4382 Inorganic Chemistry, Vol. 35, No. 15, 1996
Scholz and Go¨rls
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Li2(tBu-DAD) by methods previously reported for (tBu-DAD)2Ti.5e
More details of the preparation of 1 and 2 have been described
previously.7
Ph), 127.77 (d, JC,H ) 156.3 Hz; o/m-Ph), 127.02 (d, JC,H ) 156.8
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1
Hz; o/m-Ph), 126.16 (d, JC,H ) 159.1 Hz; p-Ph), 126.07 (d, JC,H
)
1
2
157.8 Hz; p-Ph), 89.88 (s; ZrOC), 69.13 (dd, JC,H ) 138.1 Hz, JC,H
1: orange yellow crystals; mp 148 °C dec. 1H NMR (20 °C, THF-
) 11.4 Hz; ZrNCH), 59.85 (s; CMe3), 56.85 (s; CMe3), 32.00 (q, 1JC,H
d8): δ ) 5.68 (s, 4H, NCHdCHN), 1.18 (s, 36H, NCMe3). 13C NMR
) 124.4 Hz; CMe3), 30.07 (q, JC,H ) 126.2 Hz; CMe3).
1
1
2
(25 °C, THF-d8): δ ) 104.43 (dd, JC,H ) 164.6 Hz, JC,H ) 9.8 Hz,
NCHdCHN), 56.42 (s, NCMe3), 31.84 (q, 1JC,H ) 124.9 Hz, NCMe3).
2: yellow crystals; mp 180 °C dec. 1H NMR (20 °C, THF-d8): δ
) 5.63 (s, 4H, NCH)CHN), 1.18 (s, 36H, NCMe3). 13C NMR (25
5a: pale yellow crystals; yield 80%; mp 130 °C. Anal. Calcd for
C46H60N4O2Zr: C, 69.74; H, 7.63; N, 7.07. Found: C, 69.24; H, 7.60;
N, 7.41. 1H NMR (20 °C, THF-d8): δ ) 8.06 (d, 3JH,H ) 3.1 Hz, 2H;
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3
NdCH), 7.57 (d, JH,H ) 8.4 Hz, 4H; o-Ph), 7.21 (t, JH,H ) 7.6 Hz,
4H; m-Ph), 7.07 (t, 3JH,H ) 7.4 Hz, 2H; p-Ph), 4.19 (d, 3JH,H ) 3.0 Hz,
2H; NCH), 1.82 (s, 6H; OCMe), 1.27 (s, 18H; CMe3), 1.24 (s, 18H;
CMe3). 13C NMR (25 °C, THF-d8): δ ) 181.53 (d, 1JC,H ) 162.6 Hz;
1
2
°C, THF-d8): δ ) 102.60 (dd, JC,H ) 167.1 Hz, JC,H ) 9.0 Hz,
NCHdCHN), 56.20 (s, NCMe3), 31.91 (q, 1JC,H ) 124.9 Hz, NCMe3).
General Procedure for the Preparation of 4a,b and 5a,b.
A
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solution of the ketone 3a or 3b (11.69 mmol) in 20 mL of THF was
slowly added to a stirred solution of the DAD complexes 1 (2.50 g,
5.84 mmol) or 2 (3.01 g, 5.84 mmol) in 50 mL of THF, which was
cooled to -20 °C. The reaction mixture was warmed to room
temperature and subsequently stirred for 24 h. After evaporation of
the solvent the residue was extracted with 50 mL of diethyl ether. The
solution was concentrated and stored at -20 °C. The complexes 4a,b
or 5a,b precipitated as pale yellow or colourless crystals which were
isolated by filtration and subsequently dried in vacuo. Crystals of 4a
and 5b suitable for X-ray diffraction were prepared by slow crystal-
lization at 0 °C from a saturated diethyl ether solution prepared at room
temperature.
NdCH), 150.80 (s; i-Ph), 128.17 (d, JC,H ) 157.2 Hz; o-Ph), 126.62
(d, 1JC,H ) 156.8 Hz; m-Ph), 126.16 (d, 1JC,H ) 159.4 Hz; p-Ph), 84.95
(s; HfOC), 68.78 (d, 1JC,H ) 132.4 Hz, 2JC,H ) 11.0 Hz; HfNCH), 59.63
(s; CMe3), 56.69 (s; CMe3), 33.59 (q, 1JC,H ) 127.7 Hz; OCMe), 32.09
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(q, JC,H ) 124.4 Hz; CMe3), 30.17 (q, JC,H ) 126.2 Hz; CMe3).
