Organometallics
Article
Yield of the isolated 12: 0.278 g (17%). Mp: 213−215 °C under Ar.
ASSOCIATED CONTENT
■
* Supporting Information
Anal. Calcd for C H Si Zr: C, 69.96; H, 6.20. Found: C, 69.88; H,
6
3
6
38
2
S
1
.13. H NMR (297 K, benzene-d , δ, ppm): 0.36 (s, 9H, C(1)−
6
Table of crystal data and structure refinement parameters for 8,
SiMe ); 0.65 (s, 9H, C(4)−SiMe ); 5.31 (s, 10H, Cp); 6.91 (m, 1H,
3
3
9
CC−p-Ph); 6.99 (m, 2H, CC−m-Ph); 7.19 (m, 1H, C(6)−p-
Ph); 7.35 (m, 2H, CC−o-Ph); 7.39 (m, 2H, C(6)−m-Ph); 7.49 (m,
1
3
2
(
H, C(6)−o-Ph). C NMR (297 K, benzene-d , δ, ppm): −0.5
6
C(4)−SiMe ); 1.4 (C(1)−SiMe ); 88.8 (C(5)−CC); 92.8 (C(5)−
AUTHOR INFORMATION
3
3
■
CC); 103.6 (C(2)); 106.2 (Cp); 124.3(C(6)−p-Ph), 125.4 (C
C−i-Ph), 126.4 (C(6)−o-Ph); 127.2 (CC−p-Ph); 127.9 (C(6)−m-
Ph); 128.5 (CC−m-Ph); 131.2 (CC−o-Ph); 143.6 (C(5)); 155.9
*
*
(
(
−
(
C(6)−i-Ph); 156.0 (C(4)); 162.6 (C(1)); 184.2 (C(3)); 225.0
C(6)). 29Si NMR (297 K, benzene-d , δ, ppm): −7.4 (C(1)−SiMe );
Notes
6
3
8.9 (C(4)−SiMe ) (for the numbering scheme, see Figure 5). IR
The authors declare no competing financial interest.
3
−
1
ATR, ν, cm ): 1871 (CCCC); 2188 (CC). MS (70 eV,
+
+
+
m/z): 616 [M] ; 414 [M − PhC Ph] ; 220 [Cp Zr] .
ACKNOWLEDGMENTS
2 2
■
Yield of the isolated 13: 0.048 g (2.9%). Mp: 104−105 °C under Ar.
This work was supported by the Russian Foundation for Basic
Research (project code 15-03-03485) and the Deutsche
Forschungsgemeinschaft (RO 1269/9-1).
Anal. Calcd for C H Si Zr: C, 80.59; H, 4.85. Found: C, 80.04; H,
36
38
2
1
5
(
.11. H NMR (297 K, toluene-d , δ, ppm): 5.35 (s, 10H, Cp); 6.89
8
m, 1H, CC−p-Ph); 6.95 (m, 2H, CC−m-Ph); 7.08 (m, 1H,
C(1)−p-Ph); 7.15 (m, 2H, CC−o-Ph); 7.17 (m, 1H, C(4)−p-Ph);
.18 (m, 1H, C(6)−p-Ph); 7.22 (m, 2H, C(1)−m-Ph); 7.32 (m, 2H,
C(4)−m-Ph); 7.39 (m, 2H, C(6)−m-Ph); 7.48 (m, 2H, C(6)−o-Ph) ;
DEDICATION
7
■
Dedicated to the memory of Professor Michael F. Lappert.
13
7
.59 (m, 2H, C(1)−o-Ph); 8.30 (m, 2H, C(4)−o-Ph). C NMR (297
K, toluene-d , δ, ppm): 89.5 (C(2)); 91.6 (C(5)−CC); 92.0
8
REFERENCES
■
(
C(5)−CC); 106.7 (Cp); 124.5 (C(6)−p-Ph); 125.4 (CC−i-
(
1
1) Hsu, D. P.; Davis, W. M.; Buchwald, S. L. J. Am. Chem. Soc. 1993,
15, 10394.
