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Issue 3, 2015
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A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes

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Abstract

To explore metal–metal multiple bonds between first row transition metals, Ti/Co complexes supported by two phosphinoamide ligands have been synthesized and characterized. The Ti metalloligand Cl2Ti(XylNPiPr2)2 (1) was treated with CoI2 under reducing conditions, permitting isolation of the Ti/Co complex [(μ-Cl)Ti(XylNPiPr2)2CoI]2 (2). One electron reduction of complex 2 affords ClTi(XylNPiPr2)2CoPMe3 (3), which features a metal–metal triple bond and an unprecedentedly short Ti–Co distance of 2.0236(9) Å. This complex is shown to promote the McMurry coupling reaction of aryl ketones into alkenes, with concomitant formation of the tetranuclear complex [Ti(μ3-O)(NXylPiPr2)2CoI]2 (4). A cooperative mechanism involving bimetallic C[double bond, length as m-dash]O bond activation and a cobalt carbene intermediate is proposed.

Graphical abstract: A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes

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Publication details

The article was received on 05 Dec 2014, accepted on 18 Jan 2015 and first published on 19 Jan 2015


Article type: Edge Article
DOI: 10.1039/C4SC03772C
Citation: Chem. Sci., 2015,6, 2044-2049
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    A heterobimetallic complex featuring a Ti–Co multiple bond and its application to the reductive coupling of ketones to alkenes

    B. Wu, M. W. Bezpalko, B. M. Foxman and C. M. Thomas, Chem. Sci., 2015, 6, 2044
    DOI: 10.1039/C4SC03772C

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