Organometallics
Article
1
H− Si HMBC or HMQC experiments, and 1JSiH values were
29
C H O Si Yb: C, 36.01; H, 8.31. Found: C, 36.83; H, 8.40. Mp:
24
66
3
8
1
measured from satellites in the H NMR spectra. Elemental analyses
were performed using a PerkinElmer 2400 Series II CHN/S
instrument. X-ray diffraction data were collected on a Bruker APEX
II diffractometer.
80−85 °C (dec).
Mg{Si(SiHMe
was added to a pentane suspension of MgBr
and the mixture was stirred for 24 h at room temperature.
KSi(SiHMe ) (0.0820 g, 0.335 mmol) was added at −30 °C. The
2 3
) } py (1·py
2 3 2 2 2
). Pyridine (27.2 μL, 0.340 mmol)
(0.0310 g, 0.168 mmol),
2
2
0a
KSi(SiHMe ) . KSi(SiHMe ) was previously communicated.
2
3
2 3
solution was stirred for 3 h at −30 °C and then filtered. The pentane
solution was allowed to stand at −30 °C, and this gave a yellow solid
The full experimental details and characterization data are reported
(
and KOtBu (3.95 g, 0.027 mol) were dissolved in a minimal quantity
of benzene (ca. 10 mL). The yellow homogeneous solution was
allowed to stand for 0.5 h. Over that time, the product precipitated as a
white solid. The product was further precipitated by addition of
pentane, and the solvent was decanted. The solid product was washed
with pentane (3 × 5 mL). An additional quantity of the product was
obtained by concentrating the benzene/pentane supernatant.
2
4
1
which was isolated by filtration (0.0660 g, 0.111 mmol, 65.9%). H
2 4
NMR (benzene-d , 600 MHz): δ 8.62 (br, 4 H, o-C H N), 6.79 (t, 2
6
5
5
3
H, p-C H N), 6.59 (br, 4 H, m-C H N), 4.66 (sept, 6 H, J = 4.2
Hz, J = 169 Hz, SiHMe ), 0.51 (d, 36 H, J
C{ H} NMR (benzene-d , 150 MHz): δ 149.62 (o-C H N), 139.74
5
5
5
5
HH
1
3
SiH
2
HH
= 4.2 Hz, SiHMe2).
1
3
1
6
5
5
2
9
(
p-C H N), 125.45 (m-C H N), 0.74 (SiHMe ). Si NMR (benzene-
5 5 5 5 2
d , 119.3 MHz): δ −26.3 (SiHMe ), −182.2 (Si(SiHMe ) ). IR (KBr,
6
2
2 3
−1
cm ): ν 2957 (s), 2900 (m), 2067 (s, ν ), 1595 (w), 1414 (m),
SiH
1
250 (s), 1022 (s), 887 (s), 858 (s), 834 (s), 797 (m), 752 (w), 699
(m), 677 (m), 650 (s), 623 (m). Anal. Calcd for C H MgNSi
8
Recrystallization from toluene at −30 °C gave a white crystalline
solid (5.99 g, 0.024 mol, 90.7%). H NMR (benzene-d , 600 MHz): δ
1
17 47
6
3
1
(corresponding to the loss of 1 py during analysis): C, 39.68; H, 9.21;
N, 2.72. Found: C, 40.02; H, 9.65; N, 2.28. Mp: 47−49 °C (dec).
