12848 J. Am. Chem. Soc., Vol. 119, No. 52, 1997
Xi et al.
141.50, 145.35, 145.79, 148.13; HRMS calcd for C24H24OSi 356.1596,
found 356.1588.
139.66, 142.01, 152.86, 160.32; HRMS calcd for C26H32Si 372.2273,
found 372.2259.
20D. The reaction mixture containing 19b was hydrolyzed with
DCl/D2O instead of 3 N HCl. Normal workup provided 20D, which
was then purified by means of flash chromatography (hexane/ether )
Formation of 21a. To a THF solution of zirconacyclopentene 17a
(1 equiv) was added bis(1-butynyl)diphenylsilane (1 equiv) at 0 °C.
The reaction was complete after 12 h at room temperature forming
zirconacyclopentadiene 18a in 85% NMR yield. NMR data for 18a:
1H NMR (C6D6, Me4Si) δ 0.63 (t, J ) 7.3 Hz, 3H), 0.91 (t, J ) 7.6
Hz, 3H), 1.94 (q, J ) 7.6 Hz, 2H), 2.40 (q, J ) 7.3 Hz, 2H), 6.21 (s,
10H), 6.71-8.01 (m, 20H); 13C NMR (C6D6, Me4Si) δ 13.71, 14.00,
14.04, 34.62, 84.76, 111.51, 112.58, 123.13, 126.29, 127.31, 127.84,
128.58, 129.28, 129.30, 130.5, 136.03, 138.67, 142.20, 142.81, 149.21,
161.72, 185.41, 200.33. Hydrolysis of the reaction mixture followed
by normal workup provided 21a, which was obtained as a pure
compound (sticky oil) by means of column chromatography (hexane/
ether ) 95:5). For 21a: NMR yield 85%; isolated yield 77%; 1H NMR
(CDCl3, Me4Si) δ 0.96 (t, J ) 7.4 Hz, 3H), 1.21 (t, J ) 7.4 Hz, 3H),
2.52 (q, J ) 7.4 Hz, 2H), 2.35 (q, J ) 7.4 Hz, 2H), 5.75 (s, 1H), 6.81
(s, 1H), 6.88-7.68 (m, 20H); 13C NMR (CDCl3, Me4Si) δ 13.50, 13.68,
13.89, 27.31, 79.55, 112.77, 122.62, 126.72, 127.17, 127.74, 127.83,
128.09, 128.50, 129.38, 129.68, 129.95, 134.84, 137.23, 138.80, 139.59,
145.05, 165.55; HRMS calcd for C34H32Si 468.2273, found 468.2299.
1
95:5). For 20D: NMR yield 82%; isolated yield (220 mg) 59%; H
NMR (CDCl3, Me4Si) δ 0.81 (t, J ) 7.4 Hz, 3H), 0.94 (t, J ) 7.6 Hz,
3H), 1.02 (t, J ) 7.4Hz, 6H), 2.11 (q, J ) 7.4 Hz, 2H), 2.13 (q, J )
7.4 Hz, 2H), 2.16 (q, J ) 7.6 Hz, 2H), 2.40 (q, J ) 7.4 Hz, 2H), 7.34-
7.69 (m, 10H); 13C NMR (CDCl3, Me4Si) δ 13.40, 13.53, 13.67, 14.94,
21.10, 21.98, 25.36, 29.90, 127.93, 129.81, 129.53 (t, J ) 23.8 Hz),
134.80, 135.22, 137.14, 139.61, 142.10, 152.80 (t, J ) 23.5 Hz), 160.35;
HRMS calcd for C26D2H30Si 374.2397, found 374.2422.
