G. Erker et al.
FULL PAPERS
for X-ray crystal-structure analysis. Further cooling of the mother liquor
(m, 1H; 7-H), 5.14–5.01 (m, 2H; 8-H), 3.40 ppm (dm, JH,H =6.7 Hz, 2H;
to 48C yielded another crop of crystalline product. Yield: 1.03 g
(1.25 mmol, 60%). M.p. (DSC): 1118C; H NMR (600 MHz, [D8]toluene,
298 K): d=6.38 (m, 2H; 2-H), 6.12 (m, 2H; 3-H), 6.05 (m, 2H; 8-H),
6.00 (m, 2H; 7-H), 2.76 (m, 2H; 11-H), 1.88 (m, 2H; 13-H), 1.77 (m, 2H;
12-H), 0.99 ppm (d, 3JP, H =11.5 Hz, 18H; CH3); 13C{1H} NMR (151 MHz,
6-H).
1
Preparation of 9
The allyl-substituted zirconocene 8 (200 mg, 0.602 mmol) and HBACHTUNGTRENNUNG(C6F5)2
(208 mg, 0.602 mmol) were mixed and cooled to À788C. Precooled di-
chloromethane (30 mL) was added and the reaction mixture was stirred
overnight at room temperature. The solvent was removed under reduced
pressure and pentane (25 mL) was added. The solid was triturated in an
ultrasonic bath and collected on a glass frit. Successive washing with pen-
tane (2ꢅ5 mL) and drying in vacuo yielded the product as a gray
powder. Yield: 275 mg (0.405 mmol, 67%). M.p. (DSC): 488C; 1H NMR
(500 MHz, [D2]dichloromethane, 298 K): d=6.45 (s, 5H; C5H5), 6.32 (m,
2H; 3-H), 6.18 (m, 2H; 2-H), 2.70 (m, 2H; 6-H), 2.13 (m, 2H; 8-H),
1.84 ppm (m, 2H; 7-H); 13C{1H} NMR (126 MHz, [D2]dichloromethane,
1
1
[D8]toluene, 298 K): d=147.1 (dm, JF,C ꢀ247 Hz; C6F5), 143.6 (dm, JF,C
1
ꢀ259 Hz; C6F5), 137.7 (dm, JF,C ꢀ253 Hz; C6F5), 134.0 (C-6), 124.5 (d,
2JP, C =10.8 Hz; C-2), 121.3 (d, 1JP,C =40.1 Hz; C-1), 120.1 (C-7), 117.5 (d,
3JP, C =2.5 Hz; C-3), 114.1 (br; ipso-C6F5), 111.8 (d, 3JP, C =6.4 Hz; C-8),
2
33.7 (d, 1JP, C =22.5 Hz; C
(CH3)3), 32.8 (C-11), 32.1 (C-13), 30.8 (d, JP,C
=
13.9 Hz; CH3), 26.1 ppm (C-12); 11B{1H} NMR (64 MHz, [D8]toluene,
298 K): d=71 ppm (n = ꢀ1000 Hz); 19F{1H} NMR (282 MHz, [D8]toluene,
1
2
295 K) d=À130.2 (m, 2F; o-C6F5), À147.4 (br, 1F; p-C6F5), À161.0 ppm
(br, 2F; m-C6F5); 31P{1H} NMR (122 MHz, [D8]toluene, 295 K): d=
1
1
1
33.2 ppm (n = ꢀ2 Hz); elemental analysis calcd (%) for C33H32BCl2F10PZr
298 K): d=147.3 (dm, JF,C ꢀ240 Hz; C6F5), 137.8 (dm, JC,F ꢀ252 Hz;
C6F5), 134.4 (C-1), 117.8 (C-2), 116.1 (C5H5), 112.7 (C-3), 33.1 (C-6), 32.2
(br; C-8), 26.6 ppm (C-7), not observed (n.o.) (ipso-C6F5); 11B{1H} NMR
2
(822.51 gmolÀ1): C 48.19, H 3.92; found: C 48.45, H 4.13.
Preparation of (E)-7/(Z)-7
1
(96 MHz, [D2]dichloromethane, 300 K): d=72 ppm (n = ꢀ900 Hz);
2
19F{1H} NMR (282 MHz, [D2]dichloromethane, 295 K): d=À130.0 (m,
Complex 5 (103 mg, 0.125 mmol) was dissolved in toluene (5 mL). 1-Pen-
tyne (8.5 mg, 12 mL, 0.125 mmol) was added with a microliter syringe.
The mixture was stirred for one hour and the solvent was successively re-
moved under reduced pressure. The residue was extracted with heptane
(10 mL). The solution was stored at À308C until the product precipitat-
ed, the supernatant was removed by syringe, and the pale yellow solid
2F; o-C6F5), À148.4 (br, 1F; p-C6F5), À161.7 ppm (m, 2F; m-C6F5); ele-
mental analysis calcd (%) for C25H15BCl2F10Zr (678.31 gmolÀ1): C 44.27,
H 2.23; found: C 43.93, H 2.48.