Ph); 126.7 (C(6)−o-Ph); 127.2 (CC−p-Ph); 127.9 (C(6)−m-Ph);
1
28.1 (C(4)−m-Ph); 128.2 (C(4)−p-Ph); 128.3 (C(1)−p-Ph); 128.3
(2) Burlakov, V. V.; Bogdanov, V. S.; Lyssenko, K. A.; Spannenberg,
(
(
(
CC−m-Ph); 129.2 (C(1)−m-Ph); 129.2 (C(4)−o-Ph); 131.2
CC−o-Ph); 132.5 (C(1)−o-Ph); 135.7 (C(1)−i-Ph); 139.5
C(4)−i-Ph); 140.7 (C(5)); 141.3 (C(4)); 156.0 (C(6)−i-Ph);
A.; Petrovskii, P. V.; Baumann, W.; Arndt, P.; Minacheva, M. Kh.;
Strunin, B. N.; Rosenthal, U.; Shur, V. B. Izv. Akad. Nauk, Ser. Khim.
2
(
012, 163; Russ. Chem. Bull., Int. Ed. 2012, 61, 165.
3) Rosenthal, U.; Ohff, A.; Baumann, W.; Kempe, R.; Tillack, A.;
Burlakov, V. V. Angew. Chem., Int. Ed. Engl. 1994, 33, 1605.
4) Kempe, R.; Ohff, A.; Rosenthal, U. Z. Kristallogr. 1995, 210, 707.
1
58.5 (C(1)); 167.5 (C(3)); 220.2 (C(6)) (the numbering scheme
in the seven-membered ring of 13 is analogous to that for complex 12
−1
in Figure 5). IR (ATR, ν, cm ): 1865 (CCCC). MS (70 eV,
(
+
+
+
m/z): 624 [M] ; 422 [M − PhC Ph] ; 404 [M − Cp Zr] ; 220
2
2
(5) Bredeau, S.; Delmas, G.; Pirio, N.; Richard, P.; Donnadieu, B.;
Meunier, P. Organometallics 2000, 19, 4463.
+
[
Cp Zr] .
2
Synthesis of Complex 14. A mixture of 1 (1.118 g, 1.83 mmol)
and tolane (0.351 g, 1.97 mmol) was dissolved in 20 mL of toluene,
and the resulting yellow-orange solution was heated for 16 days at 100
C. Then, the red-orange reaction mixture was evaporated in vacuo,
the oily residue was dissolved at 60 °C in 20 mL of n-hexane, and the
obtained solution, after cooling to room temperature and filtration,
was placed in dry ice. After 1 day, the precipitated fine crystalline
orange complex 14 was separated from the mother liquor by
decanting, washed with cold n-hexane, and dried in vacuo. Yield of
(
̈
6) Bredeau, S.; Ortega, E.; Delmas, G.; Richard, P.; Frohlich, R.;
Donnadieu, B.; Kehr, G.; Pirio, N.; Erker, G.; Meunier, P.
Organometallics 2009, 28, 181.
°
(7) Burlakov, V. V.; Bogdanov, V. S.; Arndt, P.; Spannenberg, A.;
Lyssenko, K. A.; Baumann, W.; Minacheva, M. Kh.; Strunin, B. N.;
Rosenthal, U.; Shur, V. B. J. Organomet. Chem. 2014, 751, 390.
(8) Burlakov, V. V.; Peulecke, N.; Baumann, W.; Spannenberg, A.;
Kempe, R.; Rosenthal, U. Collect. Czech. Chem. Commun. 1997, 62,
331.
(9) Fu, X.; Chen, J.; Li, G.; Liu, Y. Angew. Chem., Int. Ed. 2009, 48,
1
4: 0.515 g (47%). Mp: 212−213 °C under Ar. Anal. Calcd for
1
5500.
