Metathesis of [Cp'FeI]2 ((1  , Cp'= 1,2,4-(Me3C)3C5H2) 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(�-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 �. Complex 4  is an isomer to the long-known [{Cp'Fe}2(�-?4:?4-P4)] (5  ) with a cis-tetraphosphabutadiene moiety and it thermally rearranges to 5  , [{Cp'Fe}2(�-?3:?3-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.                                                                      

Reactivity studies on [Cp′FeI]<sub>2</sub>: From iron hydrides to P<sub>4</sub>-activation

243rd National Meeting (2012)

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

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