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Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7312-7317. doi: 10.1002/anie.201703175. Epub 2017 May 17.

Rearrangement of a P4 Butterfly Complex-The Formation of a Homoleptic Phosphorus-Iron Sandwich Complex.

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Institut für Anorganische Chemie der Universität Regensburg, 93040, Regensburg, Germany.
Department Chemie und Pharmazie, Institut für Anorganische Chemie, Friedrich-Alexander University Erlangen-Nürnberg, FAU, Egerlandstrasse 1, 91058, Erlangen, Germany.


The versatile coordination behavior of the P4 butterfly complex [{Cp'''Fe(CO)2 }2 (μ,η1:1 -P4 )] (1, Cp'''=η5 -C5 H2t Bu3 ) towards different iron(II) compounds is presented. The reaction of 1 with [FeBr2 ⋅dme] (dme=dimethoxyethane) leads to the chelate complex [{Cp'''Fe(CO)2 }231:1:2 -P4 ){FeBr2 }] (2), whereas, in the reaction with [Fe(CH3 CN)6 ][PF6 ]2 , an unprecedented rearrangement of the P4 butterfly structural motif leads to the cyclo-P4 moiety in {(Cp'''Fe(CO)2 )231:1:4 -P4 )}2 Fe][PF6 ]2 (3). Complex 3 represents the first fully characterized "carbon-free" sandwich complex containing cyclo-P4 R2 ligands in a homoleptic-like iron-phosphorus-containing molecule. Alternatively, 2 can be transformed into 3 by halogen abstraction and subsequent coordination of 1. The additional isolated side products, [{Cp'''Fe(CO)2 }231:1:2 -P4 ){Cp'''Fe(CO)}][PF6 ] (4) and [{Cp'''Fe(CO)2 }231:1:4 -P4 ){Cp'''Fe}][PF6 ] (5), give insight into the stepwise activation of the P4 butterfly moiety in 1.


P4 butterfly complexes; P4 transformation; cyclo-P4 ligands; iron; phosphorus


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