Related Experiment Video
Updated: Jun 12, 2026

Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Imidazoliumyl-substituted di- and iso-tetraphosphanes and their metal-mediated fragmentation reactions
Jannis Fidelius1, Clemens Taube1, Kai Schwedtmann1
1Faculty of Chemistry and Food Chemistry, Technische Universität Dresden 01062 Dresden Germany jan.weigand@tu-dresden.de.
Abstract:
Monocationic imidazoliumyl-substituted phosphanes, LCP(R)Cl+ (LC = 1,3-diisopropyl-4,5-dimethylimidazol-2-yl), were synthesized as their respective triflate salts 2a-c[OTf] (a: R = Cy; b: R = Ph; c: R = Py). These serve as versatile building blocks for the formation of the corresponding imidazoliumyl-substituted diphosphanes ((LCPR)25a-c[OTf]2) and iso-tetraphosphanes ((LCPR)3P[OTf]36a,b[OTf]3). The introduction of a cationic (onio) substituent substantially alters the preferred reaction pathways of the P-scaffolds compared to their neutral congeners and electronically predisposes selected P-P bonds toward fragmentation. DFT calculations reveal a strong localization of the LUMO orbitals on the P-P bond, indicating susceptibility to nucleophilic attack. Both 5a,b[OTf]2 and 6a[OTf]3 undergo metal-mediated fragmentation reactions. Reactions of 5a,b[OTf]2 with Pd(PPh3)4 afford two distinct dinuclear complexes, while reactions of 6a[OTf]3 with metal chlorides yield triphosphanide complexes (LCPCy)2PM[OTf]29[OTf]2: M = Pd(allyl), 10[OTf]2: M = Au(PPh3), accompanied by the formation of 2a[OTf]. Treatment of 6a[OTf]3 with the NHC IPr (1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene) provides the free triphosphanide ligand (LCPCy)2P[OTf] (11[OTf]).
More Related Videos
07:20Discovery and Synthesis Optimization of Isoreticular Al(III) Phosphonate-Based Metal-Organic Framework Compounds Using High-Throughput Methods
Published on: October 6, 2023
07:14Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
Related Concept Videos
Mass Spectrometry: Molecular Fragmentation Overview
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can occur at...
Mass Spectrometry: Cycloalkene Fragmentation
Diazonium Group Substitution: –OH and –H
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions
Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation
For example, the fragmentation of...
Mass Spectrometry: Aromatic Compound Fragmentation