Ca{Si(SiHMe ) } py (2·py ). A mixture of CaI (0.0500 g, 0.170
4
.22 (sept, 3 H, J = 4.5 Hz, J = 152 Hz, SiHMe ), 0.56 (d, 18 H,
JHH = 4.5 Hz, SiHMe ). C{ H} NMR (benzene-d , 150 MHz): δ
HH SiH 2
3
13
1
2
6
29
2
3 2
4
4
2
2
(
2
(
.47 (SiHMe2). Si NMR (benzene-d , 119.3 MHz): δ −23.8
−1
6
mmol), pyridine (55.0 μL, 0.680 mmol), and pentane (10 mL) was
SiHMe ), −202.3 (Si(SiHMe ) ). IR (KBr, cm ): ν 2959 (s),
2
2 3
stirred for 24 h, and then KSi(SiHMe ) (0.0830 g, 0.339 mmol) was
2
3
894 (s), 2020 (s, νSiH), 1419 (m), 1242 (s), 1041 (s), 872 (s), 766
added. The reaction mixture was stirred for 3 h, filtered, and
m), 685 (m), 645 (m). Anal. Calcd for C H KSi : C, 29.45; H, 8.65.
6 21 4
crystallized from the pentane solution at −30 °C, yielding a yellow
Found: C, 29.20; H, 8.51. Mp: 123−125 °C.
1
solid (0.0760 g, 0.0990 mmol, 58.7%). H NMR (benzene-d , 400
6
Mg{Si(SiHMe ) } THF (1·THF ). MgBr (0.0380 g, 0.200 mmol)
2
3 2
2
2
2
3
3
MHz): δ 8.92 (d, 8 H, J = 4.2 Hz, o-C H N), 6.87 (t, 4 H, J =
HH
5
5
HH
and KSi(SiHMe ) (0.100 g, 0.409 mmol) were dissolved in THF (10
mL). This solution was stirred for 24 h and then was filtered.
Evaporation of the solvent provided a yellow oil, which was dissolved
2
3
3
7
6
.2 Hz, p-C H N), 6.75 (t, 8 H, J = 6.0 Hz, m-C H N), 4.59 (sept,
5 5 HH 5 5
3
1
3
H, J = 4.1 Hz, J = 160 Hz, SiHMe ), 0.43 (d, 36 H, J = 4.1
Hz, Si(SiHMe ) ). C{ H} NMR (benzene-d , 150 MHz): δ 150.60
HH
SiH
2
1
3
1
2
3
6
in pentane and cooled to −30 °C to give a white solid (0.0652 g, 0.112
1
(o-C
5
H
5
N), 138.52 (p-C
N{ H} NMR (benzene-d
benzene-d , 119.3 MHz): δ −23.3 (SiHMe ), −199.3 (Si(SiHMe ) ).
5
H
5
N), 124.85 (m-C
5 5 2
H N), 1.33 (SiHMe ).
mmol, 55.1%). H NMR (benzene-d , 600 MHz): δ 4.58 (sept, 6 H,
6
15
1
29
3
1
6
, 60.6 MHz): δ −79.6. Si NMR
JHH = 4.2 Hz, J = 169 Hz, SiHMe ), 3.70 (br, 8 H, α-THF), 1.32
br, 8 H, β-THF), 0.56 (d, 36 H, JHH = 4.2 Hz, SiHMe2). C{ H}
SiH
2
(
3
13
1
6
2
2 3
(
−1
IR (KBr, cm ): ν 2963 (s), 2853 (m), 2100 (s, ν ), 1878 (w), 1598
SiH
NMR (benzene-d , 150 MHz): δ 70.44 (α-THF), 25.53 (β-THF),
0
(
2
6
(
(
m), 1440 (s), 1342 (w), 1248 (s), 1216 (w), 1150 (w), 1008 (s), 889
s), 861 (s), 840 (s), 825 (m), 806 (m), 786 (m), 734 (m). Anal.
2
9
.90 (SiHMe2). Si NMR (benzene-d , 119.3 MHz): δ −27.5
6
−1
SiHMe ), −182.3 (Si(SiHMe ) ). IR (KBr, cm ): ν 2953 (s),
2
2 3
Calcd for C H CaN Si (corresponding to the loss of 1 pyridine
27
57
3
8
896 (s), 2064 (s, νSiH), 1460 (w), 1424 (w), 1244 (s), 1023 (s), 862
during analysis): C, 47.10; H, 8.34; N, 6.10. Found: C, 46.84; H, 8.07;
N, 6.09. Mp: 83−85 °C (dec).