X-ray Crystallographic Analysis of 7. An orange prismatic crystal
of approximate dimensions 0.2 × 0.3 × 0.4 mm3 was sealed in a
capillary tube and mounted on an Enraf-Nonius CAD4 X-ray diffrac-
tometer. Intensity data were collected at room temperature with
monochromated Mo KR radiation (λ ) 0.710 73 Å). The cell constants
and orientation matrices for data collection were obtained from a least-
squares refinement using the setting angles of carefully centered 25
reflections. Crystallographic data are given in Table 2. The data were
collected in ω - 2θ mode. The intensities of three standard reflections
were checked every 2 h to ascertain crystal integrity, and the intensities
were corrected for the decay (16%). A total of 12189 reflections were
measured (2θmax ) 60°), of which 4616 unique reflections with |Fo| >
3σ(|Fo|) were used for the solution and refinement of the structure.The
structure was solved by direct methods (SHELXS-86)23 and the
following conventional Fourier techniques. Refinement was carried
out by full-matrix least-squares using Xtal3.2 software.24 All non-
hydrogen atoms were refined anisotropically, and hydrogen atoms were
fixed to the calculated positions with isotropic thermal parameters equal
to those of parent carbon atoms. Refinement of positional and thermal
parameters led to a convergence with R ) 0.051, Rw ) 0.046, and
GOF ) 1.33. The maximum and minimum peaks on the final
difference Fourier map correspond to 0.57 and -0.43 e/Å3, respectively.
Formation of 19 and 20. A General Procedure. After the
formation of zirconacyclopentadiene 18 was complete, the reaction
mixture was heated up to reflux in THF for 3 h. Zirconacyclohexadiene
19 was thus formed and obtained as solids or crystals after recrystal-
ization from hexane at low temperature (0 °C). Hydrolysis of the
reaction mixture with 3 N HCl and followed by usual workup afforded
20.
For 19a: NMR yield 89%; isolated yield 83%; 1H NMR (C6D6, Me4-
Si) δ 0.89 (t, J ) 7.3 Hz, 3H), 1.15 (t, J ) 7.6 Hz, 3H), 2.22 (q, J )
7.6 Hz, 2H), 2.41 (q, J ) 7.3 Hz, 2H), 5.92 (s, 10H), 6.49-7.93 (m,
20H); 13C NMR (C6D6, Me4Si) δ 15.44, 15.80, 28.86, 33.55, 110.85,
122.71, 125.17, 127.04, 127.67, 127.90, 128.39, 129.90, 130.78, 135.70,
137.09, 141.13, 144.85, 147.90, 151.37, 152.56, 176.13, 199.82, 231.30.
1
For 19b: NMR yield 82%; isolated yield 57%; H NMR (C6D6,
X-ray Crystallographic Analysis of 19c. A crystal of approximate
dimensions 0.2 × 0.3 × 0.3 mm3 was sealed in a capillary tube and
mounted on an Enraf-Nonius CAD4 X-ray diffractometer. Unit cell
parameters were determined by least-squares refinement of the angular
positions of 25 well-centered reflections. Crystallographic data are
listed in Table 2. Diffraction data were collected at room temperature
by using graphite-monochromated Mo KR radiation and an ω scan
technique. The intensities of three standard reflections were checked
every 2 h, and no significant loss of intensity was observed. A total
of 11 934 reflections were measured, of which 4320 reflections were
unique with |Fo| > 3σ(|Fo|). The position of zirconium atom was
determined from a Patterson map and used as the initial phasing model
for difference Fourier synthesis. All non-hydrogen atoms were refined
anisotropically, and a subsequent difference Fourier synthesis revealed
the positions of hydrogen atoms. Data reduction and structure refinment
were performed using Xtal3.2 software.24 Refinement of positional
Me4Si) δ 0.93 (t, J ) 7.3 Hz, 6H), 1.08 (t, J ) 7.4 Hz, 3H), 1.10 (t,
J ) 7.6 Hz, 3H), 1.31 (q, J ) 7.3 Hz, 2H), 2.12 (q, J ) 7.6 Hz, 2H),
2.22 (q, J ) 7.4 Hz, 2H), 2.24 (q, J ) 7.3 Hz, 2H), 5.96 (s, 10H),
7.16-7.94 (m, 10H); 13C NMR (C6D6, Me4Si) δ 15.22, 15.39, 15.80,
16.71, 17.68, 24.40, 28.81, 32.79, 110.11, 128.31, 129.70, 135.72,
137.70, 141.79, 145.50, 152.08, 172.92, 196.47, 230.81.
