Oxidation of the octa-(ethyl)diphosphaferrocene

• Published in: Journal of organometallic chemistry Vol. 671; no. 1; pp. 120 - 125
• Main Authors: Sava, Xavier, Ricard, Louis, Mathey, F., Le Floch, Pascal
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.04.2003; Elsevier
• Subjects: Cations; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Complexes; Heterocycles; Iron; Phosphorus; Physical Sciences; Science & Technology; Heterocycles; Phosphorus; Iron; Cations; Complexes; ELECTROCHEMISTRY; cations; heterocycles; REACTIVITY; iron; LIGAND; PHOSPHAFERROCENES; phosphorus; complexes
• ISSN: 0022-328X; 1872-8561
• DOI: 10.1016/S0022-328X(03)00054-8

The octa-(ethyl)-diphosphaferrocene ( 1) reacts with NOBF 4 in dichloromethane to yield a polymer ( 2) featuring diphosphaferrocene ligands ( 1) that bridge [Fe(NO) 2] units through their two phosphorus atom lone pairs. The X-ray crystal structure of 2 has been recorded. The formation of the 1-P-fluoro-2,3,4,5-tetra-(ethyl)-phosphole oxide as a by-product demonstrates that phosphaferrocenium ( 2) is sensitive towards substitution reaction at iron and nucleophilic attack at phosphorus. Oxidation of 1 with iodine in dichloromethane yielded the corresponding phosphaferrocenium cation [FeI 4] − complex ( 4) which has been characterized structurally. The formation of 4 probably results from the partial decomposition of the diphosphaferrocenium cation having [I 3] − as the counter anion. Oxidation of the octa-(ethyl)diphosphaferrocene with NOBF 4 yields a polymeric diphosphaferrocene [Fe(NO) 2] complex and the 1-P-fluoro-2,3,4,5-tetraethylphosphole oxide. The stable octa-(ethyl)diphosphaferrocenium cation was obtained through reaction with iodine in dichloromethane. X-ray crystal structures of the two complexes were recorded.