Reductive cleavage of P₄ by iron(i) centres: synthesis and structural characterisation of Fe₂(P₂)₂ complexes with two bridging P₂²⁻ ligands

Abstract

The selective transformation of white phosphorus with a β-diketiminato iron(I) toluene complex under mild reaction conditions is reported which furnishes a new dinuclear iron(III) Fe2(P2)2 complex with two bridging P2(2-) ligands. Its reduction with potassium results in the formation of the first delocalised mixed-valent bis-diphosphido iron(II,III) complex which is isostructural with the neutral Fe2P4 precursor.

Nacnac‐Cobalt‐Mediated P4 Transformations

“…Despite the application of the same reaction conditions, different products were obtained, which are sensitively dependent on small changes of the ligand substituents. 2,6‐Diisopropylphenyl (dipp) substituents as the ligands’ aromatic flanking groups support the formation of the dinuclear complexes [(L 3 Fe) 2 (μ 2 :η 4 ,η 4 ‐P 4 )] ( B ) and [(L 0 Fe) 2 (μ 2 :η 2 ,η 2 ‐P 2 ) 2 ] ( C ) . The latter was synthesized by the Driess group .…”

A New Domain of Reactivity for High‐Valent Dinuclear [M(μ‐O)2M′] Complexes in Oxidation Reactions

“…Replacement of the Co atom in [L 1 Ni(μ-O) 2 CoL 3 ] with Fe further increases the electrophilicity of the bis(μ-oxido)dimetal core to an extent that the [L 1 Ni(μ-O) 2 FeL 3 ] ( 5 ) complex becomes extremely unstable against self-decay by an intramolecular ligand hydroxylation pathway (Scheme 1). Thus, monitoring of the reaction of [L 1 Ni II O 2 ] with [L 3 Fe(C 7 H 8 )] [8] in toluene by means of UV–Vis spectroscopy (Fig S13) at −90°C did not lead to the observation of any intermediate species. The molecular structure of the resultant product 6 (> 90% yields; Fig S14, Table S7) reveals the presence of β-diketiminato-ligated Ni II and Fe II centers [9] in sq planar and tetrahedral ( T d ) coordination environments, respectively.…”

Reactions of the Lithiated Diphosphine tBu2P–P(SiMe3)Li with [(η6‐C6H6)RuCl2]2 in the Presence of Tertiary Phosphines

“…A trapezoidal P 4 unit and a Fe–Fe single bond were also found in [{(Cp′Fe)} 2 (µ‐P 4 )] (Cp′ = 1,3‐ t Bu 2 ‐C 5 H 3 ) . Recently, Driess and co‐workers prepared a diiron complex in which two P 2 units coming from white phosphorus bridge the two metal centers, as in complex 6a , whereas Scheer and co‐workers prepared a diiron complex with a cyclo ‐P 4 unit …”