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Issue 44, 2019
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Reactions of In–Zn bonds with organic azides: products that result from hetero- and homo-bimetallic behaviour

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Abstract

The indyl anion, K[In(NONDipp)] (NONDipp = [O(SiMe2NDipp)2]2−, Dipp = 2,6-iPr2C6H3) reacts with group 12 compounds M(BDIR)Cl (M = Zn, Cd; BDI = [HC{C(Me)NR}2], R = 2,4,6-Me3C6H2 (Mes), Dipp) to afford the heterobimetallic compounds (NONDipp)In–M(BDIR) that contain the first In–Zn and In–Cd bonds. The reactivity of the In–Zn bonds towards organic azides, R′N3 (R′ = Mes, Dipp, Ph) was investigated. (NONDipp)In–Zn(BDIMes) reduces MesN3via an isolable triazenide intermediate to generate the bridging imido compound, (NONDipp)In–(μ-NMes)–Zn(BDIMes). Similar reactivity is noted from early–late heterobimetallic complexes. Under the same conditions, PhN3 reacts to afford a product that contains a bridging tetraazenide ligand, which is formed from the formal (2 + 3)-cycloaddition of second azide to an indium-imido bond. However, increasing the bulk of the BDI-ligand in (NONDipp)In–Zn(BDIDipp) leads to reductive coupling of PhN3 to give the hexazene complex. This mode of reactivity is reminiscent of the reductive behaviour of homobimetallic compounds.

Graphical abstract: Reactions of In–Zn bonds with organic azides: products that result from hetero- and homo-bimetallic behaviour

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Publication details

The article was received on 10 Oct 2019, accepted on 18 Oct 2019 and first published on 21 Oct 2019


Article type: Paper
DOI: 10.1039/C9DT03990B
Dalton Trans., 2019,48, 16588-16594

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    Reactions of In–Zn bonds with organic azides: products that result from hetero- and homo-bimetallic behaviour

    M. D. Anker, Y. Altaf, M. Lein and M. P. Coles, Dalton Trans., 2019, 48, 16588
    DOI: 10.1039/C9DT03990B

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