at room temperature resulted
in the formation of red crystals. The mother liquid was decanted, and
the crystals were washed with cold hexane and dried in a vacuum for
30 min. Complex 2Ca was isolated in 95% yield (0.299 g).1H NMR
(400 MHz, C6D6) δ = 0.09 (s, 18H, SiMe3), 1.40 (m, 4H, β-CH2
THF), 1.71 (s, 3H, CH3), 2.10 (s, 3H, CH3 toluene), 2.27 (s, 3H,
CH3), 2.38 (s, 3H, CH3), 2.59 (s, 3H, CH3), 3.38 (s, 3H, OMe), 3.56
(m, 4H, α-CH2 THF), 4.74 (d, 3JHH = 7.5 Hz, 1H m-Py), 5.58 (d, 3JHH
= 8.5 Hz, 1H m-Py), 5.75 (d, 3JHH = 8.2 Hz, 1H p-Py), 6.53 (dd, 3JHH
= 16.9, 8.4 Hz, 2H Ar), 6.61 (s, 2H Ar), 6.64 (t, 3JHH = 6.7 Hz, 2H Ar),
6.81 (d, 3JHH = 7.4 Hz, 1H Ar), 6.87 (d, 3JHH = 7.0 Hz, 1H Ar), 7.03−
6.97 (complex m, 5H Ar), 7.05 (d, 3JHH = 7.2 Hz, 2H). 13C NMR (101
MHz, C6D6) δ = 2.2 (CH3, SiMe3), 17.7 (CH3), 18.0 (CH3), 18.1
(CH3), 20.4 (CH3), 21.1 (CH3 toluene), 25.5 (β-CH2 THF), 56.8
(OMe), 67.5 (α −CH2 THF), 92.9 (m-Py), 103.0 (m-Py), 111.2 (p-
Py), 121.4, 121.5, 124.5, 125.3, 128.2, 128.6, 128.9, (C Ar), 132.2 (o-C
C6H3Me2), 133.6 (o-C C6H3Me2), 137.3 (o-C C6H3Me2), 138.2 (o-C
Py), 138.9 (o-C Py), 140.8 (o-C C6H3Me2), 149.9 (o-C, C6H4OMe),
150.5 (i-C, C6H3Me2), 150.8 (i-C, C6H3Me2), 165.1 (o-C, Py).
19F{1H} NMRδ = −58.2. IR (Nujol, KBr, ν/cm−1): 1927 (w),
1783(w), 1660 (m), 1616 (s), 1603 (s), 1587 (s), 1574 (s), 1530 (s),
1495 (s), 1460 (s), 1377 (s), 1350 (s), 1288 (s), 1250 (s),1225 (s),
1188 (s), 1148 (s), 1113 (s), 1095 (s), 1049 (s), 1030 (s), 1005 (s),
977 (s), 926 (s), 881 (s), 821 (s), 772 (s), 746 (s), 716 (s), 692 (w),
662 (w), 619 (w), 608 (w), 590 (w), 565 (w), 510(w). Elem. Anal.
Calc. for C47H62CaF3N5O2Si2 (882,27 g/mol): C 63.98; H 7.08; Ca
4.54; N 7.94. Found: C 63.88; H 7.13; Ca 4.50; N 7.99.
Synthesis of [L1YbN(SiMe3)2(THF)] (1Yb). A solution of L1H
(0.165 g, 0.317 mmol) in toluene (10 mL) was added to a solution of
Yb[N(SiMe3)2](THF)2 (0.202 g, 0.317 mmol) in toluene (10 mL) at
room temperature. The color of the reaction mixture changed
immediately from red to brownish-black. Reaction mixture was stirred
for 1 h at room temperature. The volatiles were then removed under
reduced pressure, and the solid residue was dissolved in a toluene/
hexane mixture (1:1). Slow concentration of the solution at −20 °C
resulted in the formation of 1Yb as black crystals. The mother liquid
was decanted, and the crystals were washed with cold hexane and dried
in a vacuum for 30 min. Complex 1Yb was isolated in 60% yield (0.180
g).1H NMR (400 MHz, C6D6) δ = 0.08, 0.36 (s, together 18H,
SiMe3), 1.38 (compl. m, 12H, CH3CH and 4H, β-CH2 THF), 2.10 (s,
6H, CH3), 2.14 (s, 3H, CH3 toluene), 2.55 (s, 6H, CH3), 3.44 (m, 2H,
3
CHiPr), 3.50 (m, 4H, α-CH2 THF), 4.82 (d, JHH = 7.8 Hz, 1H, m-
3
Py), 5.53 (d, JHH = 8.5 Hz,1H, m-Py), 6.66 (m, 1H, p-Py), 6.77 (d,
3
3JHH = 7.2 Hz, 1H, p-CH, NC6H3iPr2), 6.83 (d, JHH Hz, 1H, p-CH,
NC6H3Me2), 7.00−7.16 (m, 5H, toluene+7H, NC6H3Me2 and
NC6H3iPr2). 13CNMR (101 MHz, C6D6) δ= 2.3, 5.9 (SiCH3), 18.0
(CH3), 19.6 (CH3), 21.0 (CH3), 21.05 (β-CH2 THF), 25.4 (CHCH3),
28.0 (CHCH3), 67.5 (α-CH2 THF), 91.9 (m-Py), 101.8(m-Py), 124.6,
