Louis Ricard

Synthesis and X-ray structure of a phosphaferrocenium

Abstract Reaction of 1-chloro-2,3,4,5-tetraethylphosphole with lithium yields the tetraethylphospholyl anion which is homocoupled to form the 1,1′-bis-(tetraethylphosphole) upon reaction with iodine. The thermal reaction of this bis-(tetraethylphosphole) with the [FeCp*(CO) 2 ] 2 dimer (Cp*=C 5 Me 5 ) affords the pentamethylcyclopentadienyl-tetraethylphosphaferrocene. Reaction of this phosphaferrocene with elemental iodine in dichloromethane at room temperature affords the corresponding pentamethylcyclopentadienyl-tetraethylphosphaferrocenium [Fe(Cp*)(C 12 H 20 P)][I 3 ] complex which was structurally characterized. The complex adopts a full-eclipsed geometry. As usually observed in classical ferrocenes, oxidation of the Fe center to +3 oxidation state results in a lengthening of the centroid-Fe bond distances.

Neutral and dianionic iron and ruthenium 1,4-diphosphabutadiene complexes

Reaction of a tetraphenyl-1,2-diphosphinyl dianion with [FeCl2(THF)1.5] or [Ru(COD)(acac)2] yields dianionic complexes which further react with Ph3SnCl to afford the corresponding bis(1,4-diphosphabutadiene) complexes.