Related Experiment Video
Updated: May 7, 2026

Preparation and Reactivity of a Triphosphenium Bromide Salt: A Convenient and Stable Source of PhosphorusI
Published on: November 22, 2016
Secondary diphosphine and diphosphido ligands: synthesis, characterisation and group 1 coordination compounds
Jamie S Ritch1, Delphine Julienne, Shayne R Rybchinski
1Department of Chemistry, The University of Winnipeg, 515 Portage Avenue, Winnipeg, MB R3B 2E9, Canada.
Abstract:
Two types of secondary diphosphines, 1,8-(ArPH)2C14H8 (1a: Ar = Tripp, 2,4,6-triisopropylphenyl; 1b: Ar = Mes, 2,4,6-trimethylphenyl) and 1,3-((t)BuPHCH2)2C6H4 (2), based on rigid 1,8-anthracene and flexible m-xylyl frameworks, respectively, have been synthesized using different strategies. Compounds 1a and 1b were formed by nucleophilic aromatic substitution of a potassium organophosphido salt onto 1,8-difluoroanthracene, while compound 2 was obtained by addition of the Grignard reagent [1,3-(ClMgCH2)2C6H4]x to a dichloroorganophosphine, followed by reduction to the diphosphine. These compounds were isolated as ca. 1 : 1 mixtures of rac and meso diastereomers as determined by multinuclear NMR spectroscopy. Borane and selenide derivatives of 2, 1,3-((t)BuPH(BH3)CH2)2C6H4 (3) and 1,3-((t)BuPH(Se)CH2)2C6H4 (4), were obtained. Preferential crystallization of one diastereomer of 3 and 4 was observed; X-ray crystallographic studies identified this as the rac isomer for diselenide 4. Metallation studies of compounds 1a and 2 yielded several alkali metal salts. The reaction of KH or K metal with 1a yielded the compounds 1,8-(TrippPK)2C14H8·xTHF (5) and 1,8-(TrippPK)2C14H10·xTHF (6), respectively; in complex 6 the central aromatic ring has been reduced to yield a bent dihydroanthracene backbone. A crown ether derivative of 6, [K(18-crown-6)(THF)2]2[1,8-(TrippP)2C14H10] (7), was characterised crystallographically. Double deprotonation of compound 2 with (n)BuLi/TMEDA (TMEDA = N,N,N',N'-tetramethylethylenediamine) afforded the yellow dilithium complex 1,3-((t)BuPLiCH2)2C6H4·TMEDA (8), which crystallized as a dimer featuring lithium-arene π interactions.
More Related Videos
07:14Author Spotlight: Experimental Approaches for the Synthesis of Low-Valent Metal-Organic Frameworks from Multitopic Phosphine Linkers
Published on: May 12, 2023
07:20Amide Coupling Reaction for the Synthesis of Bispyridine-based Ligands and Their Complexation to Platinum as Dinuclear Anticancer Agents
Published on: May 28, 2014
Related Concept Videos
Metal-Ligand Bonds
In these complexes, transition metals form coordinate covalent bonds, a kind of Lewis acid-base interaction in which both of the electrons in the bond are contributed by a donor (Lewis base) to an electron acceptor (Lewis acid). The Lewis acid in...
Coordination Compounds and Nomenclature
Valence Bond Theory
Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly,...
Coordination Number and Geometry
Diazonium Group Substitution: –OH and –H