(
s), 745 (m), 687 (s), 646 (s), 445 (w). Anal. Calcd for
C H MgOSi (corresponding to the loss of 1 THF during analysis):
1
6
50
8
Mg{Si(SiHMe ) } DMAP (1·DMAP ). Mg{Si(SiHMe ) } THF
2
2
3 2
2
2
2
3
2
C, 37.86; H, 9.93. Found C, 37.68; H, 9.62. Mp: 60−63 °C.
Ca{Si(SiHMe ) } THF (2·THF ). CaI (0.150 g, 0.510 mmol) and
KSi(SiHMe ) (0.250 g, 1.02 mmol) were stirred in THF (15 mL) for
(
0.0240 g, 0.0414 mmol) and DMAP (0.0100 g, 0.0819 mmol) were
2
3 2
3
3
2
stirred in benzene (10 mL) for 1 h. The volatile materials were
evaporated under reduced pressure, and the residue was recrystallized
from pentane at −30 °C to give a white solid (0.0150 g, 0.0221 mmol,
2
3
4
8 h. The volatile materials were removed under reduced pressure,
leaving a cream-colored residue. The product was extracted with
pentane and recrystallized from a concentrated pentane solution at
−
(
Hz, SiHMe ), 3.84 (br, 12 H, α-THF), 1.48 (br, 12 H, β-THF), 0.57
(
1
3
2
6.6%). H NMR (benzene-d , 600 MHz): δ 8.47 (d, 4 H, J = 5.4
6 HH
3
Hz, NC H NMe ), 6.03 (d, 4 H, J = 4.2 Hz, NC H NMe ), 4.85
1
5
4
2
HH
5
4
2
30 °C to give a white solid (0.187 g, 0.280 mmol, 63.7%). H NMR
benzene-d , 400 MHz): δ 4.56 (sept, 6 H, J = 4.0 Hz, J = 162
3
1
(
sept, 6 H, J = 4.2 Hz, J = 167 Hz, SiHMe ), 1.98 (s, 12 H,
HH SiH 2
3
1
3
13
1
6
HH
SiH
NC H NMe ), 0.67 (d, 36 H, J = 4.2 Hz, SiHMe2). C{ H} NMR
5 4 2 HH
2
(benzene-d , 150 MHz): δ 155.03 (ipso-NC H NMe ), 150.02 (o-
6 5 4 2
3
13
1
d, 36 H, J = 4.0 Hz, SiHMe2). C{ H} NMR (benzene-d , 100
H
H
6
NC H NMe ), 107.19 (m-NC H NMe ), 38.54 (NC H NMe ), 1.05
5 4 2 5 4 2 5 4 2
29
MHz): δ 69.78 (α-THF), 25.63 (β-THF), 1.76 (SiHMe2). Si NMR
benzene-d , 119.3 MHz): δ −24.6 (SiHMe ), −194.6 (Si(SiHMe ) ).
15
1
(SiHMe2). N{ H} NMR (benzene-d , 60.6 MHz): δ −327.3
6
(
29
6
2
2
3
(NC H NMe ). Si NMR (benzene-d , 119.3 MHz): δ −26.8
5
4
2
6
−1
IR (KBr, cm ): ν 2958 (s), 2894 (s), 2045 (s, ν ), 1421 (w), 1620
−1
SiH
(SiHMe ), −184.3 (Si(SiHMe ) ). IR (KBr, cm ): ν 2945 (s),
2
2 3
(
(
9
s), 1032 (s), 859 (s), 681 (w). Anal. Calcd for C H CaO Si
20 58 2 8
2083 (s, ν ), 1616 (s), 1536 (s), 1445 (m), 1389 (m), 1231 (s), 1114
SiH
corresponding to the loss of 1 THF during analysis): C, 40.34; H,
.82. Found: C, 40.28; H, 9.53. Mp: 104−106 °C.
