FULL PAPER
Synthesis of [(C9H6)CH3](C5HMe4)SiMe2 (5): Compound 5 was
synthesized in a manner identical to that for 4 from nBuLi (1.60 m
Synthesis of [ZrCl2({η5-C9H5(CH3)}{η5-C5Me4}SiMe2)] (9): Com-
pound 9 was synthesized in a manner identical to that for 8 from
in hexane, 21.12 mL, 33.79 mmol), 1 (4.00 g, 30.72 mmol) and ZrCl4 (2.51 g, 10.80 mmol), 5 (3.34 g, 10.80 mmol) and nBuLi
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(C5HMe4)SiMe2Cl (6.78 mL, 30.72 mmol). Yield 6.52 g (65%). H (14.86 mL, 23.78 mmol). Yield 4.650 g (91%). 1H NMR (500 MHz,
NMR (500 MHz, CDCl3): δ = –0.41, –0.17 [2 s, H each, Si- CDCl3): δ = 0.93, 1.18 [2 s, 3 H each, Si(CH3)2], 1.90, 1.95, 1.96,
(CH3)2], 1.88, 2.02, 2.03, 2.24 [4 s, 3 H each, C5(CH3)4], 3.07 (s, 1 2.02 [4 s, 3 H each, C5(CH3)4], 2.51 (s, 3 H, 10-H), 5.54 (s, 1 H, 2-
H, CH3) 3.54 (s, 1 H, 1-H), 4.01 (m, 1 H, 11-H), 6.26 (m, 1 H, 2-
H), 7.20 (m, 1 H, 6-H), 7.30 (m, 1 H, 7-H), 7.42 (m, 2 H, 5-H, 8- 7.47 (d, J = 7.6 Hz, 1 H, 5-H), 7.56 (d, J = 7.6 Hz, 1 H, 8-H) ppm.
H) ppm. 13C NMR (125 MHz, CDCl3): δ = –5.73, –5.18 [Si- 13C NMR (125 MHz, CDCl3): δ = 1.14, 1.39 [Si(CH3)2], 12.18,
(CH3)2], 12.94 (CH3), 11.25, 11.31, 14.70, 14.80 [C5(CH3)4], 42.57 12.48, 13.70, 15.29 [C5(CH3)4], 13.71 (10-C), 85.21 (3-C), 95.46 (13-
(C-11), 54.65 (C-1), 118.90 (C-5), 120.98 (C-3), 122.89 (C-8), 123.61 C), 117.33 (2-C), 124.11 (1-C), 124.19 (5-C), 125.38 (8-C), 126.19,
(C-6), 124.70 (C-7), 130.56 (C-2), 145.50 (C-4), 145.86 (C-9), 126.41 (6-C, 7-C), 128.29, 133.06, 134.99, 135.16 (14-C, 15-C, 16-
H), 7.06 (t, J = 7.6 Hz, 1 H, 6-H), 7.35 (t, J = 7.6 Hz, 1 H, 7-H),
120.98, 131.55, 136.35, 137.35 [C5(CH3)4] ppm.
C, 17-C), 145.32, 145.45 (4-C, 9-C) ppm. C21H26Cl2SiZr (468.22):
calcd. C 53.82, H 5.55; found C 53.81, H 5.52.
Synthesis of [(C9H6)CH2(C6H5)](C5HMe4)SiMe2 (6): Compound 6
was synthesized in a manner identical to that for 4 from nBuLi
(1.60 m in hexane, 13.33 mL, 21.33 mmol), 2 (4.00 g, 19.39 mmol)
and (C5HMe4)SiMe2Cl (4.20 mL, 19.39 mmol). Yield 5.99 g (80%).
1H NMR (500 MHz, CDCl3): δ = –0.46, –0.09 [2 s, H each, Si-
(CH3)2], 1.77, 1.84, 1.91, 2.01 [4 s, 3 H each, C5(CH3)4], 2.99 (s, 1
H, 1-H), 3.48 (s, 1 H, 17-H), 3.93 (s, 2 H, CH2Ph) 6.06 (m, 1 H,
2-H), 7.13–7.43 (m, 9 H, 5-H/8-H, CH2Ph) ppm. 13C NMR
(125 MHz, CDCl3): δ = –5.58, –4.23 [Si(CH3)2], 11.21, 11.25, 14.68,
14.78 [C5(CH3)4], 34.44 (CH2Ph), 37.67 (C-17), 42.55 (C-1), 119.01
(C-3), 119.31 (C-5), 123.01 (C-8), 123.72 (C-6), 124.68 (C-7),
125.98–128.89 ([C5(CH3)4], CH2Ph), 129.26 (C-2), 144.50 (C-4),
146.32 (C-9) ppm.
