A Novel [FeFe] Hydrogenase Model with a (SCH2)2P鈺怬 Moiety

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• 作者：Laith R. Almazahreh ; Ulf-Peter Apfel ; Wolfgang Imhof ; Manfred Rudolph ; Helmar G枚rls ; Jean Talarmin ; Philippe Schollhammer ; Mohammad El-khateeb ; Wolfgang Weigand
• 刊名：Organometallics
• 出版年：2013
• 出版时间：August 26, 2013
• 年：2013
• 卷：32
• 期：16
• 页码：4523-4530
• 全文大小：431K
• 年卷期：v.32,no.16(August 26, 2013)
• ISSN：1520-6041

文摘

A novel [FeFe]-hydrogenase model complex containing phosphine oxide in the dithiolato ligand, namely [Fe₂(CO)₆][(渭-SCH₂)₂(Ph)P鈺怬] (1), has been synthesized and characterized. Complex 1 was prepared via the reaction of equimolar quantities of (渭-LiS)₂Fe₂(CO)₆ and O鈺怭(Ph)(CH₂Cl)₂. The protonation properties of complex 1 have been investigated by monitoring the changes in IR (in the 谓(CO) region) and ³¹P{¹H} NMR spectra upon addition of pyridinium tetrafluoroborate, [HPy][BF₄], and HBF₄路Et₂O, suggesting protonation of the P鈺怬 functionality. In addition, high-level DFT calculations on the protonation sites of complex 1 in CH₂Cl₂ have been performed and support our experimental observations that the P鈺怬 unit is protonated by HBF₄路Et₂O. Cyclic voltammetric experiments on complex 1 showed an anodic shift of the oxidation peak upon addition of HBF₄路Et₂O, suggesting a CE process.