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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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Supplementary files

Article information


Submitted
21 ኖቬም 2019
Accepted
22 ኖቬም 2019
First published
03 ዲሴም 2019

Dalton Trans., 2019,48, 17936-17944
Article type
Paper
Author version available

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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