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Breaking the Mold: Electrophilic Hydrophosphanation Emerges
Víctor Varela-Izquierdo1, Janeth Navarro1, Judit Cano-Asensio1
1Departamento de Química Inorgánica, Facultad de Ciencias, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH) CSIC-Universidad de Zaragoza, Zaragoza, Spain.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|May 15, 2026
Summary
This study reveals a new catalytic hydrophosphanation mechanism involving electrophilic hydride attack on olefins. This discovery redefines P-H compound reactivity and expands accessible chemical space for novel transformations.
Area of Science:
- Organometallic Chemistry
- Catalysis
- Phosphorus Chemistry
Background:
- Catalytic hydrophosphanation traditionally involves nucleophilic addition of phosphanido ligands.
- Understanding the fundamental reactivity of P-H compounds with olefins is crucial for developing new synthetic methodologies.
Purpose of the Study:
- To report an unprecedented mechanism for catalytic hydrophosphanation of olefins.
- To elucidate the dichotomy between electrophilic and nucleophilic pathways.
- To explore novel reactivity modes of hydrido-phosphanido species.
Main Methods:
- Density Functional Theory (DFT) calculations.
- Experimental kinetic isotope effect (KIE) measurements.
- Catalytic reactions with various olefins.
Main Results:
- An unprecedented electrophilic hydride attack mechanism for hydrophosphanation was identified.
- The mechanism applies to activated, non-activated, and non-symmetric olefins.
- A novel intramolecular phosphanido attack on a tethered olefin yielded a diphosphaenolate.
Conclusions:
- The study redefines the fundamental reactivity of P-H compounds with C═C bonds.
- The identified mechanism expands the scope and applicability of catalytic hydrophosphanation.
- Novel reactivity modes expand the chemical space accessible via hydrophosphanation-derived pathways.
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