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The direct reactions of PI3 with –H or –C6H5 substituted diiminopyridine ligands yield the N,N′,N′′-chelated P(I) cations. The analogous chemistry with the ubiquitous –CH3 substituted derivative produces a complex mixture of products underscoring the importance of the substitution on the α-carbon atom. The I3− counteranion of the compounds could be easily exchanged with the more robust B12Cl122− dianion. Reactions of PCl3 and PBr3 with –CH3 and –C6H5 substituted ligands led to indiscernible mixtures or no reaction. However, heating PBr3 with the –H derivative in the presence of a halide trap produced the corresponding phosphorus(I) cation as the bromide salt. These species represent the first phosphorus diiminopyridine complexes reported.
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