Preparation of (E)-10/(Z)-10
1
1-Pentyne (10.0 mg, 14.1 mL, 0.147 mmol) was added to a solution of 9
(100 mg, 0.147 mmol) in toluene (5 mL) and stirred overnight. The sol-
vent was removed under reduced pressure and pentane was added to the
residue. Trituration in an ultrasonic bath yielded a gray suspension. After
the solid had settled, it was isolated by decantation and dried in vacuo.
was dried in vacuo. Integration of H NMR spectroscopic resonances pro-
vided a ratio (Z)-7/(E)-7ꢀ1.2:1. Yield: 46 mg (51.6 mmol, 41%). M.p.
1
(DSC): 698C. Compound (E)-7: H NMR (600 MHz, [D8]toluene, 298 K):
d=6.38 (m, 2H; 2-H), 6.12 (m, 2H; 3-H), 6.08 (m, 1H; 15-H), 6.06 (m,
2H; 8-H), 5.93 (m, 2H; 7-H), 2.62 (m, 2H; 11-H), 2.17 (m, 2H; 13-H),
1.73 (m, 2H; 16-H), 1.59 (m, 2H; 12-H), 1.12 (m, 2H; 17-H), 0.989 (d,
1
Integration of H NMR resonances provided a ratio (Z)-10/(E)-10ꢀ10:7.
Yield: 23 mg (30.8 mmol, 21%). (E)-10: 1H NMR (500 MHz, [D8]toluene,
298 K): d=6.09 (t, JH,H =7.8 Hz, 1H; 10-H), 5.840 (s, 5H; Cp), 5.70 (m,
2H; 2-H), 5.55 (m, 2H; 3-H), 2.48 (m, 2H; 6-H), 2.14 (m, 2H; 8-H), 1.74
(m, 2H; 11-H), 1.51 (m, 2H; 7-H), 1.13 (m, 2H; 12-H), 0.62 ppm (t,
3JP, H =11.5 Hz, 18H; CH3), 0.61 ppm (t,
J
H,H =7.4 Hz, 3H; 18-H);
13C{1H} NMR (151 MHz, [D8]toluene, 298 K): d=151.9 (C-15), 147.2
1
1
(dm, JF,C ꢀ244 Hz; C6F5), 147.1 (br; C-14), 143.8 (dm, JC,F ꢀ254 Hz),
1
137.7 (dm, JF,C ꢀ258 Hz; C6F5), 134.7 (C-6), 124.5 (d, 2JP, C =10.8 Hz; C-
1
J
H,H =7.4 Hz, 3H; 13-H); 13C{1H} NMR (126 MHz, [D8]toluene, 298 K):
2), 121.3 (d, JP, C =40.1 Hz, 1H; C-1), 119.6 (d, 2JP, C =0.9 Hz; C-7), 117.47
1
d=152.2 (C-10), 147.1 (dm, JF,C ꢀ246 Hz, C6F5), 146.9 (br; C-9), 143.8
(d, 3JP, C =2.1 Hz; C-3), 115.4 (br; ipso-C6F5), 111.88 (d, 3JP, C =6.2 Hz; C-
1
1
1
(dm, JF,C ꢀ258 Hz; p-C6F5), 137.7 (dm, JF,C ꢀ255 Hz; C6F5), 134.2 (C-1),
117.3 (C-2), 115.45 (Cp), 111.3 (C-3), 39.3 (C-8), 34.5 (C-11), 33.0 (C-7),
30.3 (C-6), 23.3 (C-12), 13.6 ppm (C-13), n.o. (ipso-C6F5); 11B{1H} NMR
8), 39.3 (C-13), 34.5 (C-16), 33.7 (d, JP, C =22.6 Hz; C
A
30.8 (d, 2JP, C =13.9 Hz; CH3), 30.2 (C-11), 23.3 (C-17), 13.6 ppm (C-18);
19F{1H} NMR (564 MHz, [D8]toluene, 298 K): d=À130.8 (m, 2F; o-F),
À148.2 (t, J=20.5 Hz, 1F; p-F), À161.9 ppm (m, 2F; m-F); 31P{1H} NMR
(160 MHz, [D8]toluene, 300 K): d=64.2 ppm (n = ꢀ1600 Hz); 19F NMR
1
2
(470 MHz, [D8]toluene, 298 K): d=À130.0 (m, 2F; o-F), À147.3 (m,1F;
1
(122 MHz, [D8]toluene, 298 K): d=33.19, 33.16 ppm (each s, each n =
2
p-F), À160.9 ppm (m, 2F; m-F). Compound (Z)-10: 1H NMR (500 MHz,
[D8]toluene, 298 K): d=6.58 (t, JH,H =7.2 Hz, 1H; 10-H), 5.843 (s, 5H;
Cp), 5.67 (m, 2H; 2-H), 5.56 (m, 2H; 3-H), 2.47 (m, 2H; 6-H), 2.23 (m,
2H; 8-H), 2.04 (m, 2H; 11-H), 1.42 (m, 2H; 7-H), 1.22 (m, 2H; 12-H),
ꢀ2 Hz). Compound (Z)-7: 1H NMR (600 MHz, [D8]toluene, 298 K): d=
