ArticleChemistry (Weinheim an der Bergstrasse, Germany)2026
Breaking the Mold: Electrophilic Hydrophosphanation Emerges.
Article in Chemistry (Weinheim an der Bergstrasse, Germany), 2026. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Not yet cited in PubMed.
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Abstract
Herein, we report an unprecedented mechanism for the catalytic hydrophosphanation of olefins in which the key step involves an electrophilic hydride attack on the olefin rather than the classical nucleophilic addition of a phosphanido ligand. This mechanistic paradigm redefines the fundamental reactivity of P-H compounds with C═C bonds under catalytic conditions. The dichotomy between electrophilic and nucleophilic pathways has been elucidated through DFT calculations and experimental kinetic isotope effect (KIE) measurements. We also demonstrate that this mechanistic pattern is applicable to both electronically activated and non-activated olefins, as well as to non-symmetric olefins. In a parallel finding, we have identified a novel reactivity mode of hydrido-phosphanido species, in which the phosphanido moiety engages in an intramolecular attack on a tethered olefin to afford a previously unreported diphosphaenolate. This transformation, due to the amphiphilic behavior of complex [Rh(Tp)(PHPh
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