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

The versatile coordination behavior of the P₄ butterfly complex [{Cp'''Fe(CO)₂ }₂ (μ,η^1:1 -P₄ )] (1, Cp'''=η⁵ -C₅ H₂^t 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 }₂ (μ₃ ,η^1:1:2 -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 )₂ (μ₃ ,η^1:1:4 -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 }₂ (μ₃ ,η^1:1:2 -P₄ ){Cp'''Fe(CO)}][PF₆ ] (4) and [{Cp'''Fe(CO)₂ }₂ (μ₃ ,η^1:1:4 -P₄ ){Cp'''Fe}][PF₆ ] (5), give insight into the stepwise activation of the P₄ butterfly moiety in 1.