Carbon-Centered Reactivity in Carbodiphosphorane-Based Ligands Allowing for Redox-Non-Innocent Ligand/Ligand Dual Bond-Activation

Philipp Schatz; Weiqin Xu; Sebastian Rynek; Leon Maser; Niels Heise; Olaf Fuhr; Dieter Fenske; Haleh Hashemi Haeri; Dariush Hinderberger; Matthias Vogt; Robert Langer

doi:10.1002/anie.202419786

Carbon-Centered Reactivity in Carbodiphosphorane-Based Ligands Allowing for Redox-Non-Innocent Ligand/Ligand Dual Bond-Activation

Angew Chem Int Ed Engl. 2025 Jan 3:e202419786. doi: 10.1002/anie.202419786. Online ahead of print.

Authors

Affiliations

¹ Institute of Chemistry, Faculty of Natural Science II, Martin Luther University Halle-Wittenberg, Kurt-Mothes-Str. 2, 06120, Halle(Saale), Germany.
² Chemistry Department, Guangdong University of Education, Guangzhou, 510303, PR China.
³ Institut für Nanotechnologie (INT) and Karlsruhe Nano Micro Facility (KNMFi), Karlsruher Institut für Technologie (KIT), Kaiserstraße 12, 76131, Karlsruhe, Germany.
⁴ Lehn Institute of Functional Materials (LIFM), School of Chemistry, Sun Yat-Sen University, Guangzhou, 510000, PR China.

PMID: 39753512
DOI: 10.1002/anie.202419786

Abstract

A pronounced nucleophilicity in combination with a distinct redox non-innocence is a unique feature of a coordinated ligand, which in the current case, leads to unprecedented carbon-centered reactivity patterns: A carbodiphosphorane-based (CDP) pincer-type rhodium complex allows to cleave two C-Cl-bonds of geminal dichlorides via two consecutive S.

Keywords: carbodiphosphoranes; homogeneous catalysis; ligand reactivity; metal-ligand-cooperation; redox noninnocence.

Abstract

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