6.57 (t, JH,H =7.2 Hz, 1H; 15-H), 6.38 (m, 2H; 2-H), 6.12 (m, 2H; 3-H),
6.07 (m, 2H; 8-H), 5.90 (m, 2H; 7-H), 2.60 (m, 2H; 11-H), 2.26 (m, 2H;
13-H), 2.03 (m, 2H; 16-H), 1.49 (m, 2H; 12-H), 1.22 (m, 2H; 17-H),
0.990 (d, 3JP, H =11.5 Hz, 18H; CH3), 0.76 ppm (t, JH,H =7.4 Hz, 3H; 18-
H); 13C{1H} NMR (151 MHz, [D8]toluene, 298 K): d=164.7 (C-15), 150.5
0.77 ppm (t,
J
H,H =7.4 Hz, 3H; 13-H); 13C{1H} NMR (126 MHz,
1
[D8]toluene, 298 K): d=164.8 (C-10), 150.4 (br; C-9), 146.3 (dm, JF,C
1
1
1
1
ꢀ244 Hz; C6F5), 142.8 (dm, JF,C ꢀ256 Hz; p-C6F5), 137.7 (dm, JF,C
ꢀ255 Hz; C6F5), 134.1 (C-1), 117.2 (C-2), 115.47 (Cp), 111.3 (C-3), 32.6
(C-11), 32.0 (C-7), 30.1 (C-6), 29.9 (C-8), 22.2 (C-12), 13.9 ppm (C-13);
19F NMR (470 MHz, [D8]toluene, 298 K): d=À131.0 (m, 2F; o-F),
À149.6 (m, 1F; p-F), À161.1 (m, 2F; m-F); elemental analysis calcd (%)
for C30H23BCl2F10Zr (746.43 gmolÀ1): C 48.27, H 3.11; found: C 47.26,
H 2.86.
(br; C-14), 146.3 (dm, JF,C ꢀ243 Hz; C6F5), 142.8 (dm, JF,C ꢀ256 Hz;
C6F5), 137.7 (dm, JF,C ꢀ258 Hz; C6F5),134.6 (C-6), 124.5 (d, JP, C
10.8 Hz; C-2), 121.4 (d, 1JP, C =40.2 Hz, 1H; C-1), 119.4 (d, 2JP, C =0.9 Hz;
1
2
=
3
3
C-7), 117.48 (d, JP, C =2.1 Hz; C-3), 114.6 (br; ipso-C6F5), 111.92 (d, JP, C
=
6.2 Hz; C-8), 33.7 (d, 1JP, C =22.6 Hz; C
AHCTUNGTRENNUNG
30.8 (d, 2JP, C =13.9 Hz; CH3), 30.1 (C-11), 30.0 (C-13), 22.2 (C-17),
13.9 ppm (C-18); 19F{1H} NMR (564 MHz, [D8]toluene, 298 K): d=
À131.9 (m, 2F: o-F), À150.5 (t, J=20.5 Hz, 1F; p-F), À162.0 ppm (m,
2F; m-F); elemental analysis calcd (%) for C38H40BCl2F10PZr
(890.62 gmolÀ1): C 51.25, H 4.53; found: C 50.69, H 4.35.
Photolysis of (E)-6/(Z)-6
Compound 6 (62 mg, 75 mmol) and ferrocene (4 mg, internal standard)
were dissolved in [D8]toluene and 1-pentyne was added (7.5 mL,
75 mmol). The mixture was flame-sealed in an NMR spectroscopy tube.
The sample was protected from ambient light and was analyzed by using
NMR spectroscopy. It was then irradiated with a water-cooled Hg high-
pressure lamp (Philips HPK 125 W) equipped with a quartz glass filter at
room temperature. 1H and 19F NMR spectra were collected after 30, 60,
and 120 min of irradiation.
Preparation of 8[18]
Complex 3 (1.0 g, 2.55 mmol) and lithium cyclopentadienide (183 mg,
2.55 mmol) were mixed and cooled to À788C. Precooled toluene (25 mL)
was added and the mixture was stirred for 3 h while warming to room
temperature. LiCl was removed by filtration over Celite. The solvent was
removed under reduced pressure and the residue was washed twice with
pentane (10 mL each). The off-white product was dried in vacuo. Yield:
592 mg (1.78 mmol, 70%). 1H NMR (200 MHz, [D2]dichloromethane,
300 K): d=6.47 (s, 5H; C5H5), 6.37, 6.23 (each m, 2H; 2-H, 3-H), 5.94
2206
ꢃ 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Asian J. 2010, 5, 2199 – 2208