Synthesis of [ZrCl2{(η5-C9H5{CH2(C6H5)})(η5-C5Me4)SiMe2}]
(10): Compound 10 was synthesized in a manner identical to that
for 8 from ZrCl4 (3.35 g, 14.39 mmol), 6 (5.53 g, 14.39 mmol) and
nBuLi (19.78 mL, 31.65 mmol). Yield 6.07 g (77%). 1H NMR
(500 MHz, CDCl3): δ = 1.01, 1.28 [2 s, 3 H each, Si(CH3)2], 1.99,
2.05, 2.07, 2.14 [4 s, 3 H each, C5(CH3)4], 4.38 (dd, JAB = 16 Hz,
2 H, CH2Ph), 5.71 (s, 1 H, 2-H), 7.15, (t, J = 7.6 Hz, 1 H, 6-H),
7.26 (d, J = 7.6 Hz, 1 H, 7-H), 7.33, 7.42 (m and t respectively, J
= 6.7, 7.6 Hz, respectively, 5 H, 12-H, 13-H, 14-H, 15-H, 16-H),
7.57 (d, J = 8.6 Hz, 1 H, 5-H), 7.57 (d, J = 8.6 Hz, 1 H, 8-H) ppm.
13C NMR (125 MHz, CDCl3): δ = 1.25, 1.56 [Si(CH3)2], 12.34,
12.67, 14.83, 15.48 [C5(CH3)4], 34.88 (10-C), 85.31 (3-C), 95.90 (19-
C), 117.49 (2-C), 124.38 (1-C), 124.47, 125.62 (5-C, 8-C), 126.45,
126.65 (6-C, 7-C), 126.24–128.86 (1-C, 13-C, 14-C, 15-C, 16-C),
128.70–135.27 (20-C, 21-C, 22-C, 23-C), 132.74 (11-C), 135.62,
140.53 (4-C, 9-C) ppm. C27H30Cl2SiZr (544.22): calcd. C 59.53, H
5.51; found C 59.59, H 5.45.
Synthesis of [(C9H6)CH2CH2(C4H7O2)](C5HMe4)SiMe2 (7): Com-
pound 7 was synthesized in a manner identical to that for 4 from
nBuLi (1.60 m in hexane, 11.88 mL, 19.08 mmol),
3 (4.00 g,
17.36 mmol) and (C5HMe4)SiMe2Cl (3.84 mL, 17.36 mmol). Yield
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6.52 g (91%). H NMR (500 MHz, CDCl3): δ = –0.48, –0.21 [2 s,
H each, Si(CH3)2], 1.31 (m, 1 H, 14-Heq), 1.79, 1.83, 1.96, 1.98 [4
s, 3 H each, C5(CH3)4], 2.08 (m, 3 H, 14-Hax, 11-H, 11Ј-H), 2.68
(m, 2 H, 10-H, 10Ј-H), 3.01 (s, 1 H, 1-H), 3.49 (s, 1 H, 16-H), 3.74
(m, 2 H, 13-Hax, 15-Hax), 4.10 (m, 2 H, 13-Heq, 15-Heq), 4.59 (m,
1 H, 12-H), 6.21 (m, 1 H, 2-H), 7.14 (m, 1 H, 6-H), 7.22 (m, 1 H,
7-H), 7.38 (m, 2 H, 5-H, 8-H) ppm. 13C NMR (125 MHz, CDCl3):
δ = –5.62, –4.72 [Si(CH3)2], 11.27, 11.31, 14.72, 14.80 [C5(CH3)4],
25.66 (C-11), 26.31 (C-14), 31.52 (C-10), 42.69 (C-1), 54.06 (C-16),
67.82 (C-13), 67.91 (C-15), 104.61 (C-12), 121.31 (C-5), 123.31 (C-
8), 125.03 (C-6), 126.86 (C-7), 127.90 (C-2), 119.01 (C-3), 120.12
(C-4), 122.05 (C-9), 124.09, 124.98, 126.02, 129.63 [C5(CH3)4] ppm.
