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Atypical “Masked” Frustrated Lewis Pair Character in a Geminal‐Linked Phosphine‐Borane

Von Wiley-VCH zur Verfügung gestellt

The new fluorene-derived phosphine-borane [iPr2P(C13H8)BCy2] (1) has been prepared. Unlike related geminal phosphine-boranes, 1 does not behave like a B/P frustrated Lewis pair (FLP), instead showing reactivity consistent with a “masked” FLP modulated by C(fluorene)-B bond scission. We exploit this behavior to perform P−Cl and N−H bond activation.


Abstract

We report the synthesis and reactivity of the geminal-linked fluorene-derived P/B frustrated Lewis pair (FLP) iPr2P(C13H8)BCy2 (1). Compound 1 displays anomalous behavior towards small molecules, acting as a “masked” FLP. This behavior stems from significant polarization of the B−C(fluorene) bond in 1, as identified by density functional theory (DFT) computations. We exploit this B−C bond polarity through reactions with PhPCl2, H3N ⋅ BH3, and iPrNH2, demonstrating P−Cl and N−H bond activation, respectively.

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