Novel Fulvalene Derivatives of Zirconium: A Facile Entry into Organozirconium(III) Chemistry†
Dr. Terence V. Ashworth
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Search for more papers by this authorDr. Tomas Cuenca Agreda
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. Terence V. Ashworth
Anorganisch-chemisches Institut der Technischen Universität München, Lichtenbergstrasse 4, D-8046 Garching (FRG)
Search for more papers by this authorDr. Tomas Cuenca Agreda
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 authorThis work was supported by the Deutsche Forschungsgemeinschaft, the Bundesministerium für Forschung und Technologie, the Alexander-von-Humboldt Foundation (Fellowships to T. V. A. and T. C. A.), and Hoechst Aktiengesellschaft.
Graphical Abstract
A universally modifiable new starting substance, the fulvalene ZrIII complex 1, is formed upon reaction of Cp2ZrCl2 and sodium amalgam. 1 is highly reactive, but nevertheless it can be isolated. The fulvalene ligand ensures that the secondary products are dinuclear, e.g. [(CpZrCl)2(C5H4−C5H4)O], the oxidation product of 1.
References
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- 7 Experimental: A solution of 1 (1.17 g, 4 mmol) in toluene (50 mL) was treated with 1% Na/Hg (0.138 g Na, 6 mmol) and stirred for 12 h under nitrogen. The resultant dark red reaction mixture was then heated under reflux for 8 h. After filtration, evaporation, and recrystallization from toluene/n-hexane, the product was obtained as a dark red air-sensitive powder. Yield: 0.76 g (75%). An analytically pure sample was obtained by vacuum sublimation (10−5 torr). At ca. 120°C the oxo derivative 3 sublimed and pure 2 was obtained at 190°C.–Spectra: EI-MS: 2, M θ 508; 3, M θ 524; both molecular ions exhibit an isotopic pattern typical of an ion containing a Zr2CI2 moiety.-IR of 3 (KBr, v̈(ZrOZr). cm−1): 735 sand 702 s.-NMR (270 MHz, C6D6, 34°C): 2: 1H: δ = 5.57 (s, 10 H, C5H5), 4.93 (pseudotriplet, 4 H), and 3.97 (pseudotriplet, 4 H). The pseudotriplets arise from an AA′BB′ spin system with Jexp. ≈ JAB ≈ 2.7 Hz.- 13C: δ = 104.7 (C5H5), 104.6 and 101.1 (C2, C3), 106.2 (Cl). -3 1H (270 MHz, CDCI3, + 28°C): δ = 6.27 (s, 10 H, C5H5), 6.75 (m*, 2 H), 6.32 (m*, 2 H); 5.97 (m*, 2 H); m* = multiplets of an ABCD system.-13C: δ = 114.2 (C5H5), 104.2, 111.8, 113.7, 114.6 (C2-5), Cl not observed.
- 8 B. A. Frenz et al.: SDP, Structure Determination Package. College Station, TX 77840 (USA). 3, pale yellow crystals (from toluene); V = 2583.9 × 106 pm3, C2/c, Z = 4, F000 = 794, p = 1.59 g cm−3, μ = 10.2 cm−1; CAD-4 (Enraf Nonius), Mokα, graphite monochromator, ω-scan (Δω = 0.80°tgθ, 2° ≤θ≤22°), tmax = 60 s, h(–16/16), k(0/13), l(–15/15), 1471 reflections (I>1σ(I)).–Solution of structure: Patterson and difference Fourier methods; all non-hydrogen atoms refined anisotropically; H-atoms calculated from ideal geometry, included in structure factor calculations, but not refined; R = 0.046, Rw = 0.055.— Further details of the crystal structure determination are available on request from the Fachinformationszentrum Energie, Physik, Mathematik GmbH, D-7514 Eggenstein-Leopoldshafen 2, on quoting the depository number CSD-51 661, the names of the authors, and the full citation of the journal.
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