228
SCHORMANN ET AL.
(79 MHz, C D ) d !4.6 (SiMe ), !0.7 (SiCycMe ); (CycMe2Si)(Me3Si)2CAlBr2 )¹HF (14)
ꢆ ꢆ
ꢃ
ꢁ
MS (70 eV) m/z (%) 345 (M-Cyc, 5), 273 (M-THF, -Cyc,
100). IR (KBr) l 1348 (m), 1296 (m), 1255 (vst), 1192, (st),
1169 (m), 1089 (m), 1036 (m), 1005 (vst), 961 (m), 910 (m),
853 (vst), 843 (vst), 769 (st), 700 (st), 671 (vst), 629 (st), 566 (m),
504 (m), 436 (m) cm\ꢀ. Anal Calcd. for C H AlOSi
To
a solution of compound (CycMe Si) (Me Si)
ꢁ
ꢃ
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CAlMe )THF (2.14g, 5.0 mmol) in toluene (20 ml) was
added dropwise bromine (1.60g, 10.0 mmol) at 03C. After
stirring for 15 min the byproduct methylbromide was
removed in vacuo. The resultant solution was concentrated
to 5 ml and stored at 03C to yield compound 14 (2.18 g, 3.9
ꢁ
ꢁꢀ ꢂꢄ
ꢃ
(428.85): C, 58.81, H, 11.51, Al, 6.29: Found: C, 58.3; H, 11.4;
Al, 6.1.
ꢀ
mmol, 78%) as colorless solid (mp 1363C). H NMR
(200 MHz, C D ) d 0.45 (s, SiCH , 6 H), 0.50 (s, SiCH , 18
ꢆ ꢆ
ꢃ
ꢃ
(CycMe2Si)(Me3Si)2CAlF2 )¹HF (12)
H), 0.95 (m, CH C1 Cyc, 1 H), 1.00 (m, OCH CH , 4 H), 1.10
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ꢁ
(m, CH C4 Cyc, 2 H), 1.35, 1.95 (m, CH C2, C3 Cyc, 8 H),
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ꢁ
A mixture of (CycMe Si)(Me Si) CAlMe )THF (2.00 g,
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ꢃ
ꢁ
ꢁ
ꢀꢃ
4.06 (m, OCH CH , 4 H); C NMR (126 MHz, C D ) d 2.8
ꢁ
ꢁ
ꢆ ꢆ
4.66 mmol) and Me SnF (1.70 g, 9.32 mmol) in THF (20 ml)
ꢃ
(SiCyc(CH ) ), 6.9 (Si(CH ) ), 25.1 (OCH CH ), 27.2 (C4
Cyc), 27.3 (C1 Cyc), 29.2 (C3 Cyc), 30.5 (C2 Cyc), 76.2
ꢃ ꢁ
ꢃ ꢃ
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ꢁ
was stirred for 12 h at room temperature. After removing
all volatile components under vacuum the residue was
dissolved in THF/hexane (20 ml:10 ml). Crystallization
at !203C a!orded the colorless compound 12 (1.44g,
ꢁꢄ
(OCH CH ); Si NMR (79 MHz, C D ) d !3.4 (SiMe ),
ꢁ
ꢁ
ꢆ ꢆ
ꢃ
0.7 (SiCycMe ); MS (70 eV) m/z (%) 403 (M-THF, -Cyc, 50),
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201 ((Me Si) (CycMe Si)C-Cyc,-Me, 100); IR (KBr) l 1349
ꢀ
ꢃ
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3.3mmol, 71%) (mp 1083C). H NMR (250 MHz, C D )
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(st), 1296 (m), 1254 (vst), 1185 (m), 1169 (m), 1088 (m), 1070
(m), 1035 (m), 998 (st), 986 (st), 955 (m), 919 (m), 884 (st), 852
(vst), 802 (vst), 774 (vst), 724 (st), 706 (m), 669 (st), 644 (m),
624 (m), 464 (m), 419 (m), 404 (vst), 343 (st) cm\ꢀ. Anal
Calcd. for C H AlBr OSi (558.60): C, 40.85; H, 7.76, Al,
d 0.40 (s, SiCH , 6 H), 0.45 (s, SiCH , 18 H), 0.90
ꢃ
ꢃ
(m, OCH CH , 4 H), 1.15 (m, CH C1 Cyc, 1 H), 1.35
ꢁ
ꢁ
(m, CH C4 Cyc, 2 H), 1.80, 2.15 (m, CH C2, C3 Cyc,
ꢁ
ꢁ
ꢀꢄ
8 H), 3.80 (m, OCH CH , 4 H); F NMR (250 MHz, C D ):
ꢁ
ꢁ
ꢆ ꢆ
ꢃ
ꢁꢄ
ꢀꢄ ꢂꢃ
ꢁ
ꢃ
d !156.5 (s); Si NMR (99 MHz, C D ) d !3.2 (SiMe ),
ꢆ ꢆ
4.83. Found: C, 40.5; H, 7.7; Al, 4.6.
0.5 (SiCycMe ); MS (70 eV) m/z (%) 217
((Me Si) (CycMe Si)C- Cyc, 100); IR (KBr) l 2957 (st),
2920 (st), 2849 (m), 1448 (m), 1254 (st), 1097 (m), 1045
(m), 1011 (m), 852 (vst), 816 (vst), 718 (m), 673 (st), 616 (m)
cm\ꢀ. Anal Calcd. for C H AlF OSi (436.78): C, 52.25,
H, 9.92; Al, 6.18, F, 8.70. Found: C, 51.5; H, 9.7; Al, 5.9;
F, 8.4.