C H Si Zr: C, 68.74; H, 6.45. Found: C, 68.53; H, 6.22. H NMR
3
4
38
2
(10) Becker, L.; Burlakov, V. V.; Arndt, P.; Spannenberg, A.;
(
297 K, benzene-d , δ, ppm): 0.14 (s, 9H, C(4)−SiMe ); 0.39 (s, 9H,
6
3
Baumann, W.; Jiao, H.; Rosenthal, U. Chem.Eur. J. 2013, 19, 4230.
C(1)−SiMe ); 5.40 (s, 10H, Cp); 6.83 (m, 1H, C(6)−p-Ph); 6.93 (m,
3
(11) Chen, J.; Li, Y.; Gao, H.; Liu, Y. Organometallics 2008, 27, 5619.
1
H, C(5)−p-Ph); 7.08 (m, 2H, C(5)−m-Ph); 7.10 (m, 2H, C(6)−m-
13
(12) Hashmi, S.; Polborn, K.; Szeimies, G. Chem. Ber. 1989, 122,
Ph); 7.20 (m, 2H, C(6)−o-Ph); 7.26 (m, 2H, C(5)−o-Ph). C NMR
2
399.
(
297 K, benzene-d , δ, ppm): −0.1 (C(4)−SiMe ); 1.5 (C(1)−
6
3
(
13) Burlakov, V. V.; Ohff, A.; Lefeber, C.; Tillack, A.; Baumann, W.;
Kempe, R.; Rosenthal, U. Chem. Ber. 1995, 128, 967.
14) Burlakov, V. V.; Bogdanov, V. S.; Lyssenko, K. A.; Petrovskii, P.
SiMe ); 104.0 (C(2)); 106.3 (Cp), 123.1 (C(6)−p-Ph); 125.8 (C(5)−
3
p-Ph); 126.9 (C(6)−o-Ph); 127.4 (C(6)−m-Ph); 127.5 (C(5)−m-
Ph); 130.6 (C(5)−o-Ph); 143.8 (C(5)−i-Ph); 155.0 (C(6)−i-Ph);
(
V.; Beweries, T.; Arndt, P.; Rosenthal, U.; Shur, V. B. Izv. Akad. Nauk,
Ser. Khim. 2008, 1294; Russ. Chem. Bull., Int. Ed. 2008, 57, 1319.
1
(
−
59.5 (C(4)); 162.5 (C(1)); 166.1 (C(5)); 185.0 (C(3)); 207.9
C(6)). 29Si NMR (297 K, benzene-d , δ, ppm): −7.5 (C(1)−SiMe );
6
3
(15) Burlakov, V. V.; Beweries, T.; Bogdanov, V. S.; Arndt, P.;
10.0 (C(4)−SiMe ) (for the numbering scheme, see Figure 6).
3
Baumann, W.; Petrovskii, P. V.; Spannenberg, A.; Lyssenko, K. A.;
Shur, V. B.; Rosenthal, U. Organometallics 2009, 28, 2864.
−1
Raman spectrum (ν, cm ): 1873 (CCCC). MS (70 eV, m/z):
+
+
5
92 [M] , 220 [CpZr] .
(
16) Beweries, T.; Burlakov, V. V.; Peitz, S.; Bach, M. A.; Arndt, P.;
Baumann, W.; Spannenberg, A.; Rosenthal, U. Organometallics 2007,
6, 6827.
17) Burlakov, V. V.; Nelyubina, Yu. V.; Lyssenko, K. A.; Shur, V. B.;
X-ray Diffraction Study. Diffraction data were collected on a
Bruker APEX II CCD diffractometer using graphite-monochromated
2
(
Mo Kα radiation. The structures were solved by direct methods and
2
refined by full-matrix least-squares procedures on F with the
Arndt, P.; Kaleta, K.; Baumann, W.; Rosenthal, U. Inorg. Chem.
Commun. 2011, 14, 975.
(18) Jemmis, E. D.; Phukan, A. K.; Rosenthal, U. J. Organomet. Chem.
2001, 635, 204.
34
SHELXTL software package. Crystallographic data for complexes
, 9, 10, 12, and 14 are presented in the Supporting Information
Table 1).
8
(
I
Organometallics XXXX, XXX, XXX−XXX