5b: colorless crystals; Yield 84% mp 154 °C. Anal. Calcd for
C46H60N4O2Hf: C, 62.82; H, 6.88; N, 6.37. Found: C, 62.49; H, 6.93;
N, 6.55. 1H NMR (20 °C, THF-d8): δ ) 8.24 (d, 3JH,H ) 2.9 Hz, 2H;
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NdCH), 7.78 (d, JH,H ) 7.3 Hz, 4H; o-Ph), 7.64 (d, JH,H ) 7.3 Hz,
3
4H; o-Ph), 7.14 (m, 8H, m-Ph), 6.99 (m, 4H, p-Ph), 5.10 (d, JH,H
)
2.9 Hz, 2H; NCH), 1.42 (s, 18H; CMe3), 0.84 (s, 18H; CMe3). 13C
NMR (25 °C, THF-d8): δ ) 181.44 (d, 1JC,H ) 163.2 Hz; HfNdCH),
4a: pale yellow crystals; yield 78%; mp 122 °C. Anal. Calcd for
C36H56N4O2Zr: C, 64.72; H, 8.45; N, 8.39. Found: C, 63.99; H, 8.52;
N, 8.50. 1H NMR (20 °C, THF-d8): δ ) 7.89 (d, 3JH,H ) 2.8 Hz, 2H;
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151.19 (s; i-Ph), 149.83 (s; i-Ph), 128.10 (d, JC,H ) 159.0 Hz; o/m-
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1
Ph), 127.69 (d, JC,H ) 157.3 Hz; o/m-Ph), 127.63 (d, JC,H ) 157.9
Hz; o/m-Ph), 126.87 (d, 1JC,H ) 156.9 Hz; o/m-Ph), 126.02 (d, 1JC,H
)
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3
NdCH), 7.55 (d, JH,H ) 7.3 Hz, 4H; o-Ph), 7.21 (t, JH,H ) 7.6 Hz,
4H; m-Ph), 7.07 (t, 3JH,H ) 7.3 Hz, 2H; p-Ph), 4.24 (d, 3JH,H ) 2.8 Hz,
2H; NCH), 1.85 (s, 6H; OCMe), 1.27 (s, 18H; CMe3), 1.23 (s, 18H;
CMe3). 13C NMR (25 °C, THF-d8): δ ) 180.04 (d, 1JC,H ) 162.0 Hz;
160.3 Hz; p-Ph), 125.94 (d, 1JC,H ) 159.8 Hz; p-Ph), 88.75 (s; HfOC),
66.75 (dd, 1JC,H ) 149.5 Hz, 2JC,H ) 10.5 Hz; HfNCH), 59.91 (s; CMe3),
56.65 (s; CMe3), 32.29 (q, 1JC,H ) 124.4 Hz; CMe3), 30.07 (q, 1JC,H
126.2 Hz; CMe3).
)
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NdCH), 150.31 (s; i-Ph), 128.15 (d, JC,H ) 157.5 Hz; o-Ph), 126.64
(d, 1JC,H ) 156.4 Hz; m-Ph), 126.17 (d, 1JC,H ) 159.3 Hz; p-Ph), 85.98
(s; ZrOC), 70.99 (d, 1JC,H ) 137.5 Hz, 2JC,H ) 11.2 Hz; ZrNCH), 59.42
(s; CMe3), 56.63 (s; CMe3), 33.49 (q, 1JC,H ) 126.5 Hz; OCMe), 31.67
Acknowledgment. We thank Professor K.-H. Thiele (Merse-
burg) for the support of this work and acknowledge financial
support by the Deutsche Forschungsgemeinschaft.
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(q, JC,H ) 126.7 Hz; CMe3), 30.03 (q, JC,H ) 126.2 Hz; CMe3).
4b: colorless crystals; yield 85%; mp 146 °C. Anal. Calcd for
C36H56N4O2Hf: C, 57.24; H, 7.47; N, 7.42. Found: C, 57.10; H, 7.58;
N, 7.63. 1H NMR (20 °C, THF-d8): δ ) 8.07 (d, 3JH,H ) 2.7 Hz, 2H;
Supporting Information Available: Tables of crystallographic
data, fractional coordinates of the non-hydrogen and hydrogen atoms
and isotropic thermal parameters, anisotropic thermal parameters of
the non-hydrogen atoms, and complete bond distances and angles and
figures showing structures with complete labeling (17 pages). Ordering
information is given on any current masthead page.
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NdCH), 7.79 (d, JH,H ) 7.3 Hz, 4H; o-Ph), 7.64 (d, JH,H ) 7.2 Hz,
3
4H; o-Ph), 7.15 (m, 8H, m-Ph), 7.01 (m, 4H, p-Ph), 5.13 (d, JH,H
)
2.8 Hz, 2H; NCH), 1.41 (s, 18H; CMe3), 0.87 (s, 18H; CMe3). 13C
NMR (25 °C, THF-d8): δ ) 179.96 (d, 1JC,H ) 163.1 Hz; ZrNdCH),
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151.30 (s; i-Ph), 149.49 (s; i-Ph), 128.20 (d, JC,H ) 157.6 Hz; o/m-
IC950513K