Yb{Si(SiHMe ) } THF (3·THF ). KSi(SiHMe ) (0.573 g, 2.34
(
(
w), 1063 (w), 1003 (s), 951 (w), 881 (m), 854 (m), 810 (s), 760
w), 675 (w), 637 (m). Anal. Calcd for C H MgN Si (correspond-
19
52
2
8
2
3 2
3
3
2
3
ing to the loss of 1 DMAP during analysis): C, 40.92; H, 9.40; N, 5.02.
Found: C, 41.18; H, 9.36; N, 4.62. Mp: 92−94 °C (dec).
mmol) and YbI (0.500 g, 1.17 mmol) were stirred in 10 mL of THF
2
at room temperature for 24 h. The resulting reddish orange suspension
was evaporated to dryness under reduced pressure and extracted with
pentane (3 × 5 mL). The extracts were combined, concentrated, and
recrystallized overnight at −40 °C to obtain reddish orange crystals of
Yb{Si(SiHMe ) } THF (0.29 g, 0.36 mmol, 30.9%). H NMR
(
Ca{Si(SiHMe ) } DMAP (2·DMAP ). Ca{Si(SiHMe ) } THF
2
3 2
4
4
2
3
2
3
(0.200 g, 0.300 mmol) and DMAP (0.146 g, 1.20 mmol) were stirred
in toluene (10 mL) for 1 h. Crystallization from the reaction mixture at
1
−30 °C gave a pale yellow solid (0.189 g, 0.200 mmol, 67.2%). H
1
2
3
2
3
NMR (benzene-d , 600 MHz): δ 8.93 (br, 8 H, NC H NMe ), 6.28
6
5
4
2
1
3
1
benzene-d , 600 MHz): δ 4.63 (m, 6 H, J = 160 Hz, SiHMe ),
.73 (m, 12 H, OCH ), 1.42 (m, 12 H, CH ), 0.61 (d, 36 H, J = 4.0
(br, 8 H, NC H NMe ), 4.94 (sept, 6 H, J = 4.2 Hz, J = 161 Hz,
6
SiH
2
5 4 2 HH SiH
3
3
3
SiHMe ), 2.05 (s, 24 H, NC H NMe ), 0.69 (d, 36 H, J = 4.2 Hz,
2 5 4 2 HH
SiHMe2). C{ H} NMR (benzene-d , 150 MHz): δ 155.14 (ipso-
2
2
HH
1
3
1
13
1
Hz, SiMe2). C{ H} NMR (benzene-d , 150 MHz): δ 69.23
(
(
IR (KBr, cm ): ν 2953 (s), 2891 (s), 2045 (w, ν ), 1460 (w), 1243
(
6
6
29
1
OCH CH ), 25.68 (OCH CH ), 1.85 (SiMe ). Si{ H} NMR
benzene-d , 119 MHz): δ −23.99 (SiHMe ), −168.11 Si(SiHMe ).
NC H NMe ), 150.99 (o-NC H NMe ), 106.91 (m-NC H NMe ),
2
2
2
2
2
5
4
2
5
4
2
5
4
2
1
5
1
6
2
2
38.43 (NC H NMe ), 1.81 (SiHMe ). N{ H} NMR (benzene-d ,
60.6 MHz): δ −321.6 (NC H NMe ). Si NMR (benzene-d , 119.3
MHz): δ −22.5 (SiHMe ), −201.5 (Si(SiHMe ) ). IR (KBr, cm ): ν
5 4 2 2 6
−1
29
SiH
5
4
2
6
−1
s), 1031 (s), 858 (w), 680 (s), 643 (s). Anal. Calcd for
2
2 3
J
Organometallics XXXX, XXX, XXX−XXX