125.3, 128.9, 129.3 (C toluene), 128.0 (p-C, NC6H3iPr2), 137.5 (m-C,
C6H3Me2 and NC6H3iPr2), 139.9 (p-Py), 149.2(i-C, C6H3Me2), 151.5
(C, o-Py), 159.2 (o-C, py), 165.3 (NC). IR (Nujol, KBr, ν/cm−1):
1938 (w), 1784 (w), 1653 (w), 1614 (s), 1580 (m), 1459 (s), 1377
(s), 1285 (s), 1253 (m), 1221 (s), 1176 (s), 1159 (s), 1128 (s), 971
(m), 928 (m), 837 (m), 826 (m), 767 (s), 747 (s), 721 (s), 671 (w),
656 (w), 608 (w), 580 (w), 560 (w), 491 (w). Elem. Anal. Calc. for
C45H67N5OSi2Yb•1/2C7H8 (969.32 g/mol): C 60.04; H 7.32; N 7.22;
Yb 17.84. Found: C 60.45; H 7.40; N 7.34; Yb 17.95.
Synthesis of [L3Ca(N(SiMe3)2)(THF)] (3Ca). A solution of L3H
(0.164 g, 0.324 mmol) in toluene (10 mL) was added to a solution of
Ca(N(SiMe3)2)(THF)2 (0.164 g, 0.324 mmol) in toluene. The color
of the reaction mixture changed immediately from pale-yellow to
bright-red. Reaction mixture was stirred for 1 h at room temperature.
The solvent was then removed under reduced pressure, and residue
was dissolved in fresh toluene. Slow concentration of the toluene
solution at room temperature resulted in the formation of red powder.
The mother liquid was decanted and the powder was washed with cold
hexane and dried in a vacuum for 30 min. Complex L3Ca(N-
(SiMe3)2)(THF) was isolated in 90% yield (0.270 g, 0.275 mmol). 1H
NMR (400 MHz, C6D6) 0.09 (s, 18H, SiMe3), 1.83 (s, 3H, CH3), 2.10
(s, 9H, CH3 toluene), 2.19 (s, 3H, CH3), 2.30 (s, 3H, CH3), 2.59 (s,
Synthesis of [L1CaN(SiMe3)2(THF)] (1Ca). A solution of L1H
(0.300 g, 0.579 mmol) in toluene (10 mL) was added to a solution of
Ca[N(SiMe3)2]2(THF)2 (0.292 g, 0.579 mmol) in toluene (10 mL).
The reaction mixture was stirred for 50 h at 50 °C. The volatiles were
then removed under reduced pressure, and the solid residue was
dissolved in mixture of solvents THF/hexane (1:3). Slow concen-
tration of THF/hexane solution at room temperature resulted in the
formation of yellowish-green crystals of 1Ca. The mother liquid was
decanted and the crystals were washed with cold hexane and dried in a
vacuum for 30 min. Complex 1Ca was isolated in 83% yield (0.345 g).
1H NMR (400 MHz, C6D6) δ = 0.09, 0.28 (s,18H, SiMe3), 1.26 (d,
3JHH = 7.0 Hz, 12H, CHCH3), 1.40 (m, 4H, β-CH2 THF), 1.93 (s, 3H,
CH3), 1.99 (s, 6H, CH3), 2.14 (s, 3H, CH3 toluene), 2.29 (s, 6H,
3
3
3H, CH3), 4.83 (d, JHH = 7.5 Hz, 1H m-Py), 5.64 (d, JHH = 8.5 Hz,
3
1H m-Py), 5.75 (d, J = 8.2 Hz, 1H m-Py), 6.53 (dd, JHH = 16.9, 8.4
Hz, 2H Ar), 6.54−7.14 (complex m, 23H Ar). 13C NMR (101 MHz,
C6D6) δ = 1.1, 2.3 (CH3, SiMe3), 17.9 (CH3), 21.1 (CH3 toluene),
25.4 (β-CH2 THF), 67.7 (α-CH2 THF), 94.9 (C, p-Py), 103.6 (C, m-
Py), 114.8, 115.0, 125.1, 125.3, 128.2, 128.4, 128.8, 128.9, 137.5, 138.1,
139.0, 139.5, 140.1(C Ar), 150.7 (i-C, Py), 165.1 (o-C, Py). 19F{1H}
NMR δ = 57.8, 127.2. IR (Nujol, KBr, ν/cm−1): 1956 (w), 1786 (w),
1655 (w), 1613 (s), 1530 (m), 1460 (s), 1377 (s), 1287 (s), 1250 (m),
1221 (s), 1188 (s), 1163 (s), 1144 (s), 1095 (s), 1032 (m), 977 (m),
932 (m), 923 (m), 862 (m), 850 (m), 837 (m), 825 (m), 778 (m),
768 (s), 748 (s), 732 (s), 721 (s), 696 (m), 671 (w), 651 (w), 620
(w), 606 (w), 586 (w), 560 (w), 497 (w), 465(m). Elem. Anal. Calc.
