The Reactivity of the Unbridged CoSn Bond in [(η5-C5H5)(η2-C2H4)CoSn{CH[Si(CH3)3]2}2]—The First Organometallic Complexes with direct CoSnChalcogen Bonding (Chalcogen = Se, Te)†
Corresponding Author
Priv.-Doz. Dr. Jörg J. Schneider
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]Search for more papers by this authorDipl.-Chem. Jörg Hagen
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]
Search for more papers by this authorDipl.-Ing. Dieter Bläser
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]
Search for more papers by this authorProf. Dr. Roland Boese
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]
Search for more papers by this authorProf. Dr. Carl Krüger
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim (Germany)
Search for more papers by this authorCorresponding Author
Priv.-Doz. Dr. Jörg J. Schneider
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]Search for more papers by this authorDipl.-Chem. Jörg Hagen
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]
Search for more papers by this authorDipl.-Ing. Dieter Bläser
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]
Search for more papers by this authorProf. Dr. Roland Boese
Anorganisch-chemisches Institut der Universität, Universitätsstrasse 5–7, D-45117 Essen (Germany), Fax: Int. code + (201) 183-2402, e-mail: [email protected]
Search for more papers by this authorProf. Dr. Carl Krüger
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim (Germany)
Search for more papers by this authorJ. J. S. thanks the Deutsche Forschungsgemeinschaft (Heisenberg-Stipendium and SCHN-375/3-1) as well as the Fonds de Chemischen Industrie for support. We thank Dr. D. Stöckigt and co-workers (Max-Planck-Institut für Kohlenforschung) for recording the mass spectra.
Graphical Abstract
Butterflylike frameworks are present in the isostructural clusters 1 and 2, in which the chalcogen atom is bound as a μ3 ligand to Co and Sn. These complexes are formed by Se/Te addition to the unbridged CoSn bond of 3 at room temperature. Compounds 1 and 2 are the first defined molecular complex compounds that contain the typical semiconductor combination Sn/E (E = Se, Te) and a ferromagnetic metal, and thus they could be of interest for applications in materials science.
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X-ray crystal structure analysis: 3a: C21H47CoSi4Sn, M = 595.64 gmol−1, T = 190 K, crystal dimensions: 0.34 × 0.27 × 0.13 mm3, R3m /V-Nicolet four-circle diffractometer (MoKα radiation, graphite monochromator), triclinic, cell dimensions (from 40 reflections, 2θ range 20–25°): a = 9.061(2), b = 11.056(3), c = 16.132(4) Å, α = 75.70(3), β = 85.86(3), γ = 67.67(3)°, V = 1447.1(3) Å3; space group P1 (no. 2), Z = 2, ρcalcd = 1.353 Mgm−3, μ = 1.685 mm−1, empiricial absorption correction with Ψ scan data, max/min transmission 1.00/0.761, Rmerg before/after correction 0.0538/0.0360, 2θmax = 45°, 5143 measured, 3770 independent, 3236 observed intensities [I > 2σ(I)] (R merg = 0.0858). Structure solution with SHELXS and refinement against F2 (SHELXTL-Plus version 5.03/Iris), 249 parameters, hydrogen atoms refined with a riding model with a common isotropic displacement factor; R1 = 0.0425 [I > 2σ(I)], wR2 = 0.0919, w−1 = σ2(F
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, +2F
)]/3 ist. 5: C33H81CoSeSi8Sn2, M = 1079.0 gmol−1, crystal dimensions: 0.12 × 0.41 × 0.36 mm3, a = 9.3161(2), b = 15.216(4), c = 36.6880(9) Å, V = 5200.5(14) Å3, T = 173 K, ρcalcd = 1.38 gcm−3, μ = 2.166 mm−1, Z = 4, orthorhombic, space group P212121 (no. 19), Siemens-SMART CCD system, λ = 0.71069 Å, 19195 measured reflections (±h, +k, +l), [(sinθ)/λ]max 0.83 Å−1, 19195 independent and 12680 observed reflections [I ≦ 2σ(I)], 406 refined parameters; heavy atom method, H atom positions calculated and not refined, R = 0.0629, R
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+2F
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) +(0.0531P)2 +18.47P, where P = [(max F
,O) + 2F
)]/3, absolute structure parameter–0.01(3). The anisotropic displacement factors of several methyl groups, particularly at C25, indicate disorder, which, however, cannot be resolved. Further details of the crystal structure investigations may be obtained from the Fachinformationszentrum Karlsruhe, D-76344 Eggenstein- Leopoldshafen (Germany), on quoting the depository numbers CSD-100065, CSD- 406237, and CSD-406 281.
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