Controlling the Reactivity of Ferrocenyl Carbocations: Routes to Enantiomerically Pure Chlorophosphites and Solid‐State Characterization of a Benzopentalene Dimer

A range of enantiopure ferrocenyl diols possessing a variety of electron‐withdrawing groups at the carbinol centre was investigated in the reaction with phosphorus trichloride. Subtle changes in the electronic properties of these groups led, after reaction with phosphorus trichloride, to distinctly different products: α‐substituted ferrocenes, (bis)phosphinic dichlorides, benzopentalene dimers or chlorophosphites. A mechanistic rationale was …