Synthesis of the First Transition Metal PI₃ Complex [CpFe(CO)₂–PI₃]⁺ [Al(OR^F)₄]⁻ by Iodination of [CpFe(CO)₂(<i>η</i>¹‐P₄)][Al(OR<sup>F</sup

Reactions targeting at a stoichiometric conversion of P 4 ‐complex [Fp−P 4 ][[Al(OR F ) 4 ] 1 (Fp = CpFe(CO) 2 ; R F = C(CF 3 ) 3 ) with iodine to give the PI 3 ‐complex [Fp−PI 3 ][Al(OR F ) 4 ] 2 , astonishingly led to variety of intermediates such as four‐membered rings and P 2 I 4 fragments coordinated to [Fp] + in the 31 P nuclear magnetic resonance (NMR) spectra. Only the reaction of 1 with a large excess of iodine (7.5:1 = I:P ratio), led to full consumption of the P 4 tetrahedron resulting in the selective formation of PI 3 and the complex [Fp−PI 3 ][Al(OR F ) 4 ] 2 in 74% yield. 2 represents the first structurally characterized metal complex of PI 3 .