Back donation, intramolecular electron transfer and N–O bond scission targeting nitrogen oxyanion reduction: how can a metal complex assist?
| Autor: | Kenneth G. Caulton, Daniel M. Beagan, Alyssa C. Cabelof |
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| Rok vydání: | 2021 |
| Předmět: | |
| Zdroj: | Dalton Transactions. 50:2149-2157 |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/d0dt03430d |
| Popis: | A density functional theory exploration studies a range of ancillary coordinated ligands accompanying nitrogen oxyanions with the goal of promoting back donation towards varied nitrogen oxidation states. Evaluation of a suite of Ru and Rh metal complexes reveals minimum back donation to the κ1-nitrogen oxyanion ligand, even upon one-electron reduction. This reveals some surprising consequences of reduction, including redox activity at pyridine and nitrogen oxyanion dissociation. Bidentate nitrate was therefore considered, where ancillary ligands enforce geometries that maximize M-NOx orbital overlap. This strategy is successful and leads to full electron transfer in several cases to form a pyramidal radical NO32- ligand. The impact of ancillary ligand on degree of nitrate reduction is probed by comparing the powerful o-donor tris-carbene borate (TCB) to a milder donor, tris-pyrazolyl borate (Tp). This reveals that with the milder Tp donor, nitrate reduction is only seen upon addition of a Lewis base. Protonation of neutral and anionic (TCB)Ru(κ2-NO3) at both terminal and internal oxygens reveals exergonic N-O bond cleavage for the reduced species, with one electron coming from Ru, yielding a RuIII hydroxide product. Comparison of H+ to Na+ electrophile shows weaker progress towards N-O bond scission. Finally, calculations on (TCB)Fe(κ2-NO3) and [(TCB)Fe(κ2-NO3)]- show that electron transfer to nitrate is possible even with an earth abundant 3d metal. |
| Databáze: | OpenAIRE |
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