Synthesis of [ZrCl2{(η5-C9H5{C2H4(C4H7O2)})(η5-C5Me4)SiMe2}]
(11): Compound 11 was synthesized in a manner identical to that
for 8 from ZrCl4 (1.753 g, 7.525 mmol), 7 (3.07 g, 7.52 mmol) and
nBuLi (10.34 mL, 16.54 mmol). Yield 3.474 g (81%). 1H NMR
(500 MHz, CD2Cl2): δ = 0.93, 1.34 [2 s, 3 H each, Si(CH3)2], 1.34
(d, J = 13.7 Hz, 1 H, 14-Heq), 1.90, 1.90, 1.95, 2.01 [4 s, 3 H each,
C5(CH3)4], 2.09 (m, 1 H, 14-Hax), 2.11 (m, 2 H, 11-H, 11Ј-H), 3.04
(m, 2 H, 10-H, 10Ј-H), 3.74 (m, 2 H, 13-Hax, 15-Hax), 4.11 (m, 2
H, 13-Heq, 15-Heq), 4.51 (t, J = 5.1 Hz, 1 H, 12-H), 5.60 (s, 1 H,
2-H), 7.06 (dd, J = 8.1, 4.1 Hz, 1 H, 6-H), 7.34 (dd, J = 8.1, 4.1 Hz,
1 H, 7-H), 7.46 (d, J = 8.1 Hz, 1 H, 5-H), 7.60 (d, J = 8.1 Hz, 1 H,
8-H) ppm. 13C NMR (125 MHz, CDCl3): δ = 1.09, 1.40 [Si(CH3)2],
12.15, 12.48, 14.67, 15.29 [C5(CH3)4], 23.19 (10-C), 25.81 (14-C),
35.27 (11-C), 66.86, 66.88 (13-C, 15-C), 84.61 (3-C), 95.74 (18-C),
101.70 (12-C), 116.30 (2-C), 124.03 (1-C), 124.40 (5-C), 125.42 (8-
C), 126.18, 126.30 (6-C, 7-C), 127.86 (6-C), 126.30 (7-C), 127.86–
13.80 (19-C, 20-C, 21-C, 22-C), 134.92, 135.34 (4-C, 9-C) ppm.
C26H34Cl2O2SiZr (568.22): calcd. C 54.90, H 5.98; found C 54.87,
H 6.15.
Synthesis of [ZrCl2{(η5-C9H6)(η5-C5Me4)SiMe2}] (8): A cooled
(–78 °C) slurry of ZrCl4 (5.40 g, 23.20 mmol) in toluene (50 mL)
was rapidly added to
a
cooled (–78 °C) solution of
Li2[(C9H7)(C5Me4)SiMe2] in Et2O (50 mL) obtained by treating 4
(7.83 g, 23.20 mmol) with nBuLi (31.95 mL, 46.50 mmol). The re-
action mixture was stirred at –20 °C for 30 min and then warmed to
room temp.; the solvent was removed in vacuo and toluene (75 mL)
added. The yellow suspension was filtered through a G4 frit with
Celite. The filtrate was concentrated to dryness under reduced pres-
sure to yield a yellowish product, which was washed with hexane
(2ϫ 20 mL) and dried to give a yellow solid. Yield 9.86 g (93%).
1H NMR (500 MHz, CDCl3): δ = 0.49, 0.67 [2 s, 3 H each, Si-
Synthesis of [ZrMe2{(η5-C9H6)(η5-C5Me4)SiMe2}] (12): MeMgBr
(3 m in Et2O, 4.08 mL, 12.25 mmol) was added to a cooled (–78 °C)
solution of 8 (2.536 g, 5.57 mmol) in THF (60 mL) over 15 min. At
(CH3)2], 1.71, 1.74, 1.87, 1.93 [4 s, 3 H each, C5(CH3)4], 5.66 (s, 1 the end of the addition, the solution was allowed to reach room
H, 2-H), 5.98 (s, 1 H, 1-H), 6.85 (t, J = 7.6 Hz, 1 H, 6-H), 7.25 (t, temp. and stirred protected from light for 4 h. The solvent was re-
J = 7.6 Hz, 1 H, 7-H), 7.29 (d, J = 7.6 Hz, 1 H, 5-H), 7.51 (d, J =
moved in vacuo and the product extracted with toluene (2ϫ
7.6 Hz, 1 H, 8-H) ppm. 13C NMR (125 MHz, CDCl3): δ = 0.98, 50 mL). The solvent was removed from the filtrate under reduced
1.23 [Si(CH3)2], 12.13, 12.35, 14.85, 15.26 [C5(CH3)4], 86.30 (3-C), pressure and the remaining solid washed with hexane (2ϫ 25 mL)
96.83 (12-C), 117.11 (2-C), 120.22 (1-C), 124.90 (5-C), 126.12 (8-
C), 126.34, 126.55 (6-C, 7-C), 128.11, 133.18, 135.39, 135.83 (14-C,
to yield the title compound as a pale-yellow solid. Yield 1.78 g
(77%). 1H NMR (500 MHz, CDCl3): δ = –1.33, –0.18 [2 s, 3 H
15-C, 16-C, 17-C), 144.31, 144.50 (4-C, 9-C) ppm. C20H24Cl2SiZr each, Zr(CH3)2], 0.49, 0.67 [2 s, 3 H each, Si(CH3)2], 1.64, 1.72,
(454.22): calcd. C 52.84, H 5.28; found C 53.01, H 5.21.
1.83, 1.85 [4 s, 3 H each, C5(CH3)4], 5.57 (s, 1 H, 2-H), 5.99 (s, 1
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Eur. J. Inorg. Chem. 2013, 1184–1196
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim