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Title: Dinuclear Coordination of a Novel Four-electron Reduced μ-η1,η3-allene Ligand with β-agostic C–H⋯Ta Interaction: Direct Addition of allene to (C5Me5)2Ta2(μ-X)4 (X = Cl, Br), and Molecular Structure of (C5Me5)2Ta2(μ-η1,η3-C3H4)(μ-Cl)Cl3
Authors: Huang, Jui-Hsien;Lee, Ting-Yu;Swenson, Dale C.;Messerle,Louis
Contributors: 化學系
Keywords: Tantalum;Organoditantalum;Allene complex;C–H agostic interaction;Dinuclear
Date: 2006-01
Issue Date: 2012-12-10T01:39:43Z
Publisher: Elsevier
Abstract: The organoditantalum complexes (η-C5Me5)2Ta2(μ-X)4 (X = Cl, Br) react with 1–5 equiv. of allene under mild conditions to afford the fluxional allene adducts (C5Me5)2Ta2(μ-η1,η3-C3H4)(μ-X)X3 as shown by spectroscopic and spectrometric data. Low-temperature-limit proton NMR data at −95 °C for (C5Me5)2Ta2(μ-η1,η3-C3H4)(μ-Cl)Cl3 show a large chemical shift range for the inequivalent allene hydrogens, with a high-field value for one hydrogen at δ −0.36, and inequivalent Cp* groups. The low-temperature-limit 13C NMR resonances for the allene ligand are found at δ 204.4 (central C), δ 70.3 (CH2, 1JCH = 154 Hz), and the substantially upfield value of δ 42.9. The latter resonance has remarkably different coupling constants (1JCH = 173, 154 Hz). The allene coordinates in a novel alkylidene-diyl fashion in the solid-state, as shown by X-ray diffractometry on (C5Me5)2Ta2(μ-η1,η3-C3H4)(μ-Cl)Cl3 at 200 K. One tantalum is doubly-bonded to the central allenic carbon (Ta1C22 distance, 2.011(7) Å) and interacts with an allene hydrogen in a probable β-agostic manner (Ta1–H21A distance of 2.25(10) Å). The second tantalum is coordinated to the allene in a hybrid of η3-allylic and sigma bonding, with Ta2–C distances to the allene methylenes of 2.206(8) and 2.276(9) Å and a Ta2–C22 bond distance to the central allenic carbon of 2.253(7) Å. The allene hydrogens are oriented above and below the C–C–C plane, consistent with appreciable σ-bonding between the Ta(2) and the allene methylenes. The bent allene ligand has a C–C–C angle of 106.0(6)° and can be viewed as reduced by four electrons, with concomitant oxidation of the two d2 tantalum centers of the organoditantalum(III) reactant. The long Ta⋯Ta nonbonded distance of 3.3052(8) Å is consistent with two d0 tantalum centers in an organoditantalum(V) product.
Relation: Polyhedron, 25(2): 559-567
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