The synthesis and characterization of a series of 1,4-dialkyl-1,2,4-triazolium iodide and tetraphenylborate salts featuring methyl, ethyl, and isopropyl substituents and their use as precursors, in conjunction with triphosphenium reagents, to generate 1,4-dialkyl-1,2,4triazol-5-ylidene-stabilized phosphorus(I) ions is described. The use of 1251 tetraphenyl borate salts of both reagents produces the most pure products. The structural and spectroscopic features of the products are compared to those of analogous ions featuring 1,3-imidazol-2-ylidene ligands.ure 1b); [20][21][22][23] Robinson and Bertrand reported NHC-and cyclic (alkyl)(amino)carbene-(cAAC-) stabilized diphos-
The cover picture illustrates the relative π‐acidity of two classes of N‐heterocyclic carbenes that have been employed to stabilize the usually very reactive P+ ion. The background depicts the packing structure of the tetraphenylborate salt of a cation featuring a P+ ion that is ligated by two 1,4‐diisopropyl‐1,2,4‐triazol‐5‐ylidene (TAZ) groups (P atoms are gold, N atoms are blue, B atoms are red, C atoms are grey). Direct comparisons of the chemical and physical properties of salts of the cations featuring TAZ ligands and those of analogous PI cations stabilized by 1,3‐diisopropylimidazol‐2‐ylidene (IMID) ligands were made using X‐ray crystallography, NMR spectroscopy and computational calculations. The data reveal a larger degree of π‐bonding across the C‐P‐C fragment in the case of the TAZ‐stabilized PI cations that is attributable to the greater π‐accepting ability of the TAZ group. More details are discussed in the article by Elnajjar et al. on pp. http://onlinelibrary.wiley.com/doi/10.1002/zaac.201600270/abstract.
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