Dinuclear Fulvalene Complexes of Tri- and Tetravalent Zirconium†
Corresponding Author
Prof. Dr. Wolfgang A. Herrmann
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)Search for more papers by this authorDr. Tomás Cuenca
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Search for more papers by this authorDr. Babil Menjón
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Search for more papers by this authorDr. Eberhardt Herdtweck
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Search for more papers by this authorCorresponding Author
Prof. Dr. Wolfgang A. Herrmann
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)Search for more papers by this authorDr. Tomás Cuenca
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Search for more papers by this authorDr. Babil Menjón
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Search for more papers by this authorDr. Eberhardt Herdtweck
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Search for more papers by this authorChemistry of Oxophilic Transition Metals, Part 3. This work was supported by the Alexander-von-Humboldt-Stiftung (T. C. and B. M. ) and by Hoechst Aktiengesellschaft.–Part 2: [4c].
Graphical Abstract
The isomers 2 count among the few unequivocally characterized ZrIII-alkyl compounds. They were prepared from 1 and MeLi exploiting the fulvalene bracketing effect. Further functionalization of 1 without fragmentation has also been achieved.
References
- 1 Recent monograph: D. J. Cardin, M. F. Lappert, C. L. Raston: Chemistry of Organozirconium and -hafnium Compounds, Horwood/Wiley, Chichester/New York 1986.
- 2 Recent examples: (a) J. H. Wengrovius, R. R. Schrock, C. S. Day, Inorg. Chem. 20 (1981) 1844; (b) J. Blenkers, P. Bruin, J. H. Teuben, J. Organomet. Chem. 297 (1985) 61.
- 3 R. Choukronn, M. Basso-Bert, D. Gervais, J. Chem. Soc. Chem. Commun., 1986 1317.
- 4(a) T. V. Ashworth, T. Cienca, E. Gerdtweck, W. A. Herrmann, Angew. Chem. 98 (1986) 278; Angew. Chem. Int. Ed. Engl. 25 (1986) 289; (b) W. A. Herrmann, T. Cuenca, U. Küsthardt, J. Organomet. Chem. 309 (1986) C 15; (c) T. Cuenca, W. A. Herrmann, T. V. Ashworth, Organometallics 5 (1986) 2514; (d) X-ray structure of 1: S. Gambarotta, M. Y. Chiang, Organometallics 6 (1987) 897.
- 5 Data for 2a/b: 1H-NMR (270 MHz, C6D6, 28 °C); δ(CH3) = −0.30/0.01 [s, 6H]; δ(C5 H5) = 5.74/5.70 [s, 10H]; δ(C10 H8) = 6.44/6.33, 5.88/5.51, 5.44/5.18, 5.02/4.98 [4m, 8H].–13 C-NMR (67.8 MHz, C6D6, 28 °C): δ(CH3) = 22.61/22.72; δ(C5H5) = 109.53/108.71; δ(C10H8) = 125.62, 124.51, 120.39, 113.58, 110.20, 108.51, 107.68, 105.48, 100.00, 95.00.–EI-MS (70 eV): m/z 468 ( M⊕ für C22H244Zr2).–Correct C, H, Zr analysis.
- 6(a) A. Schäfer, W. A. Herrmann, J. Organomet. Chem. 297 (1985) 229; (b) A. Schäfer, Dissertation, Technische Universität München 1987.
- 7 Data for 4: 1H-NMR (270 MHz, C6D6, 28 °C); δ(CH3) = −0.10 [s, 12 H]; δ(C5H5) = 5.74 [s, 10H]; δ(C10H8) = 5.91, 5.99 [2t, A2B2 system, J = 2.60 Hz, 8H].–13C-NMR (67.8 MHz, C6D6, 28 °C); δ(CH3) = 31.57; δ(C5H5) = 110.85; δ(C10H8) = 107.56, 110.08, 120.60.–EI-MS (70 eV); m/z 498 (M⊕ für C24H30Zr2).–Correct C, H, Zr analysis.
- 8 Data for 5: 1H-NMR 270 MHz, C6H5CD3, (−25°C); δ(ZrCH3) = 0.25 [s, 6H]; δ(CCH3) = 2.16 [s, 12H]; δ( t-C4H9) = 1.03 [s, 18 H]; δ(C5H5) = 5.38 [s, 10H]; δ(C10H8) = 5.2–5.6 [m, 8H].–IR (cm−1, KBr); ṽ(CN) = 1637.–EI-MS (70 eV); m/z 568 (M⊕ für C34H48N2Zr2).–Correct C,H,N analysis.
- 9 Other “η2-iminoacyl” complexes: (a) R. D. Adams, D. F. Chodosh, Inorg. Chem. 17 (1978) 41; (b) P. T. Wolczanski, J. E. Bercaw, J. Am. Chem. Soc. 101 (1979) 6450; (c) M. F. Lappert, N. T. Luong-Thi, C. R. C. Milne, J. Organomet. Chem. 174 (1979) C 35.
- 10 Data for 6: 1H-NMR(270 MHz, [D8] THF, 28 °C); δ(CH3) = 1.49 [s, 9H]; δ(C5H5) = 6.21 and 5.81 [2s, 2 × 5H]; δ(C10H8) = 6.47, 6.34, 6.21, 6.01, 5.69, 5.54, 5.06, 4.88 [8m, 8 × 1H].–13C-NMR (67.80 MHz, [D8]THF, 30 °C); δ(C5H5) = 110.89 and 110.34; δ(CH3) = 29.93; δ(C(CH3)3) = 30.82; δ(NC) = 218.12; δ(C10H8) = 94.54, 100.37, 102.91, 103.32, 103.37, 104.75, 112.43, 114.83, 118.22, 125.67.–IR (cm −1, KBr); ṽ(CN) = 1652/ 1648.–EI-MS (70 eV); m/z 538 ([M–C(CH3)3]⊕)-Correct C, H, N analysis.
- 11 X-ray structure analysis of 6: orthorhombic (from toluene/n-hexane, 25° C), space group p212121 (IT-No. 19): a = 823.3(1), b = 1689.1(2), c = 1731.2(2)pm; α = β = γ = 90°; V = 2407 × 106pm3; Z = 4; ρcalcd = 1.641 g cm−3; empirical absorption correction: μ = 10.9 cm−1: λ = 71.073 pm (MoKα radiation): T = 23+ 1 °C; Enraf-Nonius-CAD-4; measuring range 2.0 ⩽ θ ⩽ 25.0°: 4517 measured reflections, 4029 independent reflections with I > 1σ(I); R = Σ∥Fo|–|Fc∥Σ|Fo| = 0.017; Rw = [Σw(|Fo|–|Fc|)2/Σw[Fo]2]1/2 = 0.018 with w = 1/σ2 (Fo); structure solved by Patterson methods. A difference Fourier synthesis with heavy metal atom positions only, revealed almost all hydrogen positions which were calculated for ideal geometry (d(CH) = 95 pm). The hydrogen atoms and their temperature factors were included in the calculation of the structure factors but not refined. The temperature factors are the same for all hydrogen atoms. Anomolous dispersion was taken into account. The asymmetric unit contains 30 “heavy” atoms (anisotropic temperature factors), 27 H atoms: 271 parameters were “full-matrix” refined.–Shift/error < 0.00 in the last refinement cycle: residual electron density: +0.39 e/Å3. Further details of the crystal structure investigation are available on request from the Fachinformationszentrum Energie. Physik. Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen 2 (FRG), on quoting the depository number CSD-52358, the names of the authors, and the journal citation.
- 12 W. A. Herrmann, B. Menjón, E. Herdtweck, unpublished.
