Activation of group 15 based cage compounds by [CpBIGFe(CO)2] radicals

Abstract

The sterically encumbered dimer [Cp^BIGFe(CO)₂]₂ (1) (Cp^BIG = C₅(4-nBuC₆H₄)₅) is able to activate small tetrahedral molecules like P₄ and As₄ as well as the less reactive cage compounds P₄S₃ and P₄Se₃ at room temperature to give the products [{Cp^BIGFe(CO)₂}₂(μ,η^1:1-cage)] (cage = P₄ (2a), As₄ (2b), P₄S₃ (2c), P₄Se₃ (2d)) in a quantitative manner. The reaction proceeds via selective cleavage of one E–E bond (E = P, As) of the starting material. Complex 1 also reacts with CS₂ forming the binuclear compound [{Cp^BIGFe(CO)₂}{Cp^BIGFeCO}(μ,η^1:2-CS₂)] (3).