Abstract
Ferrocene-containing phosphorus derivatives are important as ligands in transition-metal catalysis. We have investigated the synthesis of ferrocene-based phosphanes from corresponding phosphinites via retro-phospha-Brook rearrangement. Ferrocenyl phosphinites isomerize to thermodynamically more stable phosphine oxides. Interestingly, retro-phospha-Brook rearrangement proceeds on the adjacent phenyl ring with the assistance of the ferrocenyl moiety. DFT calculations provided insight into the reaction mechanisms of these transformations. Isomerization probably proceeds intramolecularly with the participation of developing charge stabilization with iron´s d-orbitals. BH3 complexation seems to favor the phosphinite structure as was evidenced by 31P-11B scalar coupling. Retro-phospha-Brook rearrangement also likely proceeds as intramolecular migration of the phosphanyl group from oxygen to carbon, from both BH3 complexes and the uncomplexed starting material.
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