19c. Recrystalization from cold hexane (0°C) afforded crystals
suitable for X-ray analysis. X-ray analysis showed this complex
contained 0.5C6H14 in the crystal. For 19c: NMR yield 98%; isolated
yield 79%; 1H NMR (C6D6, Me4Si) δ 0.85 (t, J ) 7.3 Hz, 3H), 1.18 (t,
J ) 7.6 Hz, 3H), 1.27 (s, 18H), 2.37 (q, J ) 7.3 Hz, 2H), 2.38 (q, J )
7.6 Hz, 2H), 6.04 (m, 2H), 6.08 (m, 4H), 6.13 (m, 2H), 6.69-7.94 (m,
20H); 13C NMR (C6D6, Me4Si) δ 15.08, 15.67, 30.31, 31.72, 33.32,
34.41, 107.02, 107.82, 108.80, 112.51, 122.86, 125.05, 126.93, 127.24,
127.85, 128.37, 129.80, 130.76, 135.81, 136.80, 141.04, 142.68, 145.62,
149.34, 151.17, 152.88, 176.55, 200.61, 234.43.
and thermal parameters led to a convergence with R ) 0.056, Rw
0.051, and GOF ) 1.43.
)
20a. Hydrolysis of the reaction mixture containing 19a with 3 N
HCl, followed by normal workup, provided 20a, which was then
purified by means of flash chromatography (hexane/ether ) 95:5). For
Acknowledgment. The authors thank the Japanese Ministry
of Education, Science and Culture for support of this work. The
authors also thank Kanto Chemicals Co. Ltd. for the gift of
zirconocene compounds. W.S. is supported by JSPS postdoctoral
fellowship.
1
20a: NMR yield 89%; isolated yield 54%; H NMR (CDCl3, Me4Si)
δ 0.85 (t, J ) 7.4 Hz, 3H), 0.99 (t, J ) 7.4 Hz, 3H), 2.08 (q, J ) 7.4
Hz, 2H), 2.40 (qd, J ) 7.4 Hz, 1.3 Hz, 2H), 6.63 (s, 1H), 7.01-7.72
(m, 21H); 13C NMR (CDCl3, Me4Si) δ 13.50, 13.64, 25.35, 30.10,
126.32, 127.02, 127.85, 128.07, 128.41, 128.66, 129.52, 129.67, 130.01,
134.34, 135.24, 137.57, 140.23, 140.75, 141.11, 141.85, 152.72, 162.75;
HRMS calcd for C34H32Si 468.2273, found 468.2281.
Supporting Information Available: Crystallographic data,
positional and thermal parameters and lists of bond lengths and
angles for 7 and 19c (17 pages). See any current masthead
page for ordering and Internet access instructions.
20b. Hydrolysis of the reaction mixture containing 19b with 3 N
HCl, followed by normal workup, provided 19b, which was then
purified by means of flash chromatography (hexane/ether ) 95:5). For
1
20b: NMR yield 82%; isolated yield 61%; H NMR (CDCl3, Me4Si)
JA972381V
δ 0.83 (t, J ) 7.4 Hz, 3H), 0.95 (t, J ) 7.6 Hz, 3H), 1.02 (t, J )
7.4Hz, 6H), 2.11 (q, J ) 7.4 Hz, 2H), 2.12 (q, J ) 7.4 Hz, 2H), 2.16
(q, J ) 7.4 Hz, 2H), 2.40 (qd, J ) 7.6 Hz, 1.3 Hz, 2H), 5.28 (t, J )
7.3 Hz, 1H), 7.31-7.39 (m, 6H), 7.54 (t, J ) 1.3 Hz, 1H), 7.65-7.70
(m, 4H); 13C NMR (CDCl3, Me4Si) δ 13.41, 13.50, 13.66, 14.90, 21.10,
21.98, 25.30, 29.90, 127.98, 129.81, 129.94, 134.82, 135.24, 137.03,
(23) Sheldrick, G. M. SHELXS-86, Program for Crystal Structure
Determination, University of Gottingen, Germany, 1986.
(24) Hall, S. R.; Flack, H. D.; Stewart, J. M. Xtal 3.2, Program for X-Ray
Crystal Structure Analysis, Universities of Western Australia, Geneva, and
Maryland, 1992.