ꢁ
ꢃ
ꢁ
ꢁ
(CycMe2Si)(Me3Si)2CAlI2 )¹HF (15)
A solution of (CycMe Si)(Me Si) CAlMe )THF (4.28 g,
ꢁ
ꢃ
ꢁ
ꢁ
10.0 mmol) in toluene (30 ml) was reacted with a solution of
iodine (5.08 g, 20 mmol) in toluene (50 ml) at room temper-
ature. After adding 25 ml of the iodine solution, the color of
the reaction mixture turned violet. After subsequent stirring
for 15 h and "ltration, the byproduct methyliodide was
removed in vacuo. The amount of solvent was reduced to 25
ml and crystallization at 03C a!orded compound 15 (5.16g,
ꢀꢄ ꢂꢃ
ꢁ
ꢃ
(CycMe2Si)(Me3Si)2 CAlCl2 )¹HF (13)
To a solution of (CycMe Si)(Me Si) CAlMe )THF
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ꢃ
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(2.14g, 5.0 mmol) in THF (30 ml) was added slowly a solu-
ꢀ
7.9 mmol, 79%) (mp 1403C). H NMR (200 MHz, C D )
ꢆ ꢆ
tion of Me SnCl (2.00 g, 10.0 mmol) in THF (20 ml). After
d 0.48 (s, SiCH , 6 H), 0.53 (s, SiCH , 18 H), 0.99 (m, CH C1
ꢃ
ꢃ
ꢃ
stirring for 15 h at room temperature all volatile compo-
Cyc, 1 H), 1.01 (m, OCH CH , 4 H), 1.15 (m, CH C4 Cyc,
ꢁ
ꢁ
ꢁ
nents were removed under vacuum. The residue was dis-
solved in toluene (5 ml) and crystallization at 03C a!orded
the colorless compound 13 (1.76g, 3.8 mmol, 75%) (mp
2 H), 1.38, 2.00 (m, CH C2, C3 Cyc, 8 H), 4.15 (m,
ꢁ
ꢀꢃ
OCH CH , 4 H); C NMR (126 MHz, C D ) d 3.1
(SiCyc(CH ) ), 7.4 (Si(CH ) ); 24.0 (OCH CH ), 26.9 (C4
Cyc), 27.2 (C1 Cyc), 29.1 (C3 Cyc), 30.5 (C2 Cyc), 77.4
ꢁ
ꢁ
ꢆ ꢆ
ꢃ ꢁ
ꢃ ꢃ
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ꢁ
ꢀ
1103C). H NMR (200 MHz, C D ) d 0.43 (s, SiCH , 6 H),
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ꢃ
0.48 (s, SiCH , 18 H), 0.88 (m, CH C1 Cyc, 1 H), 0.97 (m,
OCH CH , 4 H), 1.10 (m, CH C4 Cyc, 2 H), 1.30, 1.90 (m,
ꢀꢃ
CH C2, C3 Cyc, 8 H), 3.97 (m, OCH CH , 4 H); C NMR
(126 MHz, C D ) d 2.6 (SiCyc(CH ) ), 6.7 (Si(CH ) ), 24.2
ꢆ ꢆ ꢃ ꢁ ꢃ ꢃ
(OCH CH ), 27.3 (C4 Cyc), 27.3 (C1 Cyc), 29.3 (C3 Cyc),
ꢁꢄ
30.4 (C2 Cyc), 75.4 (OCH CH ); Si NMR (79 MHz, C D )
d!3.4 (SiMe ), 0.6 (SiCycMe ); MS (70 eV) m/z (%) 313
(M-THF,-Cyc, 50), 201 ((Me Si) (CycMe Si)C-Cyc, -Me,
ꢁꢄ
(OCH CH ); Si NMR (79 MHz, C D ) d !3.1 (SiMe ),
ꢃ
ꢁ
ꢁ
ꢆ ꢆ
ꢃ
0.8 (SiCycMe ); MS (70 eV) m/z (%) 497 (M-THF, -Cyc, 60),
ꢁ
ꢁ
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201 ((Me Si) (CycMe Si)C-Cyc, -Me, 100); IR (KBr) l 1348
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ꢁ
ꢁ
ꢃ
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(st), 1296 (m), 1253 (vst), 1167 (m), 1088 (st), 1034 (m), 986
(m), 954 (m), 918 (m), 884 (st), 850 (vst), 799 (vst), 773 (vst),
721 (st), 667 (st), 642 (st), 466 (m), 403 (st), 322 (vst) cm\ꢀ.
Anal Calcd. for C H AlI OSi (652.58): C, 34.97; H, 6.64;
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ꢆ ꢆ
ꢃ
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ꢀꢄ ꢂꢃ
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Al, 4.13. Found: C, 35.3; H, 6.5; Al, 3.8.
ꢃ
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100); IR (KBr) l 1305 (st), 1263 (vst), 1169 (m), 1155 (m), 1076
(m), 1032 (m), 972 (m), 878 (vst), 853 (vst), 813 (vst), 676 (st),
566 (m), 509 (m) cm\ꢀ. Anal calcd. for C H AlCl OSi
[(CycMe2Si)(Me3Si)2CAl(k-O(CH2)3CH2)]2 (16)
ꢀꢄ ꢂꢃ
ꢁ
ꢃ
(469.68): C, 48.59; H, 9.23; Al, 5.74; Cl, 15.10. Found: C, 48.6;
H, 9.0; Al, 6.1; Cl, 15.1.
To a suspension of Na/K alloy (Na, 0.08 g, 3.5 mmol; K,
0.25g, 6.5 mmol) in toluene (10 ml) was added dropwise