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Issue 2, 2012
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“Rollover” cyclometalation – early history, recent developments, mechanistic insights and application aspects

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Abstract

“Rollover” cyclometalation constitutes a special case among the well-known class of cyclometalation reactions. An overview is given that covers the very first description of this reaction type, as well as recent developments. In addition, not only condensed-phase experiments are reviewed, but also investigations based on mass spectrometric techniques, together with “in silico” studies using DFT-based calculations are considered. While the latter two methods allow for a detailed analysis of the intrinsic factors that affect the reaction mechanisms, consideration of all three regimes permits to develop a coherent mechanistic picture and to address the often noted gap between condensed- and gas-phase studies. Moreover, the quite unexpected reactivity of “rollover” cyclometalated complexes in gas-phase experiments, as well as potential applications, e.g. in synthetic procedures, are discussed in some detail.

Graphical abstract: “Rollover” cyclometalation – early history, recent developments, mechanistic insights and application aspects

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Publication details

The article was received on 08 Sep 2011, accepted on 12 Oct 2011 and first published on 12 Oct 2011


Article type: Perspective
DOI: 10.1039/C1SC00651G
Citation: Chem. Sci., 2012,3, 308-326
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    “Rollover” cyclometalation – early history, recent developments, mechanistic insights and application aspects

    B. Butschke and H. Schwarz, Chem. Sci., 2012, 3, 308
    DOI: 10.1039/C1SC00651G

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