for C56H67CaF4N5Si2 (982,41 g/mol): C 68.46; H 6.87; Ca 4.08; N
7.13;.Found: C 68.50; H 6.90; Ca 4.03; N 7.08.
3
CH3), 3.15 (sept, JHH = 6.9 Hz, 2H, CHCH3), 3.56 (m, 4H, α-CH2
3
THF), 5.56 (d, 3JHH = 7.9 Hz, 1H, m-Py), 6.38 (d, JHH = 7.6 Hz,1H,
m-Py), 6.92 (complex m, 4H, NC6H3), 7.02 (complex m, 5H, toluene
+4H, NC6H3), 7.10 (m, 2H, NC6H3). 13C NMR (101 MHz, C6D6) δ
= 2.3, (CH3, SiMe3), 17.9 (CH3), 18.0 (CH3), 19.0 (CH3), 23.1 (CH3
iPr), 23.4 (CH3 iPr), 25.8 (CH3, iPr), 25.5 (β-CH2 THF), 28.1 (CH,
iPr), 67.5 (α −CH2 THF), 99.5 (m-Py), 104.5 (m-Py), 122.9, 126.4,
127.3, 128.2, 128.4, 136.5,137.2, 137.3, 137.4, 138.8 (C, C6H3Me2 and
NC6H3iPr2), 142.4 (C, p-Py), 145.8 (i-C, C6H3Me2), 155.1 (o-C, py),
156.0 (o-C, py), 156.4 (NC). IR (Nujol, KBr, ν/cm−1): 1940 (w),
1782 (w), 1649 (w), 1614 (s), 1580 (m), 1455 (s), 1377 (s), 1282 (s),
1259 (m), 1221 (s), 1171(s), 1155 (s), 1108 (s), 971 (m), 926 (m),
837 (m), 825 (m), 767 (s), 747 (s), 721 (s), 671 (w), 653 (w), 610
(w), 580 (w), 560 (w), 490 (w). Elem. Anal. Calc. for
C45H67CaN5OSi2·C7H8 (882.43 g/mol): C 70.07; H 8.49; Ca 4.53;
N 7.93. Found: C 69.79; H 8.61; Ca 4.57; N 8.02.
Synthesis of [L4Ca(N(SiMe3)2)(THF)] (4Ca). A solution of
L4(0.115g, 0.236 mmol) in toluene (10 mL) was added to a solution
of Ca(N(SiMe3)2)(THF)2 (0.119 g, 0.236 mmol) in toluene. The
color of the reaction mixture changed immediately from pale-yellow to
bright-red. Reaction mixture was stirred for 1 h at room temperature.
The solvent was then removed under reduced pressure, and residue
was dissolved in fresh hexane. Slow concentration of the hexane
solution at room temperature resulted in the formation of red powder.
The mother liquid was decanted and the powder was washed with cold
hexane and dried in a vacuum for 30 min. Complex L4Ca(N-
(SiMe3)2)(THF) was isolated in 84% yield (0.168g, 0.198 mmol).1H
NMR (400 MHz, C6D6) 0.09 (s, 18H, SiMe3), 2.03 (m, 4H, β-CH2
THF), 1.95 (s, 3H, CH3), 2.10 (s, 3H, CH3 toluene), 2.31 (s, 6H,
Synthesis of [L2Ca(N(SiMe3)2)(THF)] (2Ca). A solution of L2H
(0.182 g, 0.360 mmol) in toluene (10 mL) was added to a solution of
Ca[N(SiMe3)2]2(THF)2 (0.185 g, 0.360 mmol) in toluene (10 mL).
The color of the reaction mixture changed immediately from pale-
yellow to bright-red. Reaction mixture was stirred for 1 h at room
temperature. The volatiles were then removed under reduced pressure,
and the solid residue was redissolved in fresh toluene. Slow
CH3), 2.40 (s, 3H, CH3), 3.82 (m, 4H, α-CH2 THF), 4.76 (d, 3JHH
7.5 Hz, 1H, m-Py), 5.50 (d, 3JHH = 8.5 Hz, 1H, m-Py), 5.69 (d, 3JHH
=
=
H
Inorg. Chem. XXXX, XXX, XXX−XXX