title: Reduction of an Fe(I) mesityl complex induced by π-acid ligands.
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.
authors.affiliation: International Research Center for Elements Science (IRCELS), Institute for Chemical Research, Kyoto University, Uji, Kyoto 611-0011, Japan. ozawa@scl.kyoto-u.ac.jp.
authors.forename: Ya-Fan
authors.initials: YF
authors.lastname: Lin
authors.forename: Yumiko
authors.initials: Y
authors.lastname: Nakajima
authors.forename: Fumiyuki
authors.initials: F
authors.lastname: Ozawa