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Issue 11, 2011
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Reactivity studies on [Cp′FeI]2: From iron hydrides to P4-activation

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Metathesis of [Cp′FeI]2 (1) with KHBEt3 affords the polyhydride iron complexes [Cp′FeH2]2 (2) and [Cp′2Fe2H3] (3). The ratio in which both 2 and 3 are obtained correlates to the applied H2 pressure during synthesis. Complex 2 activates CH- or CD- bonds in aromatic compounds and shows slow H/D exchange in the presence of D2 at room temperature in cyclohexane solvent. [Cp′FeH2]2 acts as a Cp′Fe(I)-synthon when reacted with white phosphorus (P4) to give [Cp′Fe]2(μ-P4) (4) as the only P-containing product. This complex is best described as a triple-decker complex with a planar arrangement of a severely distorted kite-like cyclo-P4 unit. This distortion persists in solution and solid state as evidenced by a small PP coupling constant in the 31P{1H} NMR spectrum and a long P–P distance of 2.53 Å. Complex 4 is an isomer to the long-known [{Cp′Fe}2(μ-η44-P4)] (5) with a cis-tetraphosphabutadiene moiety and it thermally rearranges to 5, [{Cp′Fe}2(μ-η33-P3)] and [Cp′Fe(P5)]. All complexes described in this paper have been completely characterized including X-ray crystallography, variable temperature NMR studies and DFT calculations. Relaxed force constants (inverse compliance constants) are used as bond strength descriptors.

Graphical abstract: Reactivity studies on [Cp′FeI]2: From iron hydrides to P4-activation

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Supplementary files

Article information

29 Jun 2011
27 Jul 2011
First published
12 Aug 2011

Chem. Sci., 2011,2, 2120-2130
Article type
Edge Article

Reactivity studies on [Cp′FeI]2: From iron hydrides to P4-activation

M. D. Walter, J. Grunenberg and P. S. White, Chem. Sci., 2011, 2, 2120
DOI: 10.1039/C1SC00413A

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