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Issue 7, 2017
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Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

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Abstract

We report the synthesis and reactivity of paramagnetic heterometallic complexes containing a Ti(III)-μ-H-Al(III) moiety. Combining different stoichiometries amounts of Cp2TiCl and KH3AlC(TMS)3 (Cp = cyclopentadienyl, TMS = trimethylsilyl) resulted in the formation of either bimetallic Cp2Ti(μ-H)2(H)AlC(TMS)3 (2) or trimetallic (Cp2Ti)2(μ-H)3(H)AlC(TMS)3 (3) via salt metathesis pathways. While these complexes were indefinitely stable at room temperature, the bridging hydrides were readily activated upon exposure to heteroallenes, heating, or electrochemical oxidation. In each case, formal hydride oxidation occurred, but the isolated product maintained the +3 oxidation state at both metal centers. The nature of this reactivity was explored using deuterium labelling experiments and Density Functional Theory (DFT) calculations. It was found that while C–H activation from the Ti(III) bimetallic may occur through a σ-bond metathesis pathway, chemical oxidation to Ti(IV) promotes bimolecular reductive elimination of dihydrogen to form a Ti(III) product.

Graphical abstract: Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

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Publication details

The article was received on 25 Apr 2017, accepted on 09 May 2017 and first published on 31 May 2017


Article type: Edge Article
DOI: 10.1039/C7SC01835E
Citation: Chem. Sci., 2017,8, 5153-5160
  • Open access: Creative Commons BY license
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    Hydride oxidation from a titanium–aluminum bimetallic complex: insertion, thermal and electrochemical reactivity

    A. C. Brown, A. B. Altman, T. D. Lohrey, S. Hohloch and J. Arnold, Chem. Sci., 2017, 8, 5153
    DOI: 10.1039/C7SC01835E

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