What question did this study set out to answer?

The aim is to synthesize and characterize a stannyliumylidene ion and explore its reactivity and catalytic potential.

March 10, 2026Angewandte Chemie0 citations

T‐Shaped Stannyliumylidene Ion: Synthesis, Reactivity, and Redox Catalysis

ZQZhu QiChengdu University of Technology HMHuan Mu ZLZhuchunguang LiuSichuan University

Key Points

The aim is to synthesize and characterize a stannyliumylidene ion and explore its reactivity and catalytic potential.
Synthesis of T‐shaped stannyliumylidene ion with an acridane‐based pincer ligand.
Characterization using nuclear magnetic resonance spectroscopy, single crystal X-ray diffraction, and mass spectrometry.
Density functional theory calculations to analyze electronic structure and reactivity.
Mechanistic studies to elucidate the redox cycling of Sn(II)/Sn(IV) during catalysis.
The stannyliumylidene ion exhibits ambiphilic reactivity, effective in electrophilic and nucleophilic reactions.
It efficiently catalyzes transfer hydrogenation of azoarenes and imines using NH3BH3 as hydrogen source.
Density functional theory supports the dual reactivity through the unique electronic structure at the tin center.

Abstract

ABSTRACT We report the synthesis and characterization of a T‐shaped, 8‐electron stannyliumylidene ion bearing a rigid acridane‐based pincer ligand. This cationic Sn(II) complex exhibits pronounced ambiphilic reactivity, participating in electrophilic, nucleophilic, and σ‐bond activation reactions. All derived compounds were characterized by nuclear magnetic resonance spectroscopy, single crystal x‐ray diffraction analysis, and high‐resolution mass spectrometry. Density functional theory calculations reveal the coexistence of a lone pair of electrons and a vacant 5 p ‐orbital at the tin center, which rationalizes the experimentally observed dual reactivity. Remarkably, the transition metal‐like electronic structure enables this organotin(II) species to act as an efficient catalyst for transfer hydrogenation of azoarenes and imines using NH 3 BH 3 as hydrogen source. Combined experimental and computational mechanistic studies reveal a distinct catalytic platform based on Sn(II)/Sn(IV) redox cycle at a single tin(II) center. This work demonstrates the first Sn(II)/Sn(IV) catalyzed reduction of unsaturated bonds, offering a paradigm for mimicking transition metal reactivity through rationally designed main group systems in mediating diverse chemical transformations.

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