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Issue 24, 2014
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Reduction of an Fe(i) mesityl complex induced by π-acid ligands

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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.

Graphical abstract: Reduction of an Fe(i) mesityl complex induced by π-acid ligands

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Supplementary files

Article information

17 Jan 2014
11 Feb 2014
First published
11 Feb 2014

Dalton Trans., 2014,43, 9032-9037
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Reduction of an Fe(I) mesityl complex induced by π-acid ligands

Y. Lin, Y. Nakajima and F. Ozawa, Dalton Trans., 2014, 43, 9032
DOI: 10.1039/C4DT00170B

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