Chemistry of the Triplet 14-Electron Complex Fe(CO)3 in Solution Studied by Ultrafast Time-Resolved IR Spectroscopy

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• 作者：Son C. Nguyen ; Justin P. Lomont ; Matthew C. Zoerb ; Adam D. Hill ; Jacob P. Schlegel ; Charles B. Harris
• 刊名：Organometallics
• 出版年：2012
• 出版时间：May 28, 2012
• 年：2012
• 卷：31
• 期：10
• 页码：3980-3984
• 全文大小：225K
• 年卷期：v.31,no.10(May 28, 2012)
• ISSN：1520-6041

文摘

Time-resolved IR spectroscopy and density functional theory calculations indicate that the 14-electron, triplet species, ³Fe(CO)₃, generated from photolysis of Fe(CO)₅, appears to exist uncoordinated to alkyl groups in alkane solvents. In alcohols of varying lengths, triplet ³Fe(CO)₃ forms a hydroxyl-coordinated complex on the time scale of tens of picoseconds, implying that its solvation kinetics are diffusion-limited. Surprisingly, the hydroxyl-coordinated complex remains in a triplet state, in contrast to the activity of triplet ³Fe(CO)₄, which must convert to a singlet state to coordinate to a solvent molecule. To our knowledge, this study represents the first investigation into the detailed metal鈥搒olvent interactions and rearrangement kinetics of a 14-electron complex on the ultrafast time scale.