Controlling dinitrogen functionalization at rhenium through alkali metal ion pairing
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.
Additional Information
© 2019 The Royal Society of Chemistry. The article was received on 21 Nov 2019, accepted on 22 Nov 2019 and first published on 03 Dec 2019. This research was funded by the NSF (Grant No. CHE-1465188). T. D. L. thanks the U.S. DOE Integrated University Program for a graduate research fellowship. Michael A. Boreen, Jade I. Fostvedt, and Erik T. Ouellette are acknowledged for helpful discussions. Prof. Simon Humphrey (University of Texas, Austin) is thanked for a generous gift of rhenium. The Advanced Light Source (ALS) is supported by the Director, Office of Science, Office of Basic Energy Sciences, of the U.S. DOE under Contract No. DE-AC02-05CH11231. Dr Simon J. Teat is thanked for training and guidance throughout our crystallography experiments at the ALS. There are no conflicts to declare.Attached Files
Supplemental Material - c9dt04489b1_si.pdf
Supplemental Material - c9dt04489b2.cif
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Additional details
- Eprint ID
- 100176
- DOI
- 10.1039/c9dt04489b
- Resolver ID
- CaltechAUTHORS:20191204-090016184
- CHE-1465188
- NSF
- DE-AC02-05CH11231
- Department of Energy (DOE)
- Created
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2019-12-04Created from EPrint's datestamp field
- Updated
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2021-11-16Created from EPrint's last_modified field