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Issue 48, 2019
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Controlling dinitrogen functionalization at rhenium through alkali metal ion pairing

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Abstract

The rhenium(I) salt Na[Re(η5-Cp)(BDI)] can be cooled in solution under a dinitrogen atmosphere to selectively access complexes containing rhenium(III) centers bound to direduced, doubly-bonded N2 (i.e. diazenide) fragments. We demonstrate this reactivity is critically dependent on ion pairing involving the Na+ ion in the starting material, as N2 binding by Na[Re(η5-Cp)(BDI)] proved to be much less favorable when the Na+ was sequestered by benzo-12-crown-4. The analogous chemistry of Na[Re(η5-Cp)(BDI)] with carbon monoxide (CO) and 2,6-xylylisocyanide (XylNC) was also investigated, which provided structural and spectroscopic bases for determining the impact of ion pairing on π-acid activation in this system.

Graphical abstract: Controlling dinitrogen functionalization at rhenium through alkali metal ion pairing

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Publication details

The article was received on 21 Nov 2019, accepted on 22 Nov 2019 and first published on 03 Dec 2019


Article type: Paper
DOI: 10.1039/C9DT04489B
Dalton Trans., 2019,48, 17936-17944

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    Controlling dinitrogen functionalization at rhenium through alkali metal ion pairing

    T. D. Lohrey, R. G. Bergman and J. Arnold, Dalton Trans., 2019, 48, 17936
    DOI: 10.1039/C9DT04489B

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