Nucleophilic Functionalization of Activated P4 in [CpFe(CO)2-(η1‑P4)][Al(ORF)4] with Alcohols R-OH

The bonding situation in [Fp-P4][Al(ORF)4] (1) (Fp = (CO)2CpFe, RF = C(CF3)3) gives rise to an Umpolung of the P4 fragment, which should make it accessible for nucleophiles. To investigate this projected reactivity, the complex was combined with a series of hydroxy-nucleophiles - that all do not react with free P4 - leading to a variety of P1 building blocks. With excess of R-OH (R = Me, Et, Ph), the thermodynamically more stable complex salts [Fp-P(H)x(OR)3-x)][Al(ORF)4] (x = 2,1,0) (2b‑2d) are formed and show that the phosphonium type pathway is accessible. Quantum chemical calculations display a variety of reaction pathways that all lead very rapidly to the P1 building blocks. With stoichiometric amounts of R-OH, [Fp-PH3][Al(ORF)4] (2a) as well as [HP(OR)3][Al(ORF)4] (2f) were observed as products. Hence, activation of the P4-cage in complex 1 was confirmed.