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Reduction of an Fe(i) mesityl complex induced by π-acid ligands
- Source :
- Dalton Transactions. 43:9032
- Publication Year :
- 2014
- Publisher :
- Royal Society of Chemistry (RSC), 2014.
-
Abstract
- Treatment of the Fe(I) mesityl complex [Fe(Mes)(BPEP-Ph)] (BPEP-Ph = 2,6-bis[1-phenyl-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine) with π-acid ligands (L = CO, RNC) leads to one-electron reduction via Mes group migration from Fe to P, followed by homolytic elimination of the 2,4,6-tBu3C6H2 group, to afford Fe(0) complexes of the formula [Fe(L)2(BPEP-Ph*)] (BPEP-Ph* = 2-[1-phenyl-2-mesityl-2-phosphaethenyl]-6-[1-phenyl-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyl]pyridine). This reduction process is supported by radical trapping experiments and theoretical studies. The 2,4,6-tBu3C6H2˙ radical is captured by 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) in high yield. DFT calculations reveal the mechanism of Mes group migration with a reasonable energy profile.
Details
- ISSN :
- 14779234 and 14779226
- Volume :
- 43
- Database :
- OpenAIRE
- Journal :
- Dalton Transactions
- Accession number :
- edsair.doi.dedup.....597f6c8c8d1a636d79d49e3e79d9c39a