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Abstract
The synthesis of a planarized trisamidobismuthane featuring a bulky NNN pincer ligand is described. The compounds lowest unoccupied molecular orbital features Bi(6p) orbital character arising from geometric constraint. Cyclic voltammetry measurements reveal a fully reversible one-electron reduction at E1/2 = –1.85 V vs. Fc0/+. Chemical reduction with KC8 in the presence of the sequestering agent 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane (222-crypt) allows for the isolation of an unprecedented Bi(II) radical anion. Multi-frequency EPR, X-ray absorption spectroscopy and SQUID magnetometry complemented by theoretical calculations confirm localization of the unpaired electron on the bismuth center. Initial reactivity studies display radical type reactivity as shown by single-electron transfer chemistry as well as radical trapping with diphenyldiselenide.
Supplementary materials
Title
Supporting Information
Description
Synthetic details; recorded NMR, IR,
XAS and EPR spectra; SQUID and CV data; SCXRD details;
Computational details; .xyz coordinates of computed species.
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SCXRD data for 2
Description
SCXRD data for 2
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SCXRD data for 3
Description
SCXRD data for 3
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[K@crypt][PhO]
Description
[K@crypt][PhO]
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.xyz files of computed structures
Description
